FIRST IBERIAN MEETING ON SUPERCRITICAL FLUIDS 1º Encuentro Ibérico de Fluidos Supercríticos
1º Encontro Ibérico de Fluidos Supercríticos Santiago de Compostela (Spain), February 18 - 19, 2020
EIFS 2020
Book of abstracts
Picture by Carmucha Remuñán López
1
This book contains the abstracts presented at the First Iberian Meeting on Supercritical Fluids (1er Encuentro Ibérico de Fluidos Supercríticos/1º Encontro Ibérico de Fluidos Supercríticos), held in Santiago de Compostela – Spain, on 18-19 February 2020.
First Iberian Meeting on Supercritical Fluids
(1er Encuentro Ibérico de Fluidos Supercríticos/1º Encontro Ibérico de Fluidos Supercríticos)
Book of Abstracts
2
Contents
Organizers, collaborators and sponsors 3
Welcome message/preface 4
Organizing and scientific Committees 5
Practical information 6
Full conference programme 8
Plenary Lectures 17
Keynote Presentations 27
Oral Sessions 33
Poster Sessions
Extraction, Fractionation and Biorefinery 83
Reactions and CO2 capture/separation 121
Thermodynamics, Phase equilibria, and Transport
phenomena/properties 127
Materials, Biomaterials and Sterilization 141
Particle production 167
Participants list 177
Overall conference programme 193
3
Organizers
Collaborator
Sponsors
4
Welcome Message
It is with great honor and pleasure that we host the 1st Iberian Meeting on Supercritical Fluids (1er Encuentro Ibérico de Fluidos Supercríticos/1º Encontro Ibérico de Fluidos Supercríticos), and welcome all the participants to Santiago de Compostela, Spain.
The conference is organized jointly by the I+D Farma research group (University of Santiago de Compostela, Spain), by the Green and Sustainable Processes Lab (CIEPQPF, University of Coimbra, Portugal) and by Flucomp (Asociación de Expertos en Fluidos Comprimidos, Spain), and in collaboration with AeMAT (Agrupación Estratégica de Investigación en Materiales, University of Santiago de Compostela, Spain).
EIFS2020 aims at the dissemination of the high quality scientific research currently being carried out in Spain and Portugal on a wide range of fundamental and applied topics on supercritical fluids. EIFS2020 also aims to bring together, to strengthen and create new ties and collaborations between the Iberian research community and industry working around these topics, as well as to support young Iberian researchers working on these fields. Nevertheless, EIFS2020 official language is English since this event is also open to contributions from researchers all over the world.
We are pleased to provide a remarkable scientific programme and hope that EIFS2020 will offer the opportunity to discuss scientific and technological issues.
EIFS2020 will be held in parallel to the "International Conference on Aerogels for Biomedical and Environmental Applications", organized by AERoGELS CA18125 COST Action. Given the important role of supercritical fluid technology in aerogel processing, we foresee clear synergies between both events and interesting outputs from discussions of their participants.
The Organizing Committee gratefully acknowledges all authors for their contributions and all sponsors for their generous financial support.
We wish you an excellent conference both scientifically and socially, and an enjoyable stay in Santiago de Compostela.
17 February 2020
EIFS2020 Organizing Committee
5
Committees
Organizing Committee
Carlos A. García-González (Co-Chair, Univ. Santiago de Compostela) Hermínio C. de Sousa (Co-Chair, Univ. Coimbra) Carmen Alvarez Lorenzo (Univ. Santiago de Compostela) Mara Braga (Univ. Coimbra) Angel Concheiro (Univ. Santiago de Compostela) Ana Dias (Univ. Coimbra) Herminia Domínguez (Univ. Vigo) Josefa Fernández (Univ. Santiago de Compostela) Marisa Gaspar (Univ. Coimbra) José Luis Gómez Amoza (Univ. Santiago de Compostela) Mariana Landín (Univ. Santiago de Compostela) Luciana Tomé (Univ. Coimbra)
Jose A. Mendiola (Technical secretariat, CIAL-CSIC)
Scientific Committee
Sagrario Beltrán (Univ. Burgos) Albertina Cabañas (Univ. Complutense Madrid) Pedro Calado Simões (Univ. Nova Lisboa) Lourdes Calvo (Univ. Complutense Madrid) Elvira Casas (AINIA) Teresa Casimiro (Univ. Nova Lisboa) María José Cocero (Univ. Valladolid) José Coelho (Inst. Politécnico Lisboa) Eunice Costa (Hovione) Rolando Dias (Inst. Politécnico Bragança) Concepción Domingo (ICMAB-CSIC) Ana Rita Duarte (Univ. Nova Lisboa) João Fernandes (Natex) Ignacio Gracia (Univ. Castilla La Mancha) Miguel Herrero (CIAL-CSIC) Ana Leite Oliveira (Univ. Católica Portuguesa) Enrique Martínez de la Ossa (Univ. Cádiz) Ana Matias (IBET) Miguel Rodrigues (Univ. Lisboa) Carlos Silva (Univ. Aveiro) Nora Ventosa (ICMAB-CSIC)
6
Practical information Conference location
Faculty of Medicine University of Santiago de Compostela (USC) Rúa de San Francisco, s/n Santiago de Compostela, Spain GPS: 42°52´N 8°32´W
7
Tourist information Santiago de Compostela is located in the northwest of Spain and is the political capital of the Autonomous Region of Galicia. The Old Town of Santiago de Compostela has been declared a World Heritage Site by UNESCO, thanks to its architectural beauty, its outstanding conservation and the destination of a millenary pilgrimage route that emerged in the 9th century: The Way of St. James. Every year, thousands of pilgrims from all over the world live this experience of the road on foot, by bicycle, or even on horse, bringing together in the city different cultures, thoughts and beliefs. Santiago de Compostela is the most cosmopolitan city in Galicia, with numerous popular celebrations, annual music festivals, cinema and theatre and a multitude of exhibitions. Thanks to its University, founded more than 500 years ago, and which receives more than 25,000 students, nearly a hundred annual cultural events are scheduled. Santiago de Compostela symbolizes all the tradition and gastronomic treasures of a cuisine admired for the high quality of its ingredients, thanks to the sea and the land. That is why gastronomy is undoubtedly one of the main attractions of this city, from the most traditional to the most innovative. To learn more about Santiago de Compostela, please visit: http://www.santiagoturismo.com/ How to arrive from the airport By bus: From Santiago Airport to town: To arrive from the airport to the town centre there is a specific bus with departures every 30 min from 07.00 to 01.00 h. From Santiago to Airport: there are buses from 06.00 to 00.00 h, with a frequency of 30 min. Bus Stops at: Santiago (Praza de Galicia), Santiago (Rúa da Rosa, 8), Santiago (Estación de Ferrocarril/Railway Station), Santiago (Estación de Autobuses/Bus Station), Santiago (Capilla San Lázaro), Santiago (Palacio de Congresos), Santiago Airport (Terminal Building). By taxi: Estimated cost: Taxi Airport-Town: €21 (fixed rate)
8
Full Conference Programme
Tuesday Morning, 18th February
8:30 Registration
9:00 Welcome/Opening Session (Room: Salon de Actos Novoa Santos)
9:30 Plenary 1 (Chair: Carlos A García-González, Room: Salon de Actos Novoa Santos)
Aerogels: Synthesis, properties and applications Lorenz Ratke
PL1
Session 1 (Room: Aula Castelao)
Co-chairs: Carlos Silva (Univ. Aveiro), Ignacio Gracia (UCLM)
10:20 Classification of flow regimes of alginate aerogel particles in a laboratory scale Wurster fluidized bed Işık Sena Akgün, Can Erkey
O01
10:40 Morphological study and in silico modelling of biodegradable poly(-caprolactone) scaffolds with controlled architectures obtained by supercritical CO2 foaming Víctor Santos-Rosales, Marta Gallo, José L. Gómez-Amoza, Carlos A. García-González
O02
11:00 ScCO2 sterilization of natural-based hydrogel and aerogel for biomedical applications Cristiana Bento, Susana Alarico, Nuno Empadinhas, Hermínio C. de Sousa, Mara E. M. Braga
O03
11:20 Coffee break + Poster session
Session 2 (Room: Aula Castelao) Co-chairs: Manuel Nunes da Ponte (Univ. Nova de Lisboa), Josefa Fernández
(USC)
Keynote
11:50 A molecular perspective on the search for efficient processes for CO2 capture and separation - the role of modeling Lourdes F. Vega
K1
Oral Communications
12:20 Using Aluminum as reducing agent for the catalytic conversion of ammonia-based CO2 absorption derivatives Juan I. del Río, Eduardo Perez, María Dolores Bermejo, Ángel Martín
O04
12:40 Continuous fractionation of glycerol acetates. Physicochemical properties glycerol acetates + CO2 mixtures at high pressure Selva Pereda, Mariana Fortunatti-Montoya, Pablo E. Hegel
O05
13:00 Lunch break (Hospedería San Martín Pinario; Praza da Inmaculada, 3, 15704 Santiago de Compostela)
9
Tuesday Afternoon, 18th February
14:30 Plenary 2 (Chair: Carlos A García-González (Univ. Santiago de Compostela), Room: Aula Castelao)
Biorefinery of natural products using compressed fluids-based platforms Challenges, needs and answers Elena Ibáñez
PL2
Session 3 (Room: Aula Castelao)
Co-chairs: Selva Pereda (U. Nacional del Sur), Sagrario Beltrán (U. Burgos)
15:20 Research (framework) approach to convey supercritical fluid extraction of agrofood and forestry byproducts from lab to industrial exploitation Marcelo M.R. de Melo, J.A. Saraiva, I. Portugal, C.M. Silva
O06
15:40 Fish waste valorization though a biorefinery approach Rodrigo Melgosa, Liliana Rodrigues, Alexandre Paiva, Pedro Simões, Esther Trigueros, Maria Teresa Sanz, Sagrario Beltrán
O07
16:00 Process and simulation for the scCO2 extraction of bio-oil from a supercritical water ultra-fast hydrolysis of biomass Cristiana Bento, Susana Emre Demirkaya, Juan García-Serna and María José Cocero Alonso
O08
16:20 Coffee break + Poster session
Session 4 (Room: Aula Castelao) Co-chairs: José Coelho (Inst. Politécnico de Lisboa), Herminia Domínguez (U.
Vigo)
16:50 Integrated microwave and supercritical carbon dioxide extraction processes for astaxanthin recovery from brown crab residues Ana N. Nunes, Ana Roda, Luís F. Gouveia, Naiara Fernández, Ana A. Matias
O09
17:10 Recovery of proteins and free amino acids from Gelidium Sesquipedale alga residue by subcritical water extraction (SWE) Esther Trigueros, Patricia Alonso-Riaño, María Teresa Sanz, Cipriano Ramos Rodríguez, Óscar Benito-Román, Sagrario Beltrán
O10
17:30 Simultaneous extraction and purification of fucoxanthin from Tisochrysis lutea microalgae Charles Tardiff, Rocío Gallego, L. Celina Parreira, Tiago Guerra, Elena Ibáñez, Miguel Herrero
O11
17:50 Safety in supercritical extraction plants João Fernandes, Martin Sova, Eduard Lack
O12
18:10 Guided City Tour
19:30 - 21:30 Tapas dinner (Centro Abanca Obra Social; Praza de Cervantes, s/n, 15782, Santiago de Compostela)
10
Wednesday Morning, 19th February
9:30 Plenary 3 (Chair: Luísa Durães (Univ. Coimbra), Room: Salon de Actos Novoa Santos)
Aerogels as Hosts for Nanoparticles for Catalytic Applications Can Erkey
PL3
Session 5 (Room: Aula Castelao)
Co-chairs: Ana Rita Duarte (Univ. Nova Lisboa), Lourdes Calvo (UCM)
10:20 Aerogels made of graphene oxide and magnetic aplications for MRI applications Alejandro Borrás, Ana M. López-Periago, Julio Fraile, Concepción Domingo
O13
10:40 Innovative strategies for the decellularization of trabecular bone using supercritical CO2 and tri(n-butyl) phosphate Marta M. Duarte, Nilza Ribeiro, Inês V. Silva, Juliana R. Dias, Nuno M. Alves, Ana L. Oliveira
O14
11:00 Supercritical fluid technology as a key enabling technology in AERoGELS and GREENERING COST Actions Carlos A. García-González, Mónica Pérez-Cabero, Ana R. Duarte
O15
11:20 Coffee break + Poster session
Session 6 (Room: Aula Castelao) Co-chairs: Sílvio V. Melo (Univ. Federal Bahia), Nora Ventosa (ICMAB-CSIC)
Keynote
11:50 Converting batch into continuous processes — New opportunities for supercritical CO2 technology in pharmaceutical (nano)manufacturing Luís Padrela
K2
Oral Communications
12:20 Encapsulation of 5-aminosalicylic in Eudragit® S-100 by supercritical fluid extraction of emulsions D. Vizcaya, D.R. Serrano, D.F. Tirado, A. Cabañas, L. Calvo
O16
12:40 Surfactant-free CO2 based, microemulsion-like systems: promising nanostructured liquids to gain control over anti-solvent precipitations David Piña, Alessandro Triolo, Andreas Siegfried Braeuer, Nora Ventosa
O17
13:00 Lunch break (EIFS2020 site, Faculty of Medicine)
13:45 Flucomp meeting
11
Wednesday Afternoon, 19th February
14:30 Plenary 4 (Chair: Mara Braga (Univ. Coimbra), Room: Aula Castelao)
Carbon dioxide utilisation: from decaffeination to synthetic fuels Manuel Nunes da Ponte
PL4
Session 7 (Room: Aula Castelao)
Co-chairs: Pedro Simões (Univ. Nova de Lisboa), Angel Martín (Univ. Valladolid)
15:20 Analysis of the influence of different compounds and optimization of the supercritical epoxidation process of grapeseed oil Juan Catalá, M. Teresa García, Jesús M. García-Vargas, M. Jesús Ramos, Juan F. Rodríguez
O18
15:40 Polyethylene glycol-drug conjugates by click chemistry in scCO2 Sonia López, María Teresa García, Juan Francisco Rodriguez, María Jesús Ramos, Ignacio Gracia
O19
16:00 Green and smart polymer for anticancer delivery Beatriz Monteiro, Raquel Viveiros, Teresa Casimiro
O20
16:20 Coffee break + Poster session
Session 8 (Room: Aula Castelao) Co-chairs: Ana L. Oliveira (Univ. Católica Portuguesa), Concha Domingo (ICMAB-
CSIC)
16:50 Supercritical antisolvent micronization of pharmaceutical compounds José P. Coelho, Patricia Matos, António M. F. Palavra, Rui Loureiro, Beatriz P. Nobre
O21
17:10 Formation of pharmaceutical solid solutions using supercritical CO2 assisted processes Vivek Verma, Kevin M Ryan, Matteo Lusi, Luis Padrela
O22
17:30 Supercritical solvent impregnation of mango leaves extract in wound dressings Diego Valor, Antonio Montes, Clara Pereyra, Enrique J. Martínez de la Ossa
O23
17:50 Extended copaiba oleoresin release from PCL-Pluronic porous monoliths against Aedes aegypti larvae Gláucia R. Medeiros Burina, Fábio R. Formiga, Elaine C. M. Cabral-Albuquerque; Sílvio A. B. Vieira de Melo; Mara E. M. Braga; Hermínio J. C. de Sousa
O24
18:10 Closing Session
20:00 Gala dinner (Hostal-Parador de los Reyes Católicos; Praza do Obradoiro, 1, 15705 Santiago de Compostela)
12
Tuesday and Wednesday, 18th and 19th February, 11:20-11:50 and 16:20-16:50
Poster Sessions (Room: Corridor)
Extraction, Fractionation and Biorefinery
SFE extraction of aromatic and lipid compounds from shiitake mushroom (Lentinula edodes) Eva Tejedor-Calvo, Diego Morales, Pedro Marco, Alejandro Ruiz, Cristina Soler-Rivas
PE01
Supercritical carbon dioxide extraction of Portuguese rice bran oil José P. Coelho, Inês M. Fernandes, Nuno R. Neng, José M. Sardinha, José M. Nogueira
PE02
Countercurrent supercritical CO2 extraction of phenolics from the autohydrolysis extracts of Paulownia leaves Paula Rodríguez, Beatriz Díaz-Reinoso, Andrés Moure, Herminia Domínguez
PE03
Supercritical extraction of natural antioxidants from lavender essential oil Encarnación Cruz, Jesús Manuel García-Vargas, Ignacio Gracia, Juan Francisco Rodríguez, M. Teresa García
PE04
Experimental optimization of sub- and supercritical carbon dioxide extractions of carotenoids from Dunaliella salina Mónica Bueno, Clementina Vitali, J. David Sánchez-Martínez, Rocío Gallego, Jose A. Mendiola, Miguel Herrero, Elena Ibáñez
PE05
Effect of thermal pre-treatment on supercritical CO2 extraction of Castanea sativa burs Beatriz Díaz-Reinoso, Paula Rodríguez, Andrés Moure, Herminia Domínguez
PE06
Valorisation of tomato waste using supercritical fluid technologies Marta Marques, Alexandre Paiva, Susana Barreiros, Sandra Simões, Ana Costa, Marta Bento, Pedro Simões
PE07
Sequential extraction (scCO2 + pressurized ethanol) of Paulownia flowers to obtain phenolic/antioxidants compounds Paula Rodríguez-Seoane, Herminio de Sousa, Marisa C. Gaspar, Mara E. M. Braga, Herminia Domínguez
PE08
Sequential extraction of oxindole alkaloids from Uncaria tomentosa leaves by pressurized solventes José R. S. Botelho, Hermínio C. de Sousa, Mara E. M. Braga
PE09
Enriched oil in DHA omega-3 fatty acid by optimized supercritical fluid extraction of Aurantiochytrium sp. microalgae Inês Ferreira, M.M.R. de Melo, M. Sapatinha, J. Pinheiro, M.F.L. Lemos, N.M. Bandarra, I. Batista, M.C. Paulo, J. Coutinho, J.A. Saraiva, I. Portugal, C.M. Silva
PE10
Silybum marianum extracts obtained by conventional and supercritical fluid extraction techniques Ivana Lukic, Stoja Milovanovic, Milica Pantic, Vanja Tadic
PE11
13
Colombian coffee silverskin as source of bioactive extracts A.M. Escamilla-Santos, A.D.P. Sánchez-Camargo, M. Martínez-Rodríguez, G. Alvarez-Rivera, S.R.S. Ferreira, A. Cifuentes, E. Ibáñez, F. Parada-Alfonso
PE12
Valorisation of agro industrial by-products for obtaining bioactive extracts using SFE and PLE: Colombia as case study D. Ballesteros-Vivas, A.D.P. Sánchez-Camargo, J.P. Ortega-Barbosa, S.J. Morantes Medina, H.A. Martínez-Correa, A.M. Hurtado-Benavides, L.I. Rodríguez Varela, F. Parada-Alfonso
PE13
Evaluation of the antibacterial activity of Rosmarinus essential oil (Rosmarinus officinalis) obtained by supercritical fluids extraction against bacterial microbiota of rainbow trout (Oncorhynchus mykiss) Zully Suarez-Montenegro, F. Argote-Vega, E. Arteaga-Cabrera, A. López-Suárez, A. Hurtado-Benavides, M. Quiroz-Cabrera, A. Cifuentes, E. Ibañez
PE14
Subcritical water fractionation of proteins and free amino acids from Brewer’s Spent Grain (BSG) Patricia Alonso-Riaño, Esther Trigueros, María Teresa Sanz, Sagrario Beltrán, Cipriano Ramos, Óscar Benito- Román
PE16
The supercritical water approach in valorization of high lignin content biomass Tijana Adamovic, Maria Jose Cocero
PE17
Integral valorization of agro-food biomass through pressurized fluids. Case study: Brewery Spent Grain (BSG) Maria Teresa Sanz, Patrícia Alonso-Riaño, Esther Trigueros, M. Kashaninejad, D.M. Aymara, Oscar Benito-Román, M. O. Ruiz, I. Escudero, J. M. Benito, Sagrario Beltrán
PE18
Supercritical fluid extraction of triterpenoids of the lupane type from Acacia dealbata bark biomass Vítor H. Rodriguesa, Inês Portugala, Carlos M. Silvaa
PE19
Reactions and CO2 capture/separation
Direct hydrothermal conversion of CO2 capture on aqueous solutions of alkanolamines into formic acid and methane Laura Quintana Gómez, Ángel Martín Martínez, M. Dolores Bermejo Roda
PR01
Hydroxyl-functionalised ionic liquids in the synthesis of cyclic carbonates from high-pressure CO2 A. B. Paninho, A. Forte, M. E. Zakrzewskaa, K. T. Mahmudov, A. J. L. Pombeiro, M. F. C. Guedes da Silva, M. Nunes da Ponte, Luís C. Branco, Ana V. M. Nunes
PR02
Thermodynamics, Phase Equilibria, and Transport phenomena/properties
The effect of the three phase relative permeability model in low salinity water alternating supercritical CO2 injection Silvio A. B. Vieira de Melo, Arley S. Carvalhal, Gloria M.N. Costa
PT01
14
Study of volumetric behavior during asphaltene precipitation due to supercritical CO2 injection using PC-SAFT EoS Silvio A. B. Vieira de Melo, Fabio P. Nascimento, Gloria M. N. Costa
PT02
Estimation of multicomponent diffusivities in supercritical and liquid mixtures Bruno Zêzere, João Iglésias, Inês Portugal, José R. B. Gomes, Carlos M. Silva
PT03
Molecular dynamics simulation of diffusion coefficients in supercritical carbon dioxide João Iglésias, Bruno Zêzere, Inês Portugal, José R. B. Gomes, Carlos Manuel Silva
PT04
Experimental measurements of diffusion coefficients in compressed liquids and supercritical fluids Carlos Manuel Silva, Bruno Zêzere, José R. B. Gomes, Inês Portugal
PT05
Prediction of diffusivities in supercritical carbon dioxide using machine learning models José P.S. Aniceto, Bruno Zêzere, Carlos M. Silva
PT06
Materials, Biomaterials and Sterilization
Modelling the in vitro release of Gemcitabine impregnated foams by high-pressure CO2 Irene Álvarez, C. Gutiérrez, A. de Lucas, Ignacio Gracia, Juan Franciso Rodríguez, M. Teresa García
PM01
Supercritical impregnation of bioactive extracts in alginate wound dressing Elisabeth Gómez-Cepero, M. Teresa Fernández-Ponce, Cristina Cejudo, Lourdes Casas, Casimiro Mantell, Enrique Martínez de la Ossa, Clara Pereyra
PM02
Nanolubricants based on silane-coated nanoparticles using supercritical CO2 Fátima Mariño, Víctor Santos-Rosales, Carlos A. García-González, Josefa Fernández, Enriqueta R. López
PM03
Green revalorization strategy following an adsorbent-assisted supercritical CO2 extraction of terpenoids from olive leaves. Evaluation of the neuroprotective effects of the obtained extracts Zully Suárez-Montenegro, Mónica Bueno, Gerardo Álvarez-Rivera, Jose A. Mendiola, Alejandro Cifuentes, Elena Ibáñez
PM04
Strategies for the processing of medicated scaffolds for bone repair by supercritical foaming Ana Iglesias-Mejuto, Víctor Santos-Rosales, Carmen Álvarez-Lorenzo, Philip Jaeger, José Luis Gómez-Amoza, Carlos A. García- González
PM05
Aerogels made of graphene oxide and metal-organic frameworks for gas separation Alejandro Borrás, A. Rosado, J. Navarro, Julio Fraile, J. G. Planas, Ana M. López-Periago, Concepción Domingo, Amirali Yazdi
PM06
The role alginate-nanohydroxyapatite hydrogel on osteogenic response activation of mesenchymal cells Joana Barros, Maria Pia Ferraz, Joana Azeredo, M.H. Fernandes, P.S. Gomes, Fernando J. Monteiro
PM07
15
Preparation of advanced drug delivery systems containing gold nanoparticles using supercritical CO2 Albertina Cabañas, Jonathan Bermúdez, M.J. Tenorio, Eduardo Sánchez, Isaac A. Cuadra, Concepción Pando, Diego Felipe Tirado, Lourdes Calvo
PM08
Searching a way of controlling the Pine Wood Nematode insect vector with PCL based matrices obtained by supercritical CO2 foaming João Leocádio, Marisa C. Gaspar, Fernando Bernardo, Pedro Naves, Edmundo Sousa, Hermínio C. de Sousa, Luis Bonifácio, Mara E. M. Braga
PM09
Supercritical CO2 impregnation of PLA/PCL film with carvacrol for food active packaging Ivana Lukic,Jelena Vulic, Stoja Milovanovic, Jasna Ivanovic
PM10
Inactivation of Salmonella Enteritidis in liquid whole egg with supercritical carbon dioxide in isolation and in combination with cinnamaldehyde María Teresa Valverde, Diego F. Tirado, Amaury Taboada-Rodríguez, Fulgencio Marín-Iniesta, Lourdes Calvo
PM11
Inactivation of Legionella in aqueous media by supercritical CO2 D. Martín, María Teresa Valverde, Diego F. Tirado, Lourdes Calvo
PM12
Particle production
Solid lipid microparticles (SLMPs) for the local delivery of an anaesthetic agent Clara López Iglesias, Cristina Quílez, Joana Barros, Enriqueta R. López, D. Velasco, José L. Jorcano, Fernando J. Monteiro, Carmen Alvarez-Lorenzo, Josefa Fernández, Carlos A. García-González
PP01
Supercritical antisolvent precipitation of Ca/Mg acetate as precursor for Ca/Mg Oxide Luis C. S. Nobre, Paula Teixeira, Carla I.C. Pinheiro, António M. F. Palavra, Mário J. F. Calvete, Carlos A. Nieto de Castro, Beatriz P. Nobre
PP02
Using supercritical fluid technology to generate novel cocrystals of poorly soluble drugs Barry Long, Kevin M. Ryan, Luis Padrela
PP03
Microencapsulation of supercritical CO2 extracted rice bran oil in pea proteins Óscar Benito-Román, Teresa Sanz, Sagrario Beltrán
PP04
16
17
Plenary Lectures
18
19
EIFS 2020 PL1
Aerogels - Synthesis, properties and applications
Lorenz Ratke
Institute of Materials Research, German Aerospace Center, DLR, Cologne, Germany * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT Aerogels are a fascinating material: they consist mainly of air entrapped into an open porous solid network of nanoparticles. Their properties are outstanding: their density is low, typically around 100 kg/m3, their thermal conductivity can be as low as 0.01 W/mK, their specific surface area is typically between a few hundred to a few thousand m2/g. The microstructures of aerogels are characterized by well accessible branched mesopores in the range of 5 to 100 nm and a solid network of nano-particles or fibrils spans the whole volume. Aerogels can be made from inorganics, oxides like silica, but also polymers, like phenolic or resorcinol resins, polyimides and polyurethanes and a few of them can be converted into carbon aerogels. In the last decade aerogels made from biopolymers came into focus of research like cellulose, alginates, chitosans and many other polysaccharides.
Although aerogels are known since a long time and had become a focus of research in the eighties and nineties of the last century, leading to first industrial applications, they came newly into the focus of bulk nanostructured research and development since the last decade, especially due to improvements of processing and the development of new kinds of aerogels and aerogel composites widening the field of applications from purely insolation purposes to medical and food ones. This lecture shall give a brief survey on aerogels, their synthesis, properties and industrial applications and try also to outline, where fundamental research on the transformation of a solution to a gel and eventually an aerogel still deserves closer attention.
20
21
EIFS 2020 PL2
Biorefinery of natural products using compressed fluids-
based platforms. Challenges, needs and answers.
Elena Ibáñeza,*, D. Ballesteros-Vivasa,b, G. Alvarez-Riveraa, F. Parada-Alfonsob, A. Cifuentesa, Jose A. Mendiolaa, Miguel Herreroa
a Laboratory of Foodomics, Institute of Food Science Research, CIAL, CSIC, Madrid, Spain. b High Pressure Laboratory, Department of Chemistry, Faculty of Science, Universidad
Nacional de Colombia, Bogotá D.C., 111321, Colombia * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT One of the main challenges the world is facing nowadays is related to sustainability; in this sense, the roadmap towards the achievement of the SDGs (Sustainable Development Goals) by 2030 imposes some needs that have to be fulfilled and, therefore, new answers should be provided. In this sense, to fulfill with sustainability, many aspects should be considered, ranging from the rational use of resources to the modern concept of biorefinery involving biomass conversion processes and equipment to different commodities. Considering this framework, the extraction of high added-value products from natural sources (including agricultural by-products or algae) is of high interest since it can allow consolidating the idea of sustainable processes. Nevertheless, for the development of these sustainable processes the 12 principles of Green Chemistry [1] have to be closely examined, considering that effectively provide a
22
framework for designing and/or improving materials, products, processes and systems from an environment protection perspective. New challenges researchers are facing are the development of fast, selective, efficient, sustainable, green (without using toxic organic solvents) processes, providing also with high yields and at lower costs. Processes able to meet these requirements are, among others, those based on the use of compressed fluids such as supercritical fluid extraction (SFE), carbon dioxide expanded liquids extraction (CXLs), pressurized liquid extraction (PLE) and subcritical water extraction (SWE). The development of compressed-fluids based platforms able to change solvent properties by adding (or removing) carbon dioxide (at medium-high pressures) opens the door to the design of multi-unit operations in which CO2 can be used to modify the solubility properties, as a trigger for reaction/separation processes, to enhance the mass transfer and to improve energy and environmental costs, among others. Likewise, these processes have a good potential to be applied in integrated and/or intensified processes, with further integration within biorefinery approaches [2]. In this presentation, different examples of compressed fluids-based platforms for biorefinery of natural products such as tropical fruits by-products and microalgae for obtaining high added-value products will be presented. Strategies include the use of compressed fluids and alternative tools such as the use of Hansen Solubility Parameters (HSP) for green solvent selection. ACKNOWLEDGEMENTS This research was financed under projects ABACUS (Algae for a Biomass Applied to the produCtion of added value compounds—funded by the Bio Based Industries Joint Undertaking under the European Union’s Horizon 2020 research and innovation programme under grant agreement No 745668) and AGL2017-89417-R (MINECO, Spain). G.A.-R. would like to acknowledge the Ministry of Economy and Competitiveness for a “Juan de la Cierva” postdoctoral grant.
REFERENCES
[1] P.T. Anastas, J.C. Warner, Green Chemistry: Theory and Practice, Oxford University Press, New York, 1998.
[2] M. Herrero, J.A. Mendiola, E. Ibáñez, Gas expanded liquids and switchable solvents, Current Opinion in Green and Sustainable Chemistry 5 (2017) 24-30
23
EIFS 2020 PL3
Aerogels as Hosts for Nanoparticles for Catalytic Applications
Can Erkey a,*
aDepartment of Chemical and Biological Engineering, Koç University, Sarıyer 34450, Istanbul, Turkey
GRAPHICAL ABSTRACT
ABSTRACT
Aerogels are excellent materials for hosting catalytic nanoparticles due to their large surface areas and high pore volumes. Their narrow pore size distribution and high surface areas enables excellent dispersion of nanoparticles and control over the rates of diffusion of reactants and products to and from catalytic sites consisting of nanoparticles leading to higher catalytic activity. A wide variety of mono and bimetallic nanoparticles were incorporated into organic, inorganic and composite aerogels by various techniques such as wet impregnation, incipient wetness, chemical vapor deposition and supercritical deposition. Electrically conductive carbon aerogels (CAs) obtained by pyrolysis of different organic aerogels and graphene aerogel are attractive as supports for electrocatalysts for environmentally important reactions such as oxygen reduction, methanol oxidation and carbon dioxide reduction. Their high accessible surface area, adjustable pore size and pore volume enable efficient ion transport and maximizes the utilization of electroactive sites leading to high electrocatalytic activity. Furthermore, heteroatom doping (N, S, P) combined with the desirable properties of CAs also resulted in superior electrocatalytic activity compared to conventional carbonaceous materials. Furthermore, alumina and silica aerogels having high hydrothermal and mechanical stability have been investigated as supports
24
for high temperature reactions such as hydrogenation/dehydrogenation and Fischer-Tropsch synthesis with promising activities and selectivities. Unlike conventional porous materials, aerogels can also be produced in any form, such as beads, cylinders and monoliths which may be advantageous for various catalytic applications. Channels in silica aerogel monoliths with titania nanoparticles were used as optofluidic microreactors for photocatalytic phenol degradation and excellent wave guiding was achieved with promising photocatalytic activity and stability. Moreover, many different composite aerogel types can be engineered with desired properties as host materials for a targeted catalytic application. Metal-organic framework (MOF) aerogel composites (MOFACs), for example, is an emerging class of materials that have promising possibilities for catalytic applications.
25
EIFS 2020 PL4
Carbon Dioxide Utilisation: from decaffeination to synthetic fuels
Manuel Nunes da Ponte
LAQV, REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Portugal
GRAPHICAL ABSTRACT
ABSTRACT Applications of high pressure supercritical carbon dioxide in separations involving natural products started to be developed in Germany in the sixties and seventies of the last century. This work gave rise to the new field of supercritical fluids, and to two new unit operations in Chemical Engineering, extraction and fractionation with ScCO2, and also to newly built industrial plants, mostly dedicated to extraction or cleaning of natural products, but, in some cases, to chemical reactions, like hydrogenation and oxidation, or to handling of solids.
Decaffeination of coffee, as the first developed process, played an important role in the appearance of other “niche”, small volume applications, pushed as much by the special properties of supercritical carbon dioxide as by regulations aiming at replacing volatile organic solvents. Those were the times when carbon dioxide was deemed “innocuous, generally regarded as safe”.
In recent times, greenhouse gas emissions and climate change have finally reached the attention of worldwide public opinion, and carbon dioxide is now essentially regarded as a pollutant, and a dangerous substance. Paradoxically, this new situation opens new
26
opportunities for the supercritical CO2 community on a much larger scale than seen until now.
Carbon Dioxide Utilisation is a fast expanding subject of study. Due to the enormous dimension of CO2 emissions from fossil fuel burning (5 tonnes per living human being per year, and still growing), the only way that carbon dioxide utilisation can make any difference in the carbon geocycle is the production of synthetic fuels.
In this communication, some of the old and recent successes of supercritical carbon dioxide extraction and fractionation will be reviewed, followed by its application as solvent in chemical reactions, in particular hydrogenations of hydrocarbons and other organics and also in controlled oxidation of natural products. This will open the way to a brief survey of current activities in the transformation of carbon dioxide into gaseous or liquid fuels, such as syngas, methanol or hydrocarbons.
This field has been connected to Carbon Capture and Sequestration (CCS), proposed as a technology to decrease emissions from coal-fired power plants and cement factories. CO2 may be separated from other exhaust gases, compressed and buried underground in spent oil fields. As an alternative to burying, carbon dioxide might be recycled to produce carbon-based synthetic fuels as renewable electrical energy vectors, by direct electrochemical reduction or by reaction with hydrogen produced by electrolysis of water.
Examples of both strategies will be presented, where mixtures of high pressure carbon dioxide and ionic liquids were used. As a first case, results of reduction performed in a novel high pressure electrochemical cell will be presented. Using a different methodology, CO2 and hydrogen were reacted, producing methane in a highly selective fashion. Ruthenium metallic nanoparticles formed in situ were used as catalyst.
27
Keynote Presentations
28
29
EIFS 2020 K1
A molecular perspective on the search for efficient processes for CO2 capture and separation - the role of modeling
Lourdes F. Vegaa,b,c*, Ismail I. Alkhatiba,b, Ahmed Al Hajaja,b, Daniel Bahamona,b,c
a Chemical Engineering Department, Khalifa University, P.O. Box 127788, Abu Dhabi, UAE b Research and Innovation Center on CO2 and H2 (RICH Center), Khalifa University, P.O. Box
127788, Abu Dhabi, UAE c Center for Catalysis and Separation (CeCaS), Khalifa University, P.O. Box 127788, Abu
Dhabi, UAE *[email protected]
GRAPHICAL ABSTRACT
ABSTRACT In the context of sustainable development and clean energy production, one of the most important alternatives to mitigate anthropogenic CO2 emissions is to capture and separate CO2 from diluted sources, such as gases emitted from fossil fuel combustion and other industrial processes. The captured CO2 needs to be permanently stored, directly used for different purposes (such as processes using supercritical CO2, water treatment and others) or converted into final products (materials, etc.). Using the captured CO2 versus storing it offers significant advantages in the context of sustainable development, while helping to diversify the economy as new products will enter into the market or CO2 will replace other compounds more harmful to the environment. However, the challenges to accomplish it are huge, including the limitation of the market (32Gt of CO2 emitted in 2017 versus 130Mt used in the different industrial sectors) and the high stability of the CO2 molecule, which requires great amounts of energy and the development of highly efficient catalysts for its successful conversion.
Aqueous Monoethanolamine (MEA) solution, is the most mature technology for CO2 capture, currently used in industrial processes. However, the high regeneration energy consumption is the major obstacle to its large-scale utilization. Therefore, it is highly desirable to develop new chemical absorption systems or other processes that overcome
30
the drawbacks of the traditionally used aqueous MEA solvent. Different strategies are used for this purpose: (1) the identification of suitable amines as MEA replacements with less energy intensive requirement, (2) the replacement of water (fully or partially) with alternative physical solvents with lower heat capacity and evaporation enthalpy that, when combined with MEA, form physical-chemical absorbents and (3) the use of adsorption into solid materials highly attractive to CO2 or conveniently modified with amine groups for this purpose [1,2]. The three alternatives will be explored in this presentation, taking advantage of the information provided by molecular modeling techniques.
The focus of this presentation will be on how understanding the molecular interactions of complex mixtures can help the development of more efficient processes for CO2 capture and separation, obtaining as a final product CO2 with the required purity for the different industrial applications. We showcase the capabilities and results of a robust molecular based screening tool of chemical solvents for the efficient removal of CO2 and other acid gases from industrial gas streams at relevant gas separation process conditions. The screening tool is built on the molecular-based equation of state soft-SAFT [3]. Within this framework, substances are modelled as chains molecules which are characterized by a set of molecular parameters representing the chemical structure of molecules and key intermolecular interactions. The equation is able to provide accurate phase equilibria, interfacial properties and viscosities of different mixtures. The study is performed in a systematic manner, first benchmarking the performance of the equation for capturing CO2 in aqueous amines [4], followed by water-free and water-lean amine systems [5], allowing predictions of their performance at process conditions, with a very limited set of experimental data. In addition, molecular simulations were performed to understand the effect of degraded amines in the capture and separation process. Finally, examples will be provided on how molecular simulations can be used combined with process modeling for designing ad-hoc processes of CO2 separation by adsorption [6], as the third alternative to overcome the limitations of CO2 capture with aqueous amines. ACKNOWLEDGEMENTS Early contributions and several helpful discussions with Fèlix Llovell and Luis M.C. Pereira are gratefully acknowledged. This work is partially funded by ADNOC Gas Processing and its stakeholders Total, Shell and Partex, through the Gas Research Center (project GRC2018-003) and Khalifa University of Science and Technology (RC2-2019-007).
REFERENCES [1] D Bahamon, LF Vega, Chem. Eng. J. 284, 438-447, 2016.
[2] S Builes, LF Vega, J. Phys. Chem. C 116 (4), 3017-3024, 2012. [3] FJ Blas, LF Vega, Mol. Phys. 92, 135–150, 1997. [4] LMC Pereira, LF Vega, Applied Energy 232, 273-291, 2018. [5] III Alkhatib, LMC Pereira, A AlHajaj, LF Vega, J. CO2 Utilization, 2019
https://doi.org/10.1016/j.jcou.2019.09.010.
[6] D Bahamon, A Díaz-Márquez, P Gamallo, LF Vega, Chem. Eng. J. 342, 458-473, 2018
31
EIFS 2020 K2
Converting batch into continuous processes — New opportunities for supercritical CO2 technology in
pharmaceutical (nano)manufacturing
Luis Padrela*, Barry Long, Vivek Verma, Kevin M. Ryan SSPC Research Centre, Department of Chemical Sciences, Bernal Institute, University of
Limerick, Limerick, Ireland *[email protected]
GRAPHICAL ABSTRACT
ABSTRACT
Poor solubility and bioavailability of new chemical entities is a major challenge that keeps plaguing the pharmaceutical industry and jeopardizes their away to the market. Over the last decade, approximately 70% of new APIs (Active Pharmaceutical Ingredients) coming through the R&D centres of large pharmaceutical companies have failed to progress due to poor solubility. Novel nanomanufacturing methods, which include supercritical fluid technologies, and nanoparticle delivery systems have been leading to breakthroughs in the enhancement of physicochemical properties of poorly water-soluble drugs.1 However, these methods have been facing challenges regarding their full implementation in the industry. One of these challenges lies with the inherent difficulties associated when scaling-up nano-processes. Interestingly, the development of continuous and semi-continuous methodologies for drug manufacturing is providing new opportunities for a more successful adaptation of nanotechnological tools onto the industrial environment. As continuous manufacturing processes reduce the size of the manufacturing footprint, scaling-up nanomanufacturing methods becomes much more reliable or even unnecessary.2 By using smaller production facilities, continuous nanomanufacturing methods bear the potential to providing a wide
32
range of benefits for poorly soluble drugs while speeding up the whole drug development process. This presentation will provide an overview on existing methods for the production of pharmaceutical nanoparticles/nanomaterials and show case studies on the production and control of the solid state form of APIs (e.g. polymorphs, cocrystals) using batch and continuous supercritical CO2 methods.3-5 A particular focus will be provided on a novel technology that uses supercritical CO2-assisted spray drying as part of a continuous process for the production, isolation and downstream processing of API nanoparticles. Examples will be provided on API nanomaterials produced by this technology which feature optimal rheological properties (e.g. flowability, compactability) typical of large micron-sized particles, while still maintaining high dissolution rate profiles typical of nano-sized particles. ACKNOWLEDGEMENTS The authors acknowledge Science Foundation Ireland for supporting the work undertaken at the Synthesis and Solid State Pharmaceutical Centre (Grants SFI SSPC2 12/RC/2275, 15/US-C2C/I3133 and 16/ETP/3386) and Enterprise Ireland (Grant CF2017-0754-P).
REFERENCES
[1] L. Padrela, M.A. Rodrigues, A. Duarte, A.M.A. Dias, M.E.M. Braga, H.C. de Sousa, Advanced Drug Delivery Reviews, 131, 22-78, 2018.
[2] B. Long, K.M. Ryan, L. Padrela, European Journal of Pharmaceutical Sciences, 137, 104971, 2019.
[3] L. Padrela, J. Zeglinski, K.M. Ryan, Crystal Growth & Design, 17 (9), 4544-4553, 2017.
[4] L. Padrela, B. Castro-Dominguez, A. Ziaee, B. Long, K.M. Ryan, G. Walker, E. O'Reilly, CrystEngComm, 21 (18), 2845-2848, 2019.
[5] B. Long, G.M. Walker, K.M. Ryan, L. Padrela, Crystal Growth & Design, 19 (7), 3755-3767, 2019.
33
Oral Sessions
34
35
EIFS 2020 O01 Classification of flow regimes of alginate aerogel particles in a
laboratory scale Wurster fluidized bed
Işık Sena Akgün a, Can Erkey a*
aDepartment of Chemical and Biological Engineering, Koç University, Sarıyer 34450, Istanbul, Turkey
GRAPHICAL ABSTRACT
ABSTRACT
Aerogels in the form of particles are attracting increasing attention for a wide variety of applications due to their open pore structures, very high specific surface areas and pore volumes [1]. Enhancements of some of the properties of aerogels such as mechanical strength, thermal stability and appearance by coating the surface of aerogel particles with a thin polymer layer may significantly improve the performance of aerogel based products [2-5]. One of the widely used equipment to coat solid particles is a batch type fluidized bed coater which is generally classified according to the spraying technique as top spray, bottom spray, rotary tangential spray and Wurster bottom spray. Among these, Wurster fluidized bed might be particularly suitable for aerogels due to its smooth and continuous tube above the perforated plate which enables circulatory particle motion [5,6]. Particle fluidization behavior inside the bed depends on design parameters of the bed such as Wurster tube size, partition gap height and on operating parameters such air velocity and physical characteristic of particles [7]. Inappropriate selection of operating parameters may lead to particle adhesion and nonuniform coating. Thus, a classification of the flow regimes of aerogel particles in a Wurster fluidized bed is necessary to provide insight into the relation between fluidized bed design parameters, physical characteristics of particles and particle fluidization behavior. Such data are also useful for design and scale-up of
36
Wurster fluidized beds for a wide variety of treatment processes for aerogels. In the literature, particle fluidization behavior in fluidized beds is generally described using general flow regime diagrams which were developed by Kunii and Levenspiel [8]. In these diagrams, different flow regimes are mapped as a function of dimensionless air velocity (u*) and particle diameter (dp*). Six regimes are given in these diagrams which are minimum, bubbling, turbulent fluidization, pneumatic transport, fast fluidized and spouted bed. The aim of the present study was to expand the general fluidization diagrams to alginate aerogels particles. Experiments were carried out in a homemade laboratory scale Wurster fluidized bed [6]. The spherical alginate aerogel particles with different particle sizes (2 mm, 4.4 mm, 5.3 mm) and densities (0.020 g/cm3, 0.045 g/cm3, 0.094 g/cm3) were synthesized by dripping an alginate solution into a CaCl2 solution followed by drying by supercritical CO2 in an Applied Separations Speed SFE. The fluidization behavior of particles was visually observed and also recorded with a camera (Samsung ISOCELL S5K2L1). Fluidization air velocity was stepwise increased and fluidization regimes were visually observed by changing the operating and design parameters of the bed such as batch volume (200 ml and 400 ml), Wurster tube length (150 mm and 200 mm) and Wurster tube diameter (80 mm and 100 mm). Velocities at onset and offset of each regime were recorded for annular and tube zones, separately, and u* and dp* values were calculated. Three main fluidization regimes were found for annular zone which were minimum fluidization, bubbling and turbulent. In the tube zone, the minimum fluidization, bubbling, pneumatic transport regimes were recognized. Besides the already defined six regimes, two new regions which were circular motion regime in the tube zone and circulatory particle motion regime in the bed were identified. Subsequently, the boundaries for these regimes were mapped for the first time for aerogel particles. It was also found that among operating and design parameters, particle diameter and batch volume were two main parameters that significantly affected hydrodynamic behavior of the alginate particles in the bed. ACKNOWLEDGEMENTS Work carried out in the frame of the COST-Action "Advanced Engineering of aeroGels for Environment and Life Sciences" (AERoGELS, ref. CA18125) funded by the European Commission. REFERENCES [1] M.A. Aegerter, N. Leventis, M.M. Koebel, Aerogels Handbook, Springer Science & Business Media, Berlin, Germany, 2011.
[2] Z.Ulker, C. Erkey, RSC Adv., 4, 62362 – 62366, 2014.
[3] N. Murillo-Cremaes, P. Subra-Paternault, J. Saurina, A. Roig, C. Domingo, Colloid Polym. Sci., 292, 2475–2484, 2014.
[4] M. Alnaief, S. Antonyuk, C. Hentzschel, C, Leopold, S. Heinrich, I. Smirnova, Microporous Mesoporous Mater., 160, 167 – 173, 2012.
[5] Z.A. Abdul Halim, M.A. Mat Yajid, M.H. Idris, H. Hamdan, J. Dispers. Sci. Technol. 39, 1093 – 1101, 2017.
[6] I.S.Akgun, C. Erkey, Molecules, 24 (16), 2019.
[7] D. Jones, E Godek, Elsevier, Amsterdam, The Netherlands, pp. 997 – 1014, 2017.
[8] D. Kunii, O. Levenspiel, Fluidization Engineering, Elsevier, Amsterdam, The Netherlands, 2013.
37
EIFS 2020 O02
Morphological study and in silico modelling of biodegradable poly(𝜺𝜺-caprolactone) scaffolds with controlled architectures
obtained by supercritical CO2 foaming
Víctor Santos-Rosalesa,*, Marta Gallob, José L. Gómez-Amozaa and Carlos A. García-Gonzáleza
a Dept. Farmacología, Farmacia y Tecnología Farmacéutica, I+D Farma group (GI-1645), Faculty of Pharmacy, Agrupación Estratégica de Materiales (AeMAT), and Health Research Institute of Santiago de Compostela (IDIS), Universidade de Santiago de Compostela, 15782
Santiago de Compostela, Spain. b Department of Applied Science and Technology, Politecnico di Torino, Corso Duca degli
Abruzzi 24, 10129, Torino, Italy *[email protected]
GRAPHICAL ABSTRACT
ABSTRACT
Healthy bones provide a functional human skeleton that allows mobility and protection of vital organs from injuries. The high prevalence of bone diseases compromising the integrity of the osseous tissue and the increasing incidence of fortuitous severe fractures (related to the popularization of sports practice and the obesity pandemic) represent a global healthcare concern. Current gold-standard surgical procedures to repair bone defects mainly implies harvesting bone from the same patient or the use of non-osteoinductive synthetic materials, both of them not exempt from clinical complications [1]. The rising era of the biomaterials has fuelled a huge development of synthetic bone
38
grafts, known as scaffolds. These constructs are designed to temporarily surrogate natural bone and to promote the tissue formation on the bone defect until the complete recovery of the bone functionality is reached. Among the portfolio of scaffold manufacturing techniques, the supercritical CO2-assisted foaming emerges as a promising technology that operates under mild conditions and in the absence of solvents [1,2]. Nevertheless, there is a paucity of information to model the effect of the main processing variables of this technology (pressure, temperature, soaking time and depressurization rate) on the scaffold end properties (porosity, pore size distribution and interconnectivity).
In this work, a range of foaming temperatures (37-41ºC) and soaking times (1-5 h) were screened at a fixed operating pressure (140 bar) regarding their effect on the morphological and mechanical properties of poly(ε-caprolactone) (PCL) scaffolds obtained by supercritical CO2 foaming. Higher processing temperatures and longer soaking times led to increased porosity values, ranging from 59 to 73 %. Advanced X-ray microtomography (µ-CT) analyses and mercury intrusion porosimetry (MIP) measurements were performed to characterize the resulting porous architectures. The inner porous architecture (pore size distribution and interconnectivity) of these scaffolds deeply varied regarding these working parameters. Finally, in silico modelling of the experimental data was carried out to assess the functionality of the obtained PCL scaffolds (cell infiltration capacity, water permeability) and to define the feasible operating region to obtain bone grafts with enhanced performance.
ACKNOWLEDGEMENTS Work supported by Xunta de Galicia [ED431F 2016/010 & ED431C 2016/008], MINECO [SAF2017-83118-R], MCIUN [RTI2018-094131-A-I00], AeMAT [ED431E 2018/08], Agencia Estatal Investigación [AEI] and FEDER funds. V. S.-R. thanks to Xunta de Galicia (Consellería de Cultura, Educación e Ordenación Universitaria) for a predoctoral research fellowship [ED481A-2018/014]. C.A.G.-G. acknowledges to MINECO for a Ramón y Cajal Fellowship [RYC2014-15239]. Work carried out in the frame of the COST-Action "Advanced Engineering of aeroGels for Environment and Life Sciences" (AERoGELS, ref. CA18125) funded by the European Commission.
REFERENCES [1] García-González, C.A.; Concheiro, A.; Alvarez-Lorenzo, C. Bioconjug. Chem. 2015, 26, 1159–1171.
[2] García-González, C.A.; Barros, J.; Rey-Rico, A.; Redondo, P.; Gómez-Amoza, J.L.; Concheiro, A.; Alvarez-Lorenzo, C.; Monteiro, F.J. ACS Appl. Mater. Interfaces 2018, 10, 3349–3360.
39
EIFS 2020 O03
ScCO2 sterilization of natural-based hydrogel and aerogel for biomedical applications
Cristiana Bentoa, Susana Alaricob, Nuno Empadinhasb,
Hermínio C. de Sousaa, Mara E. M. Bragaa,*
aChemical Process Engineering and Forest Products Research Centre (CIEPQPF), Department of Chemical Engineering, University of Coimbra, 3030-790 Coimbra, Portugal
b Center for Neuroscience and Cell Biology, University of Coimbra, 3004-504 Coimbra, Portugal
GRAPHICAL ABSTRACT
ABSTRACT The use of biopolymers in the biomedical field has been growing, due to their properties such as biocompatibility and biodegradability [1]. However, their use requires an effective sterilization method that does not compromise their physicochemical properties, as the methods commonly used, such as autoclaving, gamma radiation, and ethylene oxide, affect these properties [2]-[4]. Supercritical carbon dioxide appears as an alternative for the sterilization of thermosensitive materials [2]. The purpose of this work is developing an effective production method of natural-based hydrogels and aerogels associated with a sterilization method to apply in regenerative medicine.
In this work, it was tested the use of scCO2 in the sterilization of natural-based hydrogels and aerogels. Two distinct polymeric matrices were developed, one alginate and gelatin PEC, cross-linked with calcium chloride, and one deacetylated chitosan and pectin PEC. The aerogel (alginate and gelatine) was dried and sterilized, with supercritical CO2 while the hydrogel (chitosan and pectin), was only sterilized. Two sterilization conditions were tested with different pressure differentials, 100 and 250 bar, and the efficiency of the method was compared to autoclaving. The samples were sterilized inside and outside of a sterilization packaging. The results of microbiological evaluation using sampling and plating in different culture media demonstrated greater efficiency of the sterilization process with ∆P = 250 bar, with contamination appearing in only one of the analysed samples. This contaminant was isolated and identified by molecular methods as a strain of a species of the
40
genus Bacillus (spore-forming bacteria). The elimination of spores formed by species of this genus using supercritical CO2 is limited [2], [5]. In the case of the sterilization condition with ∆P = 100 bar, the growth of microorganisms was verified in the culture media corresponding to the samples sterilized inside the sterilization package and no colonies were detected in the culture media corresponding to the autoclaved samples.
In the analyses carried out to identify changes in the physicochemical properties, it was observed, by FTIR analysis, that the scCO2 sterilization process doesn’t change the samples at the chemical level. However, in the case of the autoclaved sample, the spectrum obtained is altered, suggesting a possible denaturation of the gelatin. Besides, the sample presents a yellowish colour which corroborates the possibility of denaturation. Using DSC analysis this degradation was also identified. The density has not changed due to the sterilization process, and as far as porosity is concerned, it was discovered that the samples sterilized with scCO2 were not affected, but in those sterilized by autoclave, the pores collapsed. The analysis revealed that ∆P=100 bar has a minor impact on the mechanical properties of the material. In the end, it was possible to obtain, properly, sterilized aerogels, capable of being applied in regenerative medicine, however, due to the low elastic modulus, its application in bone fractures was compromised. ACKNOWLEDGEMENTS This work was financially supported by “Fundação para a Ciência e Tecnologia (FCT, Portugal)” through the project “STERILAEROGEL – Green method to prepare sterilized biopolymers based aerogel” – POCI-01-0145-FEDER-032625, and FCT-MEC (PEst-C/EQB/UI0102/2013, Est-C/EQB/UI0102/2018, PEst-C/EQB/UI0102/2019 and UID/NEU/04539/2019). M. E. M. Braga acknowledges FCT for the financial support through the Post-Doctoral FCT fellowship (SFRH/BPD/101048/2014).
REFERENCES
[1] H. Maleki, L. Durães, C. A. García-González, P. del Gaudio, A. Portugal, and M. Mahmoudi, Adv. Colloid Interface Sci., vol. 236, pp. 1–27, 2016.
[2] J. Zhang, T. A. Davis, M. A. Matthews, M. J. Drews, M. LaBerge, and Y. H. An, J. Supercrit. Fluids, vol. 38, no. 3, pp. 354–372, 2006.
[3] F. Tessarolo, Encycl. Biomater. Biomed. Eng., no. December 2016, pp. 2501–2510, 2008.
[4] Z. Dai, J. Ronholm, Y. Tian, B. Sethi, and X. Cao, J. Tissue Eng., vol. 7, no. May, 2016.
[5] A. K. Dillow, F. Dehghani, J. S. Hrkach, N. R. Foster, and R. Langer, Bacterial inactivation by using
near- and supercritical, Sci. York, vol. 96, no. August, pp. 10344–10348, 1999.
41
EIFS 2020 O04
Using Aluminum as reducing agent for the catalytic conversion of ammonia-based CO2 absorption derivatives
Juan I. del Ríoa,b, Eduardo Pereza, María Dolores Bermejoa, Ángel Martína,* a BioEcoUva. Research Institute on Bioeconomy. High Pressure Process Group. Department of Chemical Engineering and Environmental technology. Universidad de Valladolid, Valladolid,
47011, Spain, Spain b Grupo Procesos Químicos Industriales, Facultad de Ingeniería, Universidad de Antioquia
UdeA, calle 70 No.52-1, Medellín, Colombia * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT In spite of the importance that renewable energies have gained for the mitigation of the global warming, it can be foreseen that for many years it will still be necessary to use fossil fuels for the production of electricity and as fuel in the automotive industry [1]. The Carbon Capture, Storage and Utilization technologies (CCSU) are encouraged by the European Union given them potential of significantly reduce the CO2 emissions of thermal plants and chemical industries such as the production of ammonia, hydrogen, steel and cement [2]. In this sense, Amine-Based Carbon Capture Technology is one of the most attractive solutions nowadays, but the high cost of the desorption step entails to consider further possibilities. To completely avoid this step, our proposal is to reduce CO2 captured in aqueous media as a carbamate without gaseous hydrogen, while catalytically convert it into useful formic acid. This can be achieved by the implementation of an
Ammonia-basedCO2 capture
process
Catalytic hydrogenation&
Aluminum-water splitting
FORMIC ACIDAqueous NH3
42
environmentally friendly and economical hydrogen production technology like Aluminum-water splitting.
In the present work, a performance comparison of the reduction of ammonium carbamate (AC), ammonium carbonate (ACA), ammonium bicarbonate (AB) was carried out, using Pd (5%) supported in activated carbon as catalyst, at 120 ºC and 250 ºC, in a stainless steel stirred reactor from Parr instruments, with autogenous pressure. Sodium bicarbonate was used as reference feedstock, given its wide use as carbon source in previous works. To determine the effect of the main variables in the reduction process, AC was selected as the starting material and experiments were performed varying temperature (80-300˚C), reacton time (0.5-5 h), Al:AC molar ratio (1.5-9), catalysts content (7.5-60 wt% with respect to carbamate), liquid filling (50-85% of the total volume of the vessel), while the initial concentration of aqueous ammonium carbamate was 0.5 M. The concentration of AC and FA were determined by means of HPLC (Waters, Alliance separation module e2695), using an Aminex 87H (Bio-Rad) column and RI detector (Waters, 2414 module). The results suggest that, as starting materials, AC and ACA are more reactive than AB and SB at a mild temperature of 120 ºC. The time positively affects the yield, reaching 27% after 4 h of reaction and tends to level off, but with the depletion of selectivity. The highest selectivity (72%) is achieved at 0.5 h, indicating that the FA is formed faster than other possible compounds. The temperature presents a maximum yield of 20% between 120-150˚C. With respect to catalyst ratio, it is possible to obtain a yield as high as 38% using 60% catalyst with respect to the initial weight of carbamate) with a high selectivity of 85%, and conversion of 44%. On the other hand, rising the Al:AC molar ratio above 3 does not produce relevant improvements in reaction performance. The liquid filling level plays a positive effect over the process as the final autogenic pressure increases. After catalyst and reductant reutilization cycles it was found that aluminum was consumed in a signifcant proportion between the first use and the first re-use, as the yield dropped from 22.7 to 9.5%, but it is not totally oxidized. Even up to the 5th re-use the reductant is not totally exhausted as the yield was 4.8%, indicating that hydrogen is being still produced but in a deficient amount. Results demonstrate that this technology allows obtaining value-added chemicals like formic acid, without separation, purification or compression in between the CO2 capture and CO2 conversion processes, while involving a safer and efficient way of producing hydrogen from aluminum.
ACKNOWLEDGEMENTS This project has been funded by Junta de Castilla y León through project VA248P18. Juan Ignacio del Río acknowledges Universidad de Valladolid for the predoctoral fellowship. M. Dolores Bermejo thanks MINECO for Ramon y Cajal position.
REFERENCES
[1] T. Covert, M. Greenstone, C.R. Knittel, Journal of Economic Perspectives, 30, 117-138, 2016.
[2] B. Llamas, B. Navarrete, F. Vega, E. Rodriguez, L.F. Mazadiego, Á. Cámara, P. Otero, Greenhouse Gases,1st Ed, InTech, Rijeka, Croatia, pp 81-115, 2016.
43
EIFS 2020 O05
Continuous fractionation of glycerol acetates.
Physicochemical properties glycerol acetates + CO2 mixtures at high pressure
Selva Pereda a,b*, Mariana Fortunatti-Montoyaa,b, Pablo E. Hegela,b
aDepartamento de Ingeniería Química, Universidad Nacional del Sur (UNS), Argentina. bPlanta Piloto de Ingeniería Química – PLAPIQUI (UNS-CONICET), Argentina.
GRAPHICAL ABSTRACT
ABSTRACT Glycerol acetates are high-added value biosurfactants that find applications in different industrial sectors. Previous studies show the supercritical CO2 technology has a great potential for the fractionation of these highly viscous, amphiphilic, and non-volatile products (mono, di, and triacetyl glycerol) according to the quality standards of the food and cosmetic industry [1-3]. A proper design of fractionation columns and their further scale-up to commercial scale requires a robust thermodynamic model for phase equilibrium and PVT predictions [4], as well as proper correlations for physical properties like viscosity to assess the mass transfer and estimate the height of theoretical stages [5]. Physiochemical properties of these multicomponent mixtures are difficult to predict due to the complex nature of this system [6]. Thus, in this work, we determine experimentally the density and viscosity of CO2 saturated glycerol acetates mixtures at different pressures (30 bar to 150 bar), temperatures (25 °C to 50 °C) and CO2 concentrations (30 mol % to 70 mol %). Operating conditions were selected based on phase equilibrium predictions with the GCA-EOS of a high-pressure fractionation column [2]. First, a variable volume equilibrium cell is used to measure bubble points and saturated liquid molar volumes of glycerol acetates + CO2 mixtures. Thereafter, a high-pressure falling ball type viscometer is used to determine the dynamic viscosity of saturated liquid mixtures in the same range of pressure, temperature and CO2 concentrations.
44
As it is well known, temperature and CO2 concentration has a significant effect on both density and viscosity measurements (Figure 1 and 2). The measured molar volumes are between 70 cm3/mol and 130 cm3/mol, while the viscosities are between 5 mPa.s and 20 mPa.S, according to CO2 concentration and temperature. Molar volume of saturated liquid mixtures increases slightly with temperature at a given CO2 concentration and it decays drastically with CO2 concentration at constant temperature (Figure 1). Viscosity of saturated liquid mixtures is significantly affected by both variables. The presence of CO2 in the liquid mixture reduces the viscosity and this effect is more evident at temperatures lower than CO2 critical temperature. Viscosity of the saturated glycerol acetates + CO2 liquid mixtures follows the relationship proposed by Litovitz et al [7], it decays exponentially with temperature wherever the CO2 concentration in the system.
Figure 1. Molar volume of glycerol acetates + CO2 saturated liquid mixtures. Effect of temperature and CO2 concentration.
Figure 2. Viscosity of glycerol acetates + CO2 saturated liquid mixtures. Effect of temperature and CO2 concentration.
ACKNOWLEDGEMENTS The authors acknowledge the financial support granted by Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET PIP 112 2015 010 856), Secretaría de Ciencia, Tecnología e Innovación Productiva (ANPCYT PICT 2016-0907), and Universidad Nacional del Sur (UNS PGI 24/M153).
REFERENCES
[1] M. Fortunatti-Montoya, F.A. Sánchez, P.E. Hegel, S. Pereda, The Journal of Supercritical Fluids, Vol. 132, 51-64, 2018.
[2] M. Fortunatti-Montoya, F.A. Sánchez, P.E., Hegel, S. Pereda, The Journal of Supercritical Fluids, Vo. 153, 104575, 2019.
[3] M. Rezayat, H. Ghaziaskar, The Journal of Supercritical Fluids, Vol. 55(3), 937-943, 2011.
[4] E.A. Brignole, S. Pereda, Phase equilibrium engineering (Vol. 3). Newnes, Supercritical Fluid Science and Technology Series. Ed (Erdogan Kiran). Elsevier, Amsterdam, The Netherlands, 2013.
[5] G. Brunner, The journal of supercritical fluids, Vol. 47(3), 574-582, 2009.
[6] B.E. Poling, J.M. Prausnitz, J.P. O'connell, The properties of gases and liquids (Vol. 5). New York: Mcgraw-hill, (2001).
[7] A. T. Litovitz, The Journal of Chemical Physics, Vol. 20(7), 1088-1089, 1952.
45
EIFS 2020 O06
Research (framework) approach to convey supercritical fluid extraction of agrofood and forestry byproducts from lab to
industrial exploitation
Marcelo M.R. de Meloa,*, J.A. Saraiva b, I. Portugala, C.M. Silvaa , a CICECO – Aveiro Institute of Materials, Department of Chemistry, University of Aveiro,
Campus Universitário de Santiago, 3810-193 Aveiro, Portugal. b QOPNA & LAQV-REQUIMTE, Department of Chemistry, University of Aveiro, 3810-193
Aveiro, Portugal. * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT Within the quest of implementing a sustainable platform for the fractionation of agrofood and forestry byproducts, supercritical fluid extraction (SFE) is a promising and expanding technology for the production of natural extracts [1-4]. The research field is marked by a high volume of new works being published every year, but in most of them there is weak interconnection to the technical and scientific challenges that must be addressed to maximize the chances that lab research can ultimately reach an industrial scale investment.
In this context, we propose a research framework for SFE comprising six progressive stages: preliminary extraction and characterization of extracts; experimental optimization of operating conditions; measurement of kinetic extraction curves; phenomenological modeling of these kinetic curves; scale-up studies, and techno-economic analysis of industrial processes. For each of these we identify goals and points of interest that can be targeted. In addition, we also exemplify the type of analytical tools (e.g., GC-MS, FTIR-ATR, HPLC) or modeling methods (e.g., response surface methodology, broken plus
46
intact cells model, cost of manufacturing) that can be advantageously employed to fulfill the research stage objectives.
The proposed framework has been applied up to 13 types of biomass matrices in our research group, being the strongest example the valorization of Eucalyptus globulus bark by SFE, for which we have completed the six stages, starting from a lab scale of 0.5 L up to a pilot scale of 80.0 L. This case is presented in detail in this work, starting with the preliminary chemical characterization where the presence of valuable triterpenic acids was confirmed in pure supercritical CO2 extracts in amounts up to 1800 mg kgbark−1 , to the latest step of designing an industrial SFE process encompassing 2 sets of 3 extractors (20 m3 each) plus support lines and equipment. In the latter, the techno-economic impacts of using pure CO2 or ethanol as cosolvent (up to 5 wt.%) are crossed with other important operating conditions like operating pressure (120-200 bar), temperature (40-60 ºC) or flow rate (6-12 g min−1) for key responses such as Total Yield, Productivity, Cost of Manufacturing and Process Energy, and relying on both experimental and predicted data. Examples of other important byproducts addressed in the last 10 years on some of the framework stages are spent coffee grounds, grape seeds, and Turkish oak cork, and equivalent demonstrations of research will be disclosed in the presentation.
Globally, the sequential approach under analysis has the industrial implementation in its horizon, and aims to guide the research on SFE that has such ambition. The proposed stages are not intended to be considered definitive, being possible to foresee the integration of additional research steps for goals not yet covered, such as the fractions/purification of the supercritical extracts, the life cycle assessment of the designed industrial processes, or the screening of bioactivity for the products resultant from SFE processes. However, these typologies are still to become reality in the SFE research field, and thus cannot be presently considered as important as the six ones identified in this work.
ACKNOWLEDGEMENTS This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, FCT Ref. UID/CTM/50011/2019, financed by national funds through the FCT/MCTES. Authors want to thank the funding from Project AgroForWealth (CENTRO-01-0145-FEDER-000001), funded by Centro2020, through FEDER and PT2020.
REFERENCES
[1] M.M.R. Melo, A.J.D. Silvestre, C.M. Silva. Journal of Supercritical Fluids 92 (2014) 115-176.
[2] M.M.R. de Melo, I. Portugal, A.J.D. Silvestre, C.M. Silva, in: F. Pena-Pereira, M. Tobiszewski (Eds.), The Application of Green Solvents in Separation Processes, 1st Ed., Elsevier, Oxford, UK, pp. 325-348, 2017.
[3] G. Brunner, Annual Review of Chemicaland Biomolecular Engineering 1 (2010) 321–342.
[4] J. King, Annu. Rev. Food Sci. Technol. 5 (2014) 215–38.
47
EIFS 2020 O07
Fish waste valorization though a biorefinery approach
Rodrigo Melgosaa,*, Liliana Rodriguesb, Alexandre Paivaa, Pedro Simõesa, Esther
Triguerosc, Maria Teresa Sanzc, Sagrario Beltránc a LAQV-REQUIMTE, Departamento de Química. Faculdade de Ciências e Tecnologia,
Universidade Nova de Lisboa, 2829-516 Caparica, Portugal b iBET-Instituto de Biologia Experimental e Tecnológica,
Av. República, Qta. do Marquês 2780-157 Oeiras, Portugal c Departamento de Bioctecnología y Ciencia de los Alimentos. Facultad de Ciencias,
Universidad de Burgos, Pza. Misael Bañuelos s/n 09001 Burgos, España
GRAPHICAL ABSTRACT
ABSTRACT Fish processing is estimated to generate wastes equivalent to 20-75 %(w/w) of the starting raw material depending on the level of processing and type of fish [1]. To date, fish waste/byproducts are considered low value and disposed of by burning or discarding in the land or sea or used to produce fish silage, fertilizer and animal feeds [2]. Fish oil valorization through a biorefinery approach uses green solvents such as supercritical CO2 (SCCO2) and subcritical water (sCW) in order to recover valuable bioactive compounds from fish waste matrix.
In the work presented, two consecutive extractions have been performed. Firstly, raw sardine waste has been extracted with SCCO2, recovering a lipid-enriched fraction with high content in omega-3 polyunsaturated fatty acids that have applications in the nutraceutical and pharmaceutic fields [1]. Afterwards, the raffinate consisting of deoiled sardine waste has been submitted to sCW hydrolysis and extraction, obtaining fish protein hydrolysates (FPHs) composed by bioactive peptides and aminoacids, which might be of interest for food, pharmaceutical, and cosmetic applications [1].
Supercritical fluid extraction (SFE) with SCCO2 was carried out at 25 MPa and 40 ºC, in order to avoid thermal deterioration of bioactive compounds. Average extraction yield
48
was 25.5 ± 0.5 g/100 g sardine waste, accounting for ca. 94 % of Soxhlet-extractable oil with hexane at its boiling temperature. Fatty acid profile of the extract, obtained by gas chromatography [3] detected important quantities of omega-3 PUFAs, especially docosahexaenoic acid (DHA) and eicosapentaenoic acid (EPA).
Hydrolysis and extraction of the protein fraction contained in the deoiled sardine waste was performed at different temperatures, 90, 140, 190, and 250 ºC. Pressure was kept constant at 10 MPa in order to maintain water in its liquid state. Total and compound-specific accumulated extraction yield is showed in Fig. 1. Approximately, 60 g of extract per 100 g deoiled sardine waste were obtained. Highest protein concentration, measured through modified Lowry analysis [4], was observed at 140 and 190 ºC, with 90.3 and 89.5 % wt. (dry basis), respectively. Ash content was the main impurity of FPH extracts obtained at 90 ºC (up to 25 %wt.), especially Na and K-based soluble salts according to atomic emission spectroscopy. In the case of the FPHs obtained at 250 ºC, protein content decreased (84.8 %wt.). Decomposition of aminoacids into other products such as simpler aminoacids and organic acids have likely occurred due to high temperature and hydrolytic conditions.
Antioxidant activity of FPH extracts obtained at 140 and 190 ºC was evaluated through DPPH radical scavenging activity. Cytotoxicity and antiproliferative activity assays were also carried out in Caco-2 and HT-29 cell lines, respectively.
Figure 1. Left axis : Accumulated extraction yield of sCW experiments with deoiled sardine waste.
Right axis : temperature profile during sCW extraction.
ACKNOWLEDGEMENTS This work was supported by the Associate Laboratory for Green Chemistry- LAQV which is financed by national funds from FCT/MCTES (UID/QUI/50006/2019) and project PTDC/ASP-PES/28399/2017.
REFERENCES [1] A. Ghaly, V. Ramakrishnan, M. Brooks, S. Budge, D. Dave, J. Microb. Biochem. Technol. 5, 107-129, 2013.
[2] I.S. Arvanitoyannis, A. Kassaveti, Int. J. Food Sci. 43, 726-745, 2008.
[3] Association of Official Analytical Chemists, AOAC Official Method 2012.13, 2012.
[4] O.H. Lowry, N.J. Rosebrough, A.L. Farr, R.J. Randall, J. Biol. Chem. 193, 265-275, 1951.
49
EIFS 2020 O08
Process and simulation for the scCO2 extraction of bio-oil from a supercritical water ultra-fast hydrolysis of biomass
Emre Demirkaya*, Juan García-Serna and María José Cocero Alonso
High Pressure Processes Group, Bioeconomy Institute, Department of Chemical Engineering and Environmental Technology, University of Valladolid, Doctor Mergelina s/n, 47011,
Valladolid, Spain * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT In recent years, thermochemical processes have been one of the most preferred processes for lignocellulosic biomass fractionation and depolymerization in terms of product range, and high value chemicals and fuels. Hydrothermal liquefaction among these processes has a special interest since water is a green solvent, it is easy to control the process conditions, and it leads to high value products [1, 2]. There are vast amount of studies about the hydrothermal liquefaction of biomass and the main concern of these studies is to successfully convert biomass into small range of compounds [2]. However, most of these processes operate in batch, causing undesirable condensation reactions of the monomers [3].
To overcome the undesirable reactions, we developed and studied a Sudden Expansion Micro-Reactor, controlling the reactions accurately in a millisecond scale window. A tubular reactor followed by an instantaneous cooling step (performed by sudden
50
decompression valves using Joule-Thompson effect) performs with very high efficiencies [3].
Lignin valorization is a big challenge because of the recalcitrant nature of lignin. In our previous works, we successfully converted lignin into aromatic monomers via ultrafast depolymerization in supercritical water. At the end of this process, we obtained a bio-oil product that has very high water content together with small amount of other chemical groups. Organic solvent extraction opens the possibility to separate solids, light oil and heavy oil fractions [3]. Nevertheless, it is crucial to create a path for industrial applications for a selective separation of bio-oil using other options.
The aromatic product mixture from the ultrafast lignin hydrolysis in supercritical water is a bio-oil that solubilized in a high-pH water. The main idea is to use supercritical CO2 to extract and fractionate (SCF). Due to lignin depolymerization environment, bio-oil products are in low concentration and present some solids [3].
For these reasons, it is important to focus first in the SCF extraction column to continue then with the adjustment of the process, as there is no previous work that was focused on this column specifically. Therefore, our proposal is to model the SCF column and the subsequent simple separator blocks to fractionate and separate bio-oil compounds from water and solids.
The lack of experimental phase equilibrium data of bio-oil compounds and the highly varied and complex nature of bio-oil is a challenge for SCF extraction modeling [2]. Hence, a novel extraction and separation concept is developed by using improved Peng-Robinson equation of state (PR-EOS) to investigate the vapor-liquid equilibrium data. The predictive model is used only for solute-solvent interactions, by assuming negligible solute-solute interactions since scCO2 is in excess. Our preliminary models show that the predictive VLE data is in acceptable agreement with the experimental VLE data of chemical compounds that exists in bio-oil. Our study will try to answer whether the simple binary data will be enough to understand the extraction process model or not. Aspen Plus process simulations using predicted binary data for supercritical CO2 extraction and simple purification steps will be presented.
ACKNOWLEDGEMENTS The authors wish to thank MINECO Ministerio de Ciencia, Innovación y Universidades and FEDER funds for the financial support of the CTQ2016-79777-R.
REFERENCES
[1] J. Zhu, X. Zhang, X. Pan, Sustainable Production of Fuels, Chemicals, and Fibers from Forest Biomass, Vol. 1067, American Chemical Society, Washington, DC, 2011.
[2] W. Maqbool, P. Hobson, K. Dunn, W. Doherty, Industrial & Engineering Chemistry Research, 56, 3129-3144, 2017.
[3] N. A. Fernandez, E. Perez, M. J. C. Alonso, Green Chemistry, 6, 1351-1360, 2019.
51
EIFS 2020 O09
Integrated microwave and supercritical carbon dioxide extraction processes for astaxanthin recovery from brown
crab residues
Ana N. Nunesa,b,*, Ana Rodaa,c, Luís F. Gouveiad, Naiara Fernándeza, Ana A. Matiasa aiBET, Instituto de Biologia Experimental e Tecnológica, Apartado 12, 2781-901 Oeiras,
Portugal bITQB, Instituto de Tecnologia Química e Biológica António Xavier, Universidade Nova de
Lisboa, Av. Da República 2780-157 Oeiras, Portugal cLAQV-REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia,
Universidade Nova de Lisboa, 2829-516, Caparica, Portugal diMed.ULisboa, Research Institute for Medicines, Faculty of Pharmacy, Universidade de
Lisboa, Av. Professor Gama Pinto 1649-003 Lisboa, Portugal * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT Crustacean processing industry has expanded significantly during the past decades, generating a large amount of biowaste [1, 2]. The exploitation of byproducts contributes to minimize the ecological impact that the residues may cause [3]. In particular, brown crab (Cancer pagurus) is a notable source of astaxanthin [4], a carotenoid with strong antioxidant activity that has been reported to have beneficial effects on human health [5].
52
The objective of this work is focused on the optimization of an efficient and green methodology for the recovery of carotenoids, namely astaxanthin, from marine crustacean waste streams. Thus, a two steps procedure is proposed, integrating microwave pretreatment (MW) with supercritical CO2 extraction (SFE).
MW pretreatment of crab residues was optimized followed by conventional solid-liquid extraction with ethanol. The residues were initially pretreated by MW radiation with different amount of water (0-50%, v/v) and temperatures (80-120 ºC). SFE was performed using ethanol as co-solvent and process conditions, namely pressure (20-50 MPa), temperature (40-60 °C), amount of co-solvent (8-13%, w/w) and equilibrium time (0-30 min), were varied. By selecting the most favorable operating conditions for each process, MW and SFE, global extraction yield was increased. Also, astaxanthin extraction boost was remarkable. Moreover, its content in the final dry product was higher than the ones obtained for SFE alone. From the results it can be concluded that integrated MW and SFE processes can be considered as a good alternative to traditional solid-liquid extraction methods that require the use of organic solvents. With this extraction approach, not only marine crustacean waste streams have been valorized, but also a high added value natural ingredient has been isolated, allowing the subsequent use in nutraceutical formulations and functional food. ACKNOWLEDGEMENTS The authors acknowledge the financial support received from the Portuguese Fundação para a Ciência e Tecnologia (FCT) through the POCI-01-0145-FEDER-016403 project. iNOVA4Health – ID/Multi/04462/2013, a program financially supported by FCT/Ministério da Educação e Ciência through national funds and co-funded by FEDER under the PT2020 Partnership Agreement is also acknowledged. Ana A. Matias thank FCT for the financial support through the IF Starting Grant – GRAPHYT (IF/00723/2014), respectively. The authors are grateful to Tejo Ribeirinho, Lda for providing the crab shell wastes.
REFERENCES
[1] FAO, Food and Agriculture Organization of the United Nations, The State of World Fisheries and Aquaculture, 2014.
[2] I. Hamed, F. Özogul, J.M. Regenstein, Trends Food Science Technology, 48, 40–50, 2016.
[3] F. Özogul, I. Hamed, Y. Özogul, J.M. Regenstein, Encyclopedia of Food Chemistry, 33-38, 2019.
[4] C. Pires, A. Marques, M.L. Carvalho, I. Batista, Poultry, Fisheries & Wildlife Sciences, 5, 1-6, 2017.
[5] R.R. Ambati, P.S. Moi, S. Ravi, R.G. Aswathanarayana, Marine Drugs 12, 128–152, 2014.
53
EIFS 2020 O10
Recovery of proteins and free amino acids from Gelidium sesquipedale alga residue by subcritical water extraction (SWE)
Esther Triguerosa,*, Patricia Alonso-Riaño, María Teresa Sanz, Cipriano Ramos Rodríguez, Óscar Benito-Román, Sagrario Beltrán
aUniversity of Burgos, Biotechnology and Food Science Dept., Chemical Engineering Division, Pza. Misael Bañuelos s/n, 09001, Burgos (Spain)
GRAPHICAL ABSTRACT
ABSTRACT
Gelidium sesquipedale is a red alga that provides the best raw material to obtain the highest quality agar in the spanish agar industry [1]. Industrial process generates a residue that is usually discarded; however, this by-product still contains important amounts of different valuable compounds, such as structural carbohydrates, bioactive compounds and proteins. To valorize by-product supplied by Hispanagar company (Burgos), subcritical water extraction (SWE) is a promising green technology since water presents unique properties as solvent [2]. This work is focused on the valorization of the protein fraction to produce free amino acids and to extract and hydrolyze protein into small peptides. A semi-continuous reactor has been used to perform the extraction, and protein fraction hydrolysis was studied at different temperatures (125, 140, 155, 170, 185, 200ºC), times, and solvent flow rate (2 and 6 mL/min). Total protein content in alga residue was 20.11±1.53% in which it was determined free amino acids, among which VAL, LEU, ILE, PHE, LYS and HIS are majority (Table 1), being total essential amino acids found 10.50±0.16%, whereas non-essential amino acids like GLY, PRO and GLU+GLN represent 4.57±0.06%
Table 1. Amino acid content from alga residue and subcritical water extraction yields at 185ºC and 2ml/min (*essential amino acis).
amino acid alanine glycine valine leucine isoleucine threonine serine prolineaspartic acid + asparagine methionine
glutamic acid + glutamine phenylalanine lysine histidine tyrosine
code ALA GLY VAL* LEU* ILE* THR* SER PRO ASP+ASN* MET* GLU+GLN* PHE* LYS* HIS* TYR
Alga residue (mg/g dry) 6,0 7,2 22,4 17,4 17,3 3,5 3,4 10,2 7,1 2,6 4,3 19,0 12,9 9,9 6,6
SWE yield (%) 185°C - 2ml/min 24,2 29,4 6,4 4,6 3,6 6,2 21,8 7,6 30,3 10,6 12,2 3,3 4,7 4,9 10,6
standard deviation 0,2
54
Protein extraction grows with increasing temperature at constant flow, reaching a maximum at 200ºC. Moreover, when flow and temperature are increased, protein recovery shows the highest and fastest extraction because of its less residence time, what makes able to get a marked extraction yield improvement (Fig. 1). Amino acids extraction follows a
similar trend than proteins: an increasing extraction up to a maximum at 185ºC when flow rate is 2 ml/min, but lower than 6 ml/min. Greatest extraction was found for ALA, GLY, SER and the mixture of ASN+ASP; also for MET, TYR and GLU+GLN mixture, with lower but remarkable yield (Table 1). At constant flow rate, maximum extraction is reached at 185ºC for all amino acids determined, decreasing at 200ºC. Nevertheless, flow rate increasing makes 200ºC extraction much higher, about all for GLU+GLN mixture, LYS, HIS, TYR, PRO, LEU and MET (Fig. 2). This agrees with other studies carried out with fish protein and amino acids standard [3,4]. Moreover, it has been noted than amino acids extraction presents a similar behaviour according to its properties: basic amino acids extraction remains practically constant, whereas than neutral and acid, hydrophobic and sulfur amino acids extraction increase when temperature raises.
Figure 2. Amino acids extraction at different temperatures and flow rate.
(linked points = 2ml/min; non-linked points = 6ml/min flow rate).
SWE is a useful technique to extract bioactive compounds. Parameters as temperature or solvent flow rate have much influence on the protein and amino acids extraction yield. All of this makes SWE an interesting alternative to conventional treatments.
ACKNOWLEDGEMENTS To JCyL and ERDF for financial support of project BU301P18. To Hiperbaric, S.A. for financial support of Project BIOLIGNO. To JCyL and ESF for the predoctoral contracts of E. Trigueros and P. Alonso-Riaño and for the contracts of D. Benito-Bedoya and D.M. Aymara-Caiza through the YEI program..
REFERENCES [1] C. Fernández, Scientia Marina, 163, 1991. [2] C. Turner, E. Ibáñez, Contemporary Food Engineering Series, 8, 223-254, 2011. [3] Z. Xian, Z. Chao, Z. Liang, C. Hongbin, Chinese Journal of Chemical Engineering, 16(3), 456-460, 2008. [4] N. Sato, AT. Quitain, K. Kang, H. Daimon, Industrial and Engineering Chemistry, 43, 3217-3222, 2004.
25
50
75
100
125
150
175
50 100 150 200 250
Prot
ein
(mg/
g dr
y al
ga)
Time (min)
200°C - 6ml/min200°C - 2ml/min185°C170°C155°C140°C125°C
Figure 2. Total protein (mg/g dry alga) obtained by SWE at different times by using different temperatures and solvent flow rate.
55
EIFS 2020 O11
Simultaneous extraction and purification of fucoxanthin from Tisochrysis lutea microalgae
Charles Tardiff, Rocío Gallegoa,*, L. Celina Parreirab, Tiago Guerrab, Elena Ibáñeza, Miguel Herreroa
a Laboratory of Foodomics, Institute of Food Science Research (CIAL, CSIC), Nicolas Cabrera 9, Madrid 28049, Spain.
b A4F – Algae for Future, Campus do Lumiar, Estrada do Paço do Lumiar, Edif. E, R/C, 1649-038 Lisboa, Portugal.
GRAPHICAL ABSTRACT
ABSTRACT The marine microalga Tisochrysis lutea, a Haptophyta with a thin cell wall and currently used mainly in aquaculture, is a potential source of several bioactive compounds of interest. Indeed, T. lutea is rich in polyunsaturated fatty acids (PUFA), mainly docosahexaenoic acid (DHA) and carotenoids such as fucoxanthin. In the present study, the extraction of fucoxanthin from T. lutea was carried out using pressurized fluid extraction (PLE), an advanced and environmentally friendly technique widely employed for the recovery of bioactive compounds from different sources. An experimental design employing green solvents such as ethanol and ethyl acetate was applied for the selection of the optimum extraction conditions. Percentage of ethanol in the solvent mixture (0–100 %), temperature (40-150 ºC) and number of static extraction cycles (1-3) were chosen
56
as experimental factors. The maximum recovery of fucoxanthin was achieved with pure ethyl acetate at 40°C using one extraction cycle. Once the optimum extraction conditions were confirmed, the use of in-cell purification strategies using different adsorbents was studied in order to obtain fucoxanthin-enriched extracts. Activated charcoal showed a potential retention of chlorophylls allowing an effective purification of fucoxanthin in the obtained extracts. Chemical characterization of extracts was carried out by reversed-phase high-performance liquid chromatography with diode array detection (RP-HPLC-DAD). In conclusion, a selective fractionation of high valuable compounds was achieved using the proposed green downstream platform based on the use of compressed fluids. ACKNOWLEDGEMENTS Authors thank projects ABACUS (Algae for a Biomass Applied to the production of added value compounds, grant agreement No 745668, funded by the Bio Based Industries Joint Undertaking under the European Union’s Horizon 2020 research and innovation programme), AGL2017-89417-R (MINECO, Spain) and ILINK+1096 (CSIC, Spain) for financial support.
57
EIFS 2020 O12
Safety in Supercritical Extraction Plants
Joao Fernandes*, Martin Sova, Eduard Lack NATEX Prozesstechnologie GesmbH, Werkstrasse 7, 2630 Ternitz, Austria
GRAPHICAL ABSTRACT
ABSTRACT The operation of a supercritical extraction plant does entail important hazards [1]. These hazards must be taken into account both for equipment design and construction and for operation and maintenance. Safety considerations must influence any technical choice and operation and, for any case, a detailed analysis of potential hazards must be specifically conducted.
Considerations will be made on safety of plant design and safety in plant operation, pressure ranges and their design and selection or critical aspects in plant construction [2].
Moreover it will be discussed the use of safety valves and rupture disks, interlocking systems, controls and computerized systems, Hazard and Operability Analysis (HAZOP) [3] applied to supercritical extraction plants. REFERENCES
[1] M. Perrut, High Pressure Chemical Engineering, , Edts. P. R. von Rohr & C. Trepp, Elsevier, 1996, p. 627-631.
58
[2] E. Lack, E. Seidlitz, High Pressure Process Technology: Fundamentals and Applications, Ind. Chem. Lib., Elsevier, Vol. 9, pp. 430-435
[3] A. Rosenthal, Safe Design of a Supercritical Extraction System for the Extraction of Drilling Fluid from Drill Cuttings, Thesis, Guelph, Ontario, 2012.
59
EIFS 2020 O13
Aerogels made of graphene oxide and magnetic nanoparticles
for MRI applications
Alejandro Borrás, Ana M. López-Periago, Julio Fraile, Concepción Domingo* Materials Science Institute of Barcelona (ICMAB-CSIC), Campus UAB s/n, Bellaterra, 08193,
Spain *[email protected]
GRAPHICAL ABSTRACT
ABSTRACT
Nanocomposites are fascinating materials that has gained everincreasing interest from the scientific community due to the additional advantegeous and often synergistic properties of the components combination. Among them, hybridization of two-dimensional (2D) materials, like graphene of graphene oxide (GO), has been presented as one of the most interesting modes to prepare nanocomposites. Particularly, the integration of superparamagnetic iron oxide NPs, like magnetite (Fe3O4) and GO into nanocomposites is currently a hot topic of research in the areas of pollutants removal and biomedicine [1]. Fe3O4@GO composites can be prepared by both in situ and ex situ methods [2]. In the in situ techniques, the NPs are synthetized in the presence of GO flakes, e.g., by chemical deposition from solutions of Fe3+ and Fe2+ in basic media, or by hydrothermal reduction of Fe3+ salts. Contrarily, in the ex situ protocols pre-made NPs are attached onto the GO flakes. The straight assembly of pre-formed Fe3O4 NPs on GO surface was the method chosen in this work to synthetize the magnetic nanocomposites. The use of the ex situ procedure circumvent the common disadvantage of NPs uncontroled aggregation. Efforts have not only focused on methods to form the 2D nanocomposite, but also on simultaneously processing the material into a 3D user-friendly configuration, precisely,
60
in the form of a highly porous aerogel. to avoid GO reduction, a low temperature supercritical CO2 (scCO2) method was used for aerogel composite preparation [3].
A simple method to efficiently decorate GO sheets with monodispersed Fe3O4 NPs has been developed. As shown in the Scheme, this is readly achieved by first preparing monodispersed Fe3O4 NPs (a) and GO (b) suspensions in ethanol. After mixing, the NPs are homogeneously deposited onto the GO surface during the self-assembly of the graphene flakes into a gel (c). Alcogel formation is induced by the addition of scCO2, an acid gas. A dry composite, in the form of a black aerogel monolith (d), is obtained after isothermal depressurization. Note that, in the used procedure, GO flakes are keep dispersed during all the process including the drying step, thus facilitating the homogeneous distribution of the NPS on the composite surface and reducing the number of NPs encapsulated between layers. Additionally, in contarst to the high-temperature (ethanol) critical point drying procedure commonly used for aerogels preparation, the scCO2 method uses temperatures about 100 K lower, which prevents the removal of the oxygenated functionalieties on the GO structure. The as-made composite aerogel is magnetic and can be lifted by a magnet even when divided by a glass wall (e). Re-dispresion of this monoliths in water is easily achieved, reflecting the hydrophylicity of the Fe3O4@GO composite (f). The re-dispersed composite can still be easily manipulated by an external magnetic field (g).
Magnetic resonance imaging (MRI) labelling with Fe3O4 NPs and biocompatible Fe3O4 composites is a powerful technique for evaluation of the location and distribution of malignant cells. Recently, it has been demonstrated that the superparamagnetic Fe3O4@GO composite can also be used as the T2-weighted magnetic resonance contrast agent for cell labeling [4]. The performed study also investigates the Fe3O4@GO aerogel composites as potential image contrast enhancing materials in MRI, with enphasis in the significance of the arrangement of the NPs into clusters on the GO surface and the water stability/dispersability. ACKNOWLEDGEMENTS
Spanish National Plan of Research CTQ2017-83632 and Severo Ochoa Program for Centers of Excellence in R&D (SEV-2015-0496). REFERENCES
[1] V. Chabot, D. Higgins, A. Yu, X. Xiao, Z. Chen, J. Zhang, Energy Environ. Sci. 7 (2014) 1564-1575
[2] X. Yang, X. Zhang, Y. Ma, Y. Huang, Y. Wang, Y. Chen, J. Mater. Chem., 2009, 19, 2710–2714.
[3] A. Borras, G. Gonzalves, G. Marban, S. Sandoval, S, Pinto, P.A.A.P. Marques, J. Fraile, G. Tobias, A.M. Lopez-Periago, C. Domingo, Chem. Eur. J. 2018, 24, 15903 – 15911
[4] W. Chen, P. Yi, Y. Zhang, L. Zhang, Z. Deng, Z. Zhang, ACS Appl. Matre. Interf. 3 (2011) 4085-4091.
61
EIFS 2020 O14
Innovative Strategies for the Decellularization of trabecular bone using supercritical CO2 and Tri(n-butyl) phosphate
Marta M. Duartea, Nilza Ribeiroa, Inês V. Silvaa, Juliana R. Diasb, Nuno M. Alvesb, Ana
L. Oliveiraa,* a CBQF – Centro de Biotecnologia e Química Fina, Laboratório Associado, Escola Superior de
Biotecnologia, Universidade Católica Portuguesa, 4200-375 Porto, Portugal b CDRSP – Centre for Rapid and Sustainable Product Development, Polytechnic of Leiria,
2430-028 Marinha Grande, Portugal * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT Decellularization is a process that focuses on the removal of immunogenic cellular material from a tissue or organ. It has become an appealing methodology for the creation of functional and bioactive scaffolds to be implanted with the purpose of restoring of normal tissue function. Several scaffolds deriving from decellularized tissues and organs have been used with varying degrees of success for human clinical applications [1,2].
The present work proposes new methodologies for the decellularization of biological tissues in order to preserve, in the best way possible, its properties. For this purpose, the effectiveness of three different decellularization protocols for porcine trabecular bone tissue was investigated using Tri(n-butyl) phosphate (TnBP), supercritical carbon dioxide (scCO2) and, for the first time, a combination of both. TnBP is herein proposed as an alternative decellularization agent to harsh chemicals such as detergents, since it has been reported to better preserve the extracellular matrix (ECM), leading to better biological and mechanical properties of the resulting scaffold [2]. On the other hand, the use of supercritical CO2 is expected to lead to accelerate the decellularization process [3,4], not only reducing the period in which the tissues are exposed to potentially harmful agents,
62
but also resulting in lower costs for the process. scCO2 technology has recently risen as an important sterilization technique [5] due to its appealing properties (inexpensive, low pressure and temperature of operation and non-toxic).
Fresh samples of trabecular bone were here used as a challenging model for testing our proposed decellularization strategies. Trabecular bone samples were extracted from the distal ends of porcine femurs and cut into Ø6x3 mm cylinders, followed by a preliminary cell lysis procedure through 6 cycles of freezing with liquid nitrogen (-196ºC) and melting (room temperature). Three different protocols were implemented: immersion in 1% (v/v) TnBP aqueous solution with agitation, during 48 hours; scCO2 treatment, in a batch mode reactor at 40ºC and 240 bar, for periods of 1 and 3 hours, and scCO2 treatment with 0.1% (w/v) TnBP, in a batch mode reactor at 40ºC and 240 bar for periods of 1 and 3 hours. Due to the innovative nature of this work, time variants to protocols were implemented to investigate any possible harmful effects caused by prolonged exposure to scCO2 treatment. The samples’ structure and morphology were characterized using µ-CT and SEM imaging. Mechanical properties of samples were analyzed using via uniaxial compression testing. Decellularization efficiency was evaluated via hematoxylin–eosin (H&E) staining and DNA quantification.
The results revealed that both TnBP and scCO2 were able to extract the DNA content from the scaffolds, being this effect more pronounced in treatments that used TnBP as a co-solvent. Mechanical analysis of TnBP-treated samples revealed a general increase of the ultimate strength and yield strain, suggesting some degree of crosslinking of collagen fibers occurred. Meanwhile, the use of scCO2 led to dehydration of samples, increasing values for Young’s modulus and ultimate strength. The combined protocol of scCO2-TnBP resulted in a decrease in DNA content to about half of that measured for untreated samples, demonstrating the potential of this methodology and opening new possibilities for future optimizations to achieve the required decellularization levels. ACKNOWLEDGEMENTS This work was supported by National Funds from FCT - Fundação para a Ciência e a Tecnologia through project UID/Multi/50016/2013, UID/Multi/04044/2019 and ROTEIRO/0328/2013-nº 022158). The authors also acknowledge Interreg V-A POCTEP Programme through FEDER funds from the European Union (0245_IBEROS_1_E).C.A. and "Biotherapies- Bioengineered Therapies for Infectious Diseases and Tissue Regeneration" (NORTE-01-0145-FEDER-000012). This work was also supported by the European Union through PT2020 and Centro2020 (CENTRO-01-0145-FEDER-000014). REFERENCES [1] M. Parmaksiz, A. Dogan, S. Odabas, A. Elçin, Y Elçin, Biomedical Materials, 11(2), 022003, 2016.
[2] P. Crapo, T. Gilbert, S. Badylak, Biomaterials, 32(12), 3233–3243, 2011.
[3] D. Casali, R. Handleton, T. Shazly, M. Matthews, Journal of Supercritical Fluids, 131, 72-81, 2018
[4] S. Guler, B. Aslan, P. Hosseinian, H. Aydin, Tissue Engineering Part C: Methods, 23(9), 540-547, 2017.
[5] G. Soares, D. Learmonth, M. Vallejo, S. Davila, P. González, R. Sousa, A. Oliveira, Materials Science
& Engineering C, 99, 520-540, 2019.
63
EIFS 2020 O15
Supercritical fluid technology as a key enabling technology in AERoGELS and GREENERING COST Actions
Carlos A. García-Gonzáleza,*, Mónica Pérez-Caberob, Ana R. Duartec, **
a Department of Pharmacology, Pharmacy and Pharmaceutical Technology, I+D Farma group (GI-1645), Faculty of Pharmacy, Agrupación Estratégica de Materiales (AeMAT) and Health
Research Institute of Santiago de Compostela (IDIS), Universidade de Santiago de Compostela, E-15782 Santiago de Compostela, Spain
b COST Association, Avenue Louise 149, 1050 Brussels, Belgium c LAQV-REQUIMTE, Chemistry Department, Faculty of Science and Technology, Nova
University of Lisbon, 2829-516 Caparica,Portugal * [email protected]; ** [email protected]
GRAPHICAL ABSTRACT
ABSTRACT COST (European Cooperation in Science and Technology) is a funding agency for research and innovation networks, the so-called Actions [1]. COST Actions help connect research initiatives across Europe and beyond as well as to enable scientists to grow their ideas by sharing them with their peers and take new initiatives across all fields of science and technology, while promoting multi‐ and interdisciplinary approaches. COST Actions involve more than 45,000 researchers and innovators and are described as Open and Inclusive, Multi and interdisciplinary, Pan-European and Career enhancing.
Supercritical fluid technology represents a key enabling technology for certain fields since it may be either the only technological option to obtain the required material specifications, or the most effective and environmentally friendly processing alternative for certain uses. In this work, two COST Actions (CA18125 –AERoGELS, Advanced Engineering and Research of aeroGels for Environment and Life Sciences– [2], and
64
CA18224 –GREENERING, Green Chemical Engineering Network towards upscaling sustainable processes– [3]) with supercritical fluid technology as a topic of utmost concern in their scope are presented.
Aerogels are a special class of mesoporous materials with very high porosity and tunable physicochemical properties, and usually obtained by supercritical fluid-assisted drying of gels. AERoGELS COST Action intends to bring together the knowledge on research and technology of aerogels at the European level from academia, industry and regulatory experts [2]. In AERoGELS Action, the use of aerogels specifically for environmental and life sciences applications is explored. The scope of AERoGELS Action is to advance the state‐of‐ the art on the topic by joining the knowledge and efforts of the most renowned experts on cutting‐ edge aerogel technology, on advanced characterization of materials as well as on biomedical and environmental research. AERoGELS Action will set a forum to disseminate knowledge to society, to boost the industry‐academia interactions and to train European young researchers on research, innovation and entrepreneurial skills via technical schools, publications and short-term research stay (STSM) exchanges.
GREENERING COST Action intends to promote Europe industrial leadership in which concerns the use of green technologies for the development of sustainable processes. To achieve this, the GREENERING consortium gathers experts from academia, industry and technology transfer institutions with the aim to: i) create a network with common interests; ii) create working groups to influence decision makers and stakeholders in adopting sustainable processes; iii) create competitive consortiums able to apply to H2020 competitive calls and iv) increase the entrepreneurial mindset of researchers and particularly young students who with their youth and willful energy will be able to transpose technology into products.
ACKNOWLEDGEMENTS Work carried out in the frame of the COST Actions CA18125 “Advanced Engineering and Research of aeroGels for Environment and Life Sciences” (AERoGELS) and CA18224 “Green Chemical Engineering Network towards upscaling sustainable processes” (GREENERING) and funded by the European Commission. Work supported by Xunta de Galicia [ED431F 2016/010 & ED431C 2016/008], MCIUN [RTI2018-094131-A-I00], Agrupación Estratégica de Materiales [AeMAT-BIOMEDCO2, ED431E 2018/08], Agencia Estatal de Investigación [AEI] and FEDER funds. C.A.G.-G. acknowledges to MINECO for a Ramón y Cajal Fellowship [RYC2014-15239].
REFERENCES
[1] COST Association website, https://www.cost.eu/
[2] CA18125 AERoGELS COST Action website, https://cost-aerogels.eu/
[3] CA18224 GREENERING COST Action website, https://www.cost.eu/actions/CA18224/ #tabs|Name:overview
65
EIFS 2020 O16
Encapsulation of 5-aminosalicylic in Eudragit® S-100 by
supercritical fluid extraction of emulsions
D. Vizcayaa, D.R. Serranob, D.F. Tiradoa, A. Cabañasc, L. Calvoa* a Department of Chemical and Materials Engineering, b Department of Galenic Pharmacy and
Food Technology, C Department of Physical Chemistry I Universidad Complutense de Madrid, 28040 Madrid, Spain.
GRAPHICAL ABSTRACT
ABSTRACT
5-Aminosalicylic acid (5-ASA) is a drug commonly employed in the treatment of inflammatory bowel disease (IBD). The targeting of 5-ASA in the intestine is challenging. This work aimed to produce a nanoparticle-based delivery system to enable the controlled release of 5-ASA preferentially in the colon, preventing adverse effects in the stomach, and improving patient compliance. Supercritical fluid extraction of emulsions (SFEE) was selected to manufacture these nanoparticles. This technique is based on the use of supercritical CO2 to rapidly extract the organic phase from an emulsion. The removal of the organic solvent provokes the precipitation of both the drug and the carrier, which were previously dissolved in. Solvent evaporation (SE), in which the organic phase is removed by heating, was also tested and the results were compared. Eudragit® S100 (EU S100), a pH-sensitive polymer based on methacrylic acid was employed as the carrier, and Tween 80 (T80), as the surfactant to produce the oil-in-water emulsions (O/W). Due to the hydrophilic nature of 5-ASA, it was necessary to use a mix of solvents as the organic phase. Acetone was used to dissolve the EU S100 and dimethyl
0
20
40
60
80
100
0 30 60 90 120 150 180 210 240
5-A
min
osal
icyl
ic r
elea
se (%
)
Time (min)
SFEE at 40 °C and 9 MPaSE at 45 °C and 0.03 MPaPentasa®
SIMULATED GASTRIC FLUID (pH 1.2)
SIMULATED INTESTINAL FLUID (pH 6.8)
66
sulfoxide (DMSO) to dissolve the polymer. Many initial formulations were tested, varying the ratio of the polymer and the drug, the surfactant concentration, and the agitation mode. In the most adequate one, the aqueous phase was formed by dissolving T80 (0.08 %) in water. The organic phase was formed by a mixture of acetone/DMSO (7:3 v/v) + 5-ASA (0.2 % in mass fraction) + the triple of EU S100. The W:O mass ratio was 80:20. To disperse the O phase on the continuous W phase, magnetic agitation at 600 rpm for 5 min was used. The formed emulsion had a droplet size of 80 nm. Then, 30 mL of this emulsion was subjected to SFEE in a 100 mL vessel where the CO2 was continuously micro-bubbled through a sparger. The operating conditions were: 9 MPa, 40 ºC, CO2 flow rate of 5 g/min, and 60 min. The obtained nanoparticles were compared with those formed by SE at 45 ºC and vacuum of 30 kPa for 45 min. They were characterized in terms of particle size distribution through DLS, morphology by TEM, encapsulation efficiency with HPLC and solvent residual content by elemental analysis. Smooth spherical nanoparticles were obtained, with narrow size distribution (span from 0.5 to 1) and sizes ranging from 84 nm to 75 nm, for SFEE and SE, respectively. This size was in both cases similar to the emulsion droplet. The particles also had a high encapsulation efficiency, being 84 % for SFEE and 98 % for SE. The advantage of SFEE vs SE relies on the possibility of continuous production in columns where the emulsion and the CO2 can be contacted counter-currently with recirculation of both the organic solvent and the CO2 in a simple and integrated process. Besides, as the DMSO boiling temperature is high (198 ºC), it was more difficult to remove it by evaporation; thus, the residual sulphur content in the SE particles was on average 21%, while it was < 4 % in the SFEE particles. Dissolution studies were performed to assess the drug release ability of the manufactured nanoparticles by SFEE and SE. Results were compared with, a commercially available formulation of 5-ASA at the same dose. A pronounced burst release at acidic pH was observed with both SFEE and SE nanoparticles compared to Pentasa® (see Figure in the Graphical Abstract), which can be linked to the higher surface area of the nanoparticles compared to commercial granules of several micrometres. Drying and tabletting of the manufactured nano-particles are proposed to minimise the burst effect in acid media. ACKNOWLEDGEMENTS This research was financed by the Spanish Ministry of Science and Innovation project: RTI2018-097230-B-I00.
67
EIFS 2020 O17
Surfactant-free CO2 based, microemulsion-like systems:
promising nanostructured liquids to gain control over anti-solvent precipitations
David Piñaa, b, Alessandro Trioloc, Andreas Siegfried Braeuerd, Nora Ventosaa, b, *
a Institut de Ciencia de Materials de Barcelona (ICMAB-CSIC) b Centro de Investigacion Biomedica en Red de Bioingenieria, Biomateriales y Nanomedicina
c Laboratorio Liquidi Ionici, Istituto di Struttura della Materia-CNR (ISM-CNR) d Technische Universität Bergakademie Freiberg (TUBAF)
GRAPHICAL ABSTRACT
ABSTRACT Microemulsions are thermodynamically stable systems formed by at least three components: a mixture of (1) a polar one, usually water, (2) a nonpolar one, usually oil, mediated by (3) an amphiphilic compound, normally a surfactant. They are macroscopically homogeneous, and isotropic. As they contain both polar and nonpolar domains, these ternary systems can be considered as universal solvents, and attract a large interest as template for material processing [1]. However, an important drawback of conventional microemulsions is the use of environmentally harmful surfactants and oils or organic solvents. Purification of these products affects the sustainability of microemulsions in terms of costs and environmental impact. In this context, it has been discovered that the addition of compressed CO2 (cCO2) to a mixture of a polar and a nonpolar solvent could yield microemulsion-like systems at some thermodynamic
68
conditions. These systems are surfactant-free and contain smaller amounts of conventional organic solvents compared to traditional microemulsions. Moreover, CO2 is low cost, nonflammable, environmentally benign, bio- and food-compatible, and naturally abundant.
Specifically, the exploration of the mixture “water/acetone/CO2” (WACO2) has led to the discovery of the existence of a structured liquid phase when the mixture is brought to P = 10 MPa and T = 308 K. Raman spectroscopy has indicated the presence of water-rich and water-lean nanodomains in this liquid. It should be pointed out that at these conditions, water and CO2 are not miscible while acetone is miscible with the other two. Therefore, the coexistence of these nanodomains is attributed to the presence of acetone, which could behave as a mediator between the non-miscible components [3]. Furthermore, it has been observed by Small Angle Neutron Scattering (SANS) that the nanostructure of this cCO2-based system can be tuned by changing the pressure [4]. This is convenient in terms of processability because pressure changes can be transmitted much faster and in a homogeneous way throughout all the mixture. This supposes an advantage compared to traditional microemulsions which can only be modified by changes in T and composition, properties which are transmitted much slower. In this sense, these systems are green, with easily tunable properties, high range of solubility and thermodynamic stability, which makes them appealing candidates to be used as ON/OFF nanoreactors for highly accurate molecular material processing.
In this way, these systems could be used as nanoreactor templates. Hydrophobic active organic molecules (AOMs) can be dissolved in the water-lean nanometric domains, when the mixture is in its nanostructured state (ON-mode) and by changing the conditions, the nanostructuration can be destroyed (OFF-mode) mixing the water-lean and the water-rich nanodomains, and causing the anti-solvent precipitation of AOMs in a reproducible and homogeneous way.
ACKNOWLEDGEMENTS
A.S.B. thanks funding from the European Research Council under ERC starting grant agreement no. 637654. The authors appreciate the economic support from DGI, MINECO, Spain (Grant MAT2016-80826-R and “ Severo Ochoa” Programme for Centres of Excellence in R&D (SEV- 2015-0496)), and the Instituto de Salud Carlos III, through “ Acciones CIBER”. The ICTS U6 of “Nanbiosis” for the performance of some experiments.
REFERENCES
[1] Microemulsions: Background, New Concepts, Applications, Perspectives, ed. C. Stubenrauch, Wiley, 2009..
[2] M. L. Klossek, D. Touraud, T. Zemb, W. Kunz, ChemPhysChem 2012, 13, 4116.
[3] P.E. Rojas, R.F. Hankel, M. Cano, S.Sala, J. Veciana, A. Bräuer, N. Ventosa, Chem. Commun., 2014, 50, 8215.
[4] N. Grimaldi, P. E. Rojas, S. Stehle, A. Cordoba, R. Schweins, S. Sala, S. Luelsdorf, D. Piña, J. Veciana, J. Faraudo, A. Triolo, A.S. Braeuer and N. Ventosa, ACS Nano, 2017, 11, 10774-10784.
69
EIFS 2020 O18
Analysis of the influence of different compounds and optimization of the supercritical epoxidation process of
grapeseed oil
Juan Cataláa,*, M. Teresa Garcíaa, Jesús M. García-Vargasa, M. Jesús Ramosa, Juan F. Rodrígueza
a Universidad de Castilla La Mancha, Ciudad Real, 13071, Spain * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT Polyurethanes (PUs) cover around 7.5% of European plastics converter demand [1], and are known to be a commodity polymer with a wide range of applications, such as coatings, adhesives, sealings and foams [2]. Nevertheless, PUs have a strong environmental and human health impact during their life cycle. Both of the PUs raw materials (a polyol and a monomer with isocyanate groups) are non-renewable petro-based resources. As isocyanates are being synthesized, phosgene, a lethal gas, is needed. Also, they have been classified as carcinogenic, mutagenic and reprotoxic [3]. All these implications make necessary the development of an alternative synthesis route.
Non-isocyanate polyurethanes (NIPUs) currently arise as an option whose synthesis procedure is based on the reaction between polycarbonates and polyfunctional. They have the advantage that polycarbonates can be obtained from renewable resources, such as unsaturated plant oils, through consecutive reactions of epoxidation of the double bonds present in the triglycerides and oxirane ring opening by means of the introduction of carbon dioxide into the molecule.
Castilla-La Mancha, a region located in central Spain, embraces one of the largest wine industry sectors in the world. As a result of its activity, approximately 100,000 tonnes of grape seeds are produced per year, with a content of oil near to 20 wt.% [4]. Its availability, relatively low price, high content in functionalizable unsaturated bonds, and the fact of being a sustainable resource make grapeseed oil an attractive choice as the backbone for the new chemical manufacturing.
70
With all these, the epoxidation of the oil becomes the first stage and that from which will derive the rest of processes that can lead to the obtaining of a clean polyurethane and respectful with the environment and the human health. In addition, an epoxy product can be used for multiple applications that differ from this, such as epoxy resins, painting, plasticizers or thermosets.
Usually the processes that have been used to prepare epoxidized vegetable oils are based on the Prileschajew reaction which consists on the substitution of an unsaturation by an oxirane ring caused by a percarboxylic acid (peracetic or performic) that is formed in situ [5]. Soluble mineral acids, commonly sulfuric acid, are used as catalysts for this reaction. Therefore, environmental concerns related to the handling of salts formed during the neutralization of the catalyst and technical and economic problems associated with corrosion and separation operations, expose the need of a substitute for this technology.
Carbon dioxide reacts with H2O to form carbonic acid, and by analogy, with hydrogen peroxide (H2O2), it is supposed form the corresponding peracid, named as peroxycarbonic acid [6]. This acid could replace traditional peracids as a cleaner alternative for the epoxidation of olefins.
Being so, not only CO2, but supercritical CO2 (scCO2) could be a great substitute for the common carboxylic acids used in Prileschajew reaction. Such claim is based on the properties of the supercritical fluids, with a density high enough to grant them a considering solvating power, also a lower viscosity and a molecular diffusivity significatively higher than the corresponding to the liquid phase, both of them related to the improvement of mass transfer. All these properties in addition to the non- explosiveness of the scCO2 make it a really attractive carrier in the epoxidation reaction process [7]. Finally, the use of the supercritical technology implies a main advantage consisting on the obtaining of a nearly pure epoxidized product, due to the ease separation of the scCO2 through a simple depressurization.
This work will focus on the study of the viability of the epoxidation reaction of grape seed oil in supercritical medium, as well as on the analysis of the influence of different compounds capable of affecting the development of the process and its operating conditions, always with the aim of optimizing the overall yield and obtaining the most suitable product possible.
ACKNOWLEDGEMENTS This research is being funded thanks to a project granted by the regional government of Castilla La Mancha.
REFERENCES [1] PlasticsEurope, Annual Report Plastics Europe, 2018. [2] R. Chen, C. Zhang, M. R. Kessler, Journal of applied polymer science, 132, 41213, 2014. [3] R.W. Kapp, Isocyanates, in: P.B.T.-E. of T. (Third E. Wexler (Ed.), Academic Press, Oxford, pp. 1112–1131, 2016. [4] J. de Haro Sánchez, I. Izarra Pérez, J. Rodríguez, Á. Pérez, M. Carmona, Journal of cleaner production, 138, 70-76, 2016. [5] A.F. Aguilera, P. Tolvanen, K. Eränen, J. Wärnå, S. Leveneur, T. Marchant, T. Salmi, Chem. Eng. Sci. 199, 426–438, 2019. [6] S.A. Nolen, J. Lu, J.S. Brown, P. Pollet, B.C. Eason, K.N. Griffith, R. Gläser, D. Bush, D.R. Lamb, C.L. Liotta, C.A. Eckert, G.F. Thiele, K.A. Bartels, Ind. Eng. Chem. Res. 41, 316–323, 2002. [7] S.M. Hitchen, J.R. Dean, Properties of supercritical fluids BT - Applications of Supercritical Fluids in Industrial Analysis, in: J.R. Dean (Ed.), Springer Netherlands, Dordrecht, pp. 1–11, 1993.
71
EIFS 2020 O19
Polyethylene glycol-drug conjugates by click chemistry in
scCO2
Sonia Lópeza*, María Teresa Garcíaa, Juan Francisco Rodrigueza, María Jesús Ramosa, Ignacio Graciaa.
aInstitute of Chemical and Environmental Technology (ITQUIMA), Department of Chemical Engineering, University of Castilla- La Mancha, Avda. Camilo José Cela 12, 13071 Ciudad
Real, España. * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT The field of natural products with an anticarcinogenic profile is currently being exploited with the aim of developing drugs to reduce side effects, as the clinical application of chemotherapy drugs is limited due to these effects. Natural coumarins or synthetic analogues, are of great interest due to their pharmacological properties. In this work focuses on the conjugation of a polymer, polyethylene glycol (PEG)[1], with a bioactive molecule, coumarin, by means of click chemistry[2].
However, was replaced the organics solvents commonly used for this reaction for supercritical carbon dioxide. Synthesis and characterization of PEG-Coumarin was successfully reported using FTIR, 1H NMR and MALDI TOF. Additionally, was carried out a statistical experimental study of the most important variables in supercritical media, pressure, temperature and load of catalyst with a 23 full factorial design with two central points [3,4].
THERAPEUTIC AGENT
PEG
AZIDE LIGAND
72
The purification of click conjugate was carried out due to this type of reaction require copper as a catalyst, which is the most discussed disadvantages of click chemistry is the associated potential toxicity. Column chromatography of alumina was used to remove the CuSO4·5H2O and in addition copper wire was used as heterogenous catalyst.
ACKNOWLEDGEMENTS We gratefully acknowledge funding from the Ministry of economy and competitiveness through funding the projects Ref. CTQ2016-79811-P. The authors also acknowledge the support of the Ministry of economy and competitiveness for the fellowship of Ms. López Quijorna Ref. BES-2017-079770. The authors state that they have not conflict of interest with any public or private body.
REFERENCES
[1] Ringsdorf, H., Journal of Polymer Science: Polymer Symposia, 1975. 51(1): p. 135-153.
[2] Zou, Y., et al., Journal of Controlled Release, 2018. 273: p. 160-179.
[3] Grignard, B., et al., The Journal of Supercritical Fluids, 2010. 53(1): p. 151-155.
[4] Grignard, B., et al., Green Chemistry, 2009. 11(10): p. 1525-1529.
73
EIFS 2020 O20
Green and smart polymer for anticancer delivery
Beatriz Monteiro, Raquel Viveiros, Teresa Casimiro*
CleanMIPTech group, LAQV-REQUIMTE, Chemistry Department, NOVA School of Sciences
and Technology, NOVA University of Lisbon, 2829-516 Caparica, Portugal
GRAPHICAL ABSTRACT
ABSTRACT
Drug delivery systems have been widely evaluated and have grown rapidly, in the last few decades [1]. In particular, biomimetic materials have shown to be very attractive agents, demonstrating the importance of inherent properties of efficiently delivering drugs to the targeted sites in biological systems [2].
Bioinspired materials have been developed by Molecular Imprinting Technique in supercritical CO2 technology, for several fields such as drug delivery, on-off sensors, separation, enrichment and purification [3], taking advantage of CO2 that is abundant, easily available in high purity, non-toxic, non-flammable and aprotic.
A novel smart molecularly imprinted polymer (MIP) based on N-isopropylacrylamide, itaconic acid and ethylene glycol dimethacrylate was developed as a potential body-friendly oral anticancer drug delivery system for natural phenols. MIP was synthesized using a molar ratio of template, monomers, crosslinker (T:M:C), 1:50:50, using supercritical carbon dioxide (scCO2) technology. Moreover, natural phenol was impregnated also in scCO2 environment. Polymers were characterized physical, chemical and morphologically. Imprinted polymer presented higher uptake ability to impregnate natural phenol. The water uptake measurements revealed that matrices swelled more at pH 2.2 than at 7.4. In vitro drug release experiments presented different release profiles at different pHs, where MIP could release higher amounts of curcumin at pH 2.2 than pH
74
7.4. Moreover, the experimental data was fitted using the empirical Korsmeyer-Peppas model.
ACKNOWLEDGEMENTS
The authors would like to thank the financial support from the Fundação para a Ciência e Tecnologia, Ministério da Ciência, Tecnologia e Ensino Superior (FCT/MCTES), Portugal, through project PTDC/EQU-EQU/32473/2017 and the Associate Laboratory Research Unit for Green Chemistry – Clean Technologies and Processes– LAQV-REQUIMTE is financed by national funds from FCT/MCTES (UID/QUI/50006/2019) and co-financed by the ERDF under the PT2020 Partnership Agreement (POCI-01-0145-FEDER – 007265).
REFERENCES
[1] S.A. Zaidi, Drug Delivery, 23, 2262–2271, 2016.
[2] P.K. Paul, A. Treetong, R. Suedee, Acta Pharmaceutica, 67, 149–168, 2017.
[3] https://sites.fct.unl.pt/clean-mip-tech/.
75
EIFS 2020 O21
Supercritical Antisolvent micronization of pharmaceutical
compounds
José P. Coelho.a, b*, Patricia Matosa, António M.F. Palavra.b, Rui Loureiroc, Beatriz P. Nobre,b
a CIEQB/ISEL - Instituto Politécnico de Lisboa, 1959-007 Lisboa, Portugal. b Centro de Química Estrutura, Instituto Superior Técnico, Universidade de Lisboa, Lisboa,
Portugal c Faculdade de Farmácia, Universidade de Lisboa, Lisboa, Portugal
GRAPHICAL ABSTRACT
ABSTRACT
Fusidic acid is a naturally occurring antibiotic with a molecular formula of C31H48O6. This antibiotic has a bacteriostatic action, inhibiting bacteria from replicate, and is used to treat both topical and systemic skin and eye infections caused by staphylococci and other gram-positive species. On the other hand, this compound is the most important antibiotic from the fusidane family and can be obtained from the fermentation broth of Fuzidium coccineum [1,2].
Particle size of active pharmaceutical ingredients can play a significant role in the amount of the active principle absorbed by the human body and with many compounds it is possible to provide dosages well below the toxicity threshold by increasing the
76
bioavailability [3]. Particle size of pharmaceutical ingredients to be used in ophthalmic ointments and solutions should range between 1 and 3 µm. Supercritical anti-solvent (SAS) micronization is considered one of the most suitable techniques for the precipitation of active pharmaceutical ingredients since it combines the high solvent power of supercritical fluids to dissolve the organic solvent and the low solubility of the pharmaceutical compounds in the supercritical fluids [4-6].
In this work the micronization of fusidic acid dissolved in acetone using the SAS micronization process was carried out. The effect of different conditions on the mean particle size was studied, using the design of experiments.
A fractional factorial design (FFD) was used for screening the most significant experimental parameters. Four factors were considered: the temperature, with values between 40 °C and 60 °C, the pressure, varied between 100 bar and 200 bar, concentration ranging between 10 mg/ml and 40 mg/ml and the solvent injection flow rate with values between 0.5 mL/min and 3 mL/min, being the mean particle size the response factor. The statistical analysis of FFD showed that temperature and flow rate were the significant factors of the process.
Moreover, Central Composite Design was used to perform the optimisation of the significant parameters, temperature and flow-rate that minimize the mean particle size. Optimisation estimated that the smallest mean particle size would be 0.223μm at the working conditions of 40 ºC, 100 bar, 40 mg/mL and 0.5 mL/min. The expected working conditions to obtain a mean particle size between 1 and 3 µm, were temperature ranging from 40 to 45 ºC and flow-rate from 0.560 to 2.552 mL/min, maintaining the pressure at 100bar and the concentration at 40 mg/mL. ACKNOWLEDGEMENTS
The authors thank Fundação para a Ciência e Tecnologia (FCT, Portugal) for the financial support through the funding UID/QUI/00100/2019.
REFERENCES
[1] I. Sotofte, T. Duvold, Acta Crystallographica, Section E57 (9), p.o829-831, 2001
[2] J. Turnidge, International Journal of Antimicrobial Agents, 12 (2), .S23-24, 1999.
[3] R. M. Atkinson, Nature,193, 588-589, 1962.
[4] B. Y. Shekunov, K. P. Yorge, J. Cryst. Growth, 211, 122- 136, 2000.
[5] P. M. Gallagher, M.P. Coffey, V. J. Krukonis, N. Klasutis, ACS Symposium Series, 406, 334-354, 1989.
[6] E. Reverchon, J. Supercrit. Fluids,15, 1-21, 1999.
77
EIFS 2020 O22
Formation of pharmaceutical solid solutions using
supercritical CO2 assisted processes Vivek Verma, Kevin M Ryan, Matteo Lusi,* Luis Padrela*
Synthesis and Solid State Pharmaceutical Centre, Bernal Institute, Department of Chemical Sciences, University of Limerick, Ireland, V94T9PX
*[email protected]; [email protected]; [email protected]
GRAPHICAL ABSTRACT
ABSTRACT Crystal engineering aims to design crystalline materials (single and multi-component) of APIs (Active Pharmaceutical Ingredients). In fact, chemical composition and structures affect physicochemical properties such as shape, and solubility of the crystals. Hence, the rational design of crystal structure allows controlling these physicochemical properties [1]. A solid solution, a multi-component crystalline material, originates upon co-crystallization of two or more structurally similar species that mutually substitute each other in the same structure and hence occupy equivalent crystallographic positions. The mutual substitution of isostructural molecules in the crystal lattice provides the opportunity to modify structural and physicochemical properties of solids including stoichiometry, in continuum [2]. Unfortunately, strict thermodynamic requirements limit the realisation of solid solutions.
Supercritical fluid (SCF) technologies have emerged as techniques that allow generating single and multi-component crystalline forms of APIs that are not reproducible by other techniques. SCF methods provide benefits over conventional precipitation methods in regards to generating high levels of supersaturation, polymorphic control, and particle
78
size control due to their ability to arrest the molecular configuration in milliseconds [3, 4]. Hence, the flash precipitation ability of supercritical CO2 techniques, which use either the anti-solvent or atomization enhancement properties of supercritical CO2, was applied to generate solid solutions of isostructural entities. To the best of our understanding, over the last 20 years there has been no work published in the literature addressing the production of solid solutions using SCF methods.
A complete series of solid solutions containing hydrocortisone, an anti-inflammatory drug, and cortisone, a prodrug of hydrocortisone were successfully prepared using a batch Gas anti-solvent (GAS) approach, which previous attempts to prepare the same solid solutions by conventional techniques (e.g. solvent evaporation, solid state grinding) had been unsuccessful. Indeed cortisone and hydrocortisone have a different H-bond capability and a different crystal structure. Despite such diversity, a solid solution was produced using GAS as a batch process and supercritical assisted spray drying (SASD) as a continuous process. The generation of solid solutions was confirmed using powder X-ray diffraction (PXRD) and ssNMR. The SASD process enabled the continuous production of solid solutions in the respective molar ratios without compromising the purity of solid solutions as obtained from the GAS process.
Furthermore, solid solutions obtained from the GAS process were subjected to dissolution studies. The dissolution of cortisone and hydrocortisone from solid solutions was similar to cortisone and hydrocortisone processed by GAS under the same experimental conditions, which suggests that the solid solutions retained the physicochemical properties of both molecular entities. Therefore, supercritical CO2 processes provide novel and effective approaches to generate solid solutions of isostructural molecules with patient friendly dosage form.
ACKNOWLEDGEMENTS This work was undertaken as part of the SSPC Research Centre supported by the Science Foundation Ireland (SFI) and was cofunded under the European Regional Development Fund (Grant SFI SSPC2 12/RC/2275). The authors also acknowledge Enterprise Ireland for the Grant CF2017-0754-P.
REFERENCES [1] M. Lusi, Crystal Growth & Design, 18(6), 3704-3712, 2018.
[2] M. Lusi, CrysEngComm, 20, 7042-7052, 2018.
[3] L. Padrela, J. Zeglinski and K. M. Ryan, Crystal Growth & Design, 17(9), 4544-4553, 2017.
[4] B. Long, G. Walker, K. M. Ryan, L. Padrela, Crystal Growth & Design, 19(7), 3755-3767, 2019
79
EIFS 2020 O23
Supercritical solvent impregnation of mango leaves extract in wound dressings
Diego Valora*, António Montesa, Clara Pereyraa, Enrique J. Martínez de la Ossaa
a Department of Chemical Engineering and Food Technology, Faculty of Sciences, University of Cadiz, International Excellence Agrifood Campus (CeiA3), Campus Universitario Río San
Pedro, 11510, Puerto Real (Cadiz), Spain * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT Usually, the impregnation of active agents into polymeric matrices has been carried out either during the synthesis or processing of polymers or by immersion and soaking of the polymeric materials in a solution containing the bioactive substances. These processes can lead to unwanted reactions between substances, thermal degradation of some of them and also involve the use of toxic organic solvents that must be removed from the matrices. Supercritical solvent impregnation (SSI), a more efficient and environmentally friendly technique solves some of those problems. The solvating capacity of the CO2 as carrier and its high diffusivity favour an easier and faster penetration of the active agent through the matrix [1]. The impregnation of active molecules occurs as a consequence of the interaction balance between the active substance, the matrix and the supercritical phase, which results in an adsorption or a physicochemical attachment of molecules to the matrix.
In this work, a mango leaves extract obtained by enhanced solvent extraction (ESE) with high antioxidant was used as the active substance in supercritical solvent impregnation of cotton fabrics. The predominant compounds in the extract were iriflophenone 3-C-β-D-
80
glucoside, gallic acid, 3-C-(2-O-galloyl)-β-D-glucoside, mangiferin and quercetin glycosides among others. The antioxidant, anti-inflammatory and antibacterial properties of the extract used make it an ideal candidate for impregnation [2]. Different operating conditions, such as pressure, temperature, co-solvent %, contact time and depressurization rate were evaluated. Tests were carried out in high pressure equipment supplied by Iberfluid (semi-continuous process), which includes two vessel (500 mL) with a thermostatic jacket, two high pressure pump (one for CO2 and another for the liquid extract), supercritical carbon dioxide (scCO2), and an automatic back pressure regulator (BPR) to control the system pressure. The first vessel was used to solubilize the mango leaves extract into scCO2. For that, the extract was injected in continuous agitation at 1 mL/min to improve the total solubilization of the liquid extract in the supercritical phase before coming into contact with the matrix, while the CO2 flow rate was 10 g/min. In the second vessel, the material to be impregnated was placed and a washing time was carried out after the injection of the extract. The most favorable conditions for the total polyphenols loading were 300 bar and 35 °C, obtaining an impregnation of 56 mg per gram of injected mango leaves extract. The antioxidant capacity of the processed samples was verified by DPPH assay [3], antimicrobial activity was also measured and the structural changes of the wound dressings as well as the success of the SSI process by SEM to evaluate the surface morphology of the samples before and after impregnation process.
ACKNOWLEDGEMENTS We gratefully acknowledge the Spanish Ministry of Economy, Industry and Competitiveness (Project CTQ2017-86661-R and UNCA15-CE-3567) for financial support.
REFERENCES
[1] M. Pantic, Z. Knez, Z. Novak, Journal of Non-Crystalline Solids, 432, 519-526, 2016.
[2] M. T. Fernández-Ponce, Z. Soto, P. Castro, L. Casas, C. Mantell, E. Martínez de la Ossa, Chemical Engineering Transactions, 75, 2019.
[3] R. Scherer, H.T. Godoy, Food Chem, 112(3), 654-658, 2009.
81
EIFS 2020 O24
Extended copaiba oleoresin release from PCL-Pluronic
porous monoliths against Aedes aegypti larvae
Gláucia R. Medeiros Burina,*, Fábio R. Formigab, Elaine C. M. Cabral-Albuquerquec; Sílvio A. B. Vieira de Meloc; Mara E. M. Bragaª; Hermínio J. C. de Sousaa,*
a CIEPQPF, FCTUC, University of Coimbra, Coimbra, Portugal b LEITV, Gonçalo Moniz Institute - FIOCRUZ, Salvador, Brazil
c Escola Politécnica, Universidade Federal da Bahia, Salvador, Brazil * [email protected]; [email protected]
GRAPHICAL ABSTRACT
ABSTRACT Aedes aegypti L. (Culicidae) has become a serious problem of public health, mainly in tropical and subtropical countries, since it is responsible for transmitting dengue, yellow fever and, more recently, chikungunya and zika viruses [1]. Copaiba tree is native to the tropical regions of South America and Western Africa, also growing in several states of Brazil. Copaiba oleoresin has several biological and pharmacological activities, including anti-inflammatory, antimicrobial, antioxidant, and larvicide [2].
In this study, copaiba oleoresin was incorporated by means of scCO2 foaming in two different types of poly(ε-caprolactone) (PCL), named PCL45 (homo-polyester, hydrophobic, 45 kDa) and PCL50 (co-polyester diol, less hydrophobic, 50 kDa). A surfactant and porogenic agent, Pluronic F-68, was also incorporated in monoliths to favor the copaiba release in aqueous medium. All scCO2 foaming assays were performed in duplicate at temperature of 35 ºC, scCO2 density of 750 and 850 kg m-3, soaking time of 2.5 h, and depressurization rate of 5 bar min-1. Morphological and physicochemical
82
properties of porous monoliths were evaluated as well as the in vitro copaiba release and its larvicidal activity against A. aegypti.
Copaiba oleoresin was successfully incorporated in PCL-Pluronic porous monoliths by scCO2 foaming. The highest amount of copaiba oleoresin was incorporated in PCL50 at 750 kg m-3 (285 ± 16 mg copaiba/g monolith), whereas the lowest amount was obtained for PCL45 at 850 kg m-3 (106 ± 35 mg copaiba/g monolith). Both PCL’s presented crystallinity degree in the range of 60-65%, typical of semicrystalline polymers. The melting temperature (Tm) and crystallinity degree of PCL45 was higher than PCL50, which probably explains the difference between the incorporated amount of copaiba oleoresin. A reduction in Tm and crystallinity degree of porous materials were observed after copaiba incorporation due to its temporary plasticizing effect. The characteristic chemical groups of copaiba oleoresin and PCL did not disappear or shift, as visualized by ATR-FTIR spectroscopy, suggesting that neither chemical bonding nor structural modifications have occurred between the molecules during scCO2 foaming. Copaiba oleoresin release from monoliths to the atmospheric air reached only 30% of total release during 70 days of gravimetric measurements under controlled conditions (23 ± 2 °C; 49 ± 7 % relative humidity). Copaiba oleoresin release in water (28 °C) reached 80% of total release during 30 days of experiment, except for samples of PCL45 processed at 850 kg m-3 that reached a plateau of 30% in a sustained release profile. The larvicidal activity of copaiba oleoresin released from porous monoliths evidenced a promising result for PCL45 samples processed at 850 kg m-3, showing 73.3% of larval mortality after 48 h. Although these samples presented the lowest amount of incorporated copaiba, the sustained release profile coupled with the smallest droplet size of copaiba emulsified in water after in vitro release, 227 ± 17 nm measured by DLS analysis, favored the observed mortality level. In fact, the predominant feeding mode of A. aegypti larvae is collecting-filtering the particulate matter within the nanometer scale [3]. Copaiba oleoresin loaded PCL-Pluronic monoliths are very promising sustainable materials to control A. aegypti proliferation.
ACKNOWLEDGEMENTS This work was financially supported by COMPETE 2020, Fundação para a Ciência e Tecnologia (FCT, Portugal), through the Projects FCT-MEC (PEst-C/EQB/UI0102/2013, Est-C/EQB/UI0102/2018 and PEst-C/EQB/UI0102/2019), and FCT-CAPES FCT/4990/6/4/2018/S. M. E. M. Braga and G. R. Medeiros acknowledges FCT (SFRH/BPD/101048/2014) and CAPES (CAPES/FCT 88887.307384/2018-00) for the financial support, respectively.
REFERENCES [1] G.A.A. Dória, W.J. Silva, G.A. Carvalho, P.B. Alves, S.C.H. Cavalcanti, Pharmaceutical Biology, 48(6), 615-620, 2010.
[2] D.K.R. Bardají, J.J.M. da Silva, T.C. Bianchi, D.S. Eugênio, P.F. de Oliveira, L.F. Leandro, H.L.G. Rogez, R.C.S. Venezianni, S.R. Ambrosio, D.C. Tavares, J.K. Bastos, C.H.G. Martins, Anaerobe, 40, 18-27, 2016.
[3] L.A. Kanis, J.S. Prophiro, E.S. Vieira, M.P. do Nascimento, K.M. Zepon, I.C. Kulkamp-Guerreiro, O.S. da Silva, Parasitology Research, 110(3), 1173-1178, 2012.
83
Poster Sessions
84
85
EIFS 2020 PE01
SFE extraction of aromatic and lipid compounds from shiitake mushroom (Lentinula edodes)
Eva Tejedor-Calvoa,b*, Diego Moralesa, Pedro Marcob, Alejandro Ruiz a, Cristina Soler-
Rivasa, a Department of Production and Characterization of Novel Foods, Institute of Food Science
Research –CIAL (UAM–CSIC), Spain b Forest Resources Department, Agrifood Research and Technology Centre of Aragon (CITA),
Agrifood Institute of Aragón–IA2 (CITA-Zaragoza University), Zaragoza, Spain * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT
Shiitake (Lentinula edodes) is a very popular mushroom in the Asiatic cuisine and it is used in many food products as flavor enhancer because of its aromatic and non-aromatic compounds including lenthionine, more than 60 volatile compounds, certain lipids, amino acids and nucleotides [1, 2]. Supercritical fluid extraction (SFE) is an environmentally friendly technology used mainly to obtain non-polar extracts of interest for the food industry. In this study, aromatic compounds from shiitake mushroom were extracted by a SFE plant using CO2 as solvent. Grape seed oil was added to the separators in some tests to investigate whether it could be used to help trapping the aromatic fraction. Obtained fractions and residual cake were analyzed by HS-GC-MS (Headspace gas chromatography) and compared to initial raw material. Other interesting lipid compounds were also quantified such as fungal sterols due to their hypocholesterolemic properties.
Shiitake powder contained an average of 2.87 mg/g of total sterols most of them extracted when submitted to SFE. Fractions obtained from the separators including oil showed higher amount of sterols (156.7 mg/g) than the ones recovered when oil wasn´t added (136.3 mg/g). The aromatic compounds identified in the obtained extracts and the remaining cakes were studied by means of Principal Component Analysis (PCA), and the
86
plots indicated large differences in the aroma profiles between extracts and the initial shiitake powder whereas no significant differences were observed when oil was added in the separator. The extract obtained using oil in the separator showed higher amount of aromatic compounds compared to control without oil, indicating that oil might enhance the recovery of the aromatic fraction due to its integration in the fat matrix.
ACKNOWLEDGEMENTS This research was supported by national R+ D program from the Spanish Ministry of Science and Innovation (project AGL2014-56211-R) and by National Institute for Agronomic Research (INIA) in Spain (project RTA2015-00053-00-00).
REFERENCES [1] D. Morales, A.J. Piris, A. Ruiz‐Rodriguez, M . Prodanov, C. Soler‐ Rivas, Biotechnology Progress, 34(3), 746-755, 2018.
[2] Y. Tian, Y. Zhao, J. Huang, H. Zeng, B. Zheng, Food Chemistry, 197, 714-722, 2016.
87
EIFS 2020 PE02
Supercritical carbon dioxide extraction of Portuguese rice bran oil
José P. Coelhoa,b*, Inês M. Fernandesa, Nuno R. Nengc, José M. Sardinhad,e, José M.
Nogueirac a CIEQB/ISEL - Instituto Politécnico de Lisboa, 1959-007 Lisboa, Portugal.
b CQE, IST, Universidade de Lisboa, 1049-001 Lisboa, Portugal. c CQE, FC, Universidade de Lisboa, 1749-016 Lisboa, Portugal
d Department of Chemical Engineering, IST, Universidade de Lisboa, 1049-001, Lisboa, Portugal. e CERENA, IST, Universidade de Lisboa, 1049-001, Lisboa, Portugal
GRAPHICAL ABSTRACT
ABSTRACT Rice bran is a by-product (about 8 % of rice paddy) originated from the rice grinding process in which the outer layers of the rice kernel are removed. Rice bran consists of 11–15% proteins, 34–62% carbohydrates, 7–11% crude fibers, 7–10% ashes and 15–20% lipids, which are a by-product of the rice-refining process [1]. Supplement of rice bran in various foods provides to the progress of value-added foods or functional foods that now are of increasing benefit to the society. Rice bran has been profitably enhanced in bread, cakes, noodles, pasta, and ice creams without any negative effect on their functional and textural properties [2].
Supercritical carbon dioxide extraction, scCO2, of oils from samples of rice bran, 16 g, was carried out in the flow apparatus, from Applied Separations, (Spe-edTM SFE) at
88
temperatures from 313.2 to 333.2 K, pressures up to 40.0 MPa and CO2 flow rates from 0.12 kg/h to 0.32 kg/h [3].
Analysis of the extracted oils by GC-FID, revealed the composition of the oils being oleic acid 52%, the main compound, followed linoleic acid 29%, palmitic acid 15%, and stearic acid 1.6%. To estimate the susceptibility to oxidation of oils, the allylic position equivalent (APE) and bis-allylic position equivalent (BAPE) [4] indexes and oxidizability (OX) [5] were calculated using the content of each fatty acid. Moreover, there was a slight difference in extraction kinetics in the relative percentage of the total unsaturation index (UI).
A discussion of the modelling of our data on supercritical fluid extraction of rice bran oil was carried out. The results obtained at different extraction conditions using only one [6] or two [7] adjustable parameter, provided a fairly good agreement between the model curves and the experimental data, which evidence the capability of these models.
ACKNOWLEDGEMENTS J.P. Coelho acknowledge the funding received from the European Union’s Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant agreement Nº 778168 and are thankful for the financial support from Fundação para a Ciência e a Tecnologia, Portugal, under projects UID/QUI/00100/2019.
REFERENCES
[1] B.O. Juliano, P.A. Hicks, Food Rev. Int., 12, 71–103, 1996.
[2] P. Sookwong, S. Mahatheeranont, J. Oleo Sci., 66(6), 557-564, 2017.
[3] J.P. Coelho, A.F. Mendonça, A.F. Palavra, R.P. Stateva, Ind. Eng. Chem. Res., 50, 4618-4624, 2011.
[4] G. Knothe, J. Am. Oil Chem. Soc., 79, 847-854, 2002.
[5] M. Kumar, M.P. Sharma, J. Renew. Sust. Energy Rev., 44, 814-823, 2015.
[6] H. Sovová, Chem. Eng. Sci., 49(3), 409-414, 1994.
[7] H. Sovová, J. Supercritical Fluids, 33(1), 35-52, 2005.
89
EIFS 2020 PE03
Countercurrent supercritical CO2 extraction of phenolics
from the autohydrolysis extracts of Paulownia leaves
Paula Rodrígueza,b, Beatriz Díaz-Reinosob, Andrés Mourea,b, Herminia Domínguez,a, b* a Department of Chemical Engineering, University of Vigo (Campus Ourense), Edificio
Politécnico, As Lagoas, 32004 Ourense, Spain b CITI-Universidad de Vigo, Parque Tecnolóxico de Galicia, 32900 Ourense, España.
GRAPHICAL ABSTRACT
ABSTRACT Supercritical carbon dioxide (sc-CO2) is a good alternative solvent to liquid-liquid extraction processes using conventional organic toxic solvents. The good solvation power at moderate densities, low viscosity, and high solute diffusivity as well as the enhanced mass transfer, the process selectivity, and the easy separation of solvent from the final product are the major advantages.
Continuous countercurrent packed columns have been applied to the fractionation of lipid mixtures, essential oils, and alcoholic beverages [1]. Among the main applications are the supercritical deterpenation of citrus oils, to obtain a more stable and more soluble in water product maintaining flavour [2]; fractionation of bio-oil, which has a high water content, pyrolytic lignin and other compounds including acids, sugars, esters, aldehydes, ketones, phenol, and phenol derivatives [3]; and the deacidification of free fatty acids from cold-pressed olive oil [4].
Liquid-liquid extraction with supercritical carbon dioxide has also been proposed for the removal of polar materials from water [5]. Countercurrent extraction of organic
H20
PAULOWNIA LEAVES HYDROLYSATES
PAULOWNIALEAVES
CO2
CO2
RAFFINATE
EXTRACT
HYDROTHERMAL TREATMENT COUNTERCURRENT SUPERCRITICAL FLUID EXTRACTION
Analytical characterization
10 20 30
Norm.
0
5
10
15
20
DAD1 E, Sig=280,20 Ref=550,100 (TESIS PAULOWNIA\FENOLES\13JUNIO2019 PRUEBAS COLUMNA FSC\13JUN0000004.D)
90
compounds from aqueous samples has been used for the continuous fractionation of complex liquid mixtures, including dealcoholization or isolation of aromas from beverages, such as brandy, wine or cider [6].
In order to assess the potential of the countercurrent supercritical carbon dioxide fractionation of hydrolysates from Paulownia leaves, the behavior of different components has to be evaluated. The aim of this work was to study the extraction of the phenolic fraction from the liquid phase obtained during autohydrolysis.
Autohydrolysis extracts or hydrolysates from Paulownia elongata x tomentosa leaves contain a number of components, including water soluble oligosaccharides, minerals, phenolic fractions, carboxylic acids, aldehydes, ketones, and nitrogen containing compounds. Paulownia leaves hydrolysates were contacted with supercritical carbon dioxide in a countercurrent pilot-plant scale column, 2.8 m long, inner diameter of 30 mm, filled with protruded stainless steel packing, operating at 45 ºC, 10-20 MPa, during 2 h with solvent-to-feed (S/F) mass ratios of 5 and 15. A standard solution of selected phenolic compounds was fractionated at 45°C, 150 bar, during 6 h with with S/F 15.
The supercritical extracts were recovered in one separator, where depressurization occurs, and the raffinate was collected at the exit of the column. At selected operational conditions, the extraction efficiencies from a model solution and from hydrolysates were compared. The phenolic recovery in the standard solution was 0.61 %, whereas in the hydrolysate ranged from 0.06 to 0.28 %. A similar behaviour of the antiradical properties was observed.
ACKNOWLEDGEMENTS The authors are grateful for the financial support of the Ministry of Economy, Industry and Competitiveness of Spain (research project CTM2015-68503-R). PRS is also grateful for financial support from the Ministry of Economy, Industry and Competitiveness of Spain (FPI grant BES-2016-076840).
REFERENCES
[1] A. Bejarano, P. C. Simões, J. M. Del Valle, J. Supercrit. Fluids, 107, 321-348, 2016.
[2] N. Gañán, E.A. Brignole, J. Supercrit. Fluids, 58(1), 58-67, 2011.
[3] W. Maqbool, P. Hobson, K. Dunn, W. Doherty, Ind. Eng. Chem. Res., 56(12), 3129-3144, 2017.
[4] L. Vázquez, A.M. Hurtado-Benavides, G. Reglero, T. Fornari, E. Ibáñez, F.J. Señoráns, J. Food Eng., 90(4), 463-470, 2009.
[5] J.L. Hedrick, L.T. Taylor, J. High Res. Chromatogr., 13(5), 312-316, 1990.
[6] A. Ruiz-Rodriguez, T. Fornari, E. J. Hernández, F.J. Señorans, G. Reglero, J. Supercrit. Fluids, 52(2), 183-188, 2010.
91
EIFS 2020 PE04
Supercritical extraction of natural antioxidants from lavender essential oil
Encarnación Cruz a,*, Jesús M. García-Vargas a, Ignacio Gracia a, Juan F. Rodríguez a,
M. Teresa García a a Institute of Chemical and Environmental Technology (ITQUIMA). University of Castilla-La
Mancha Avda. Camilo José Cela s/n, 13071, Ciudad Real, Spain.
GRAPHICAL ABSTRACT
ABSTRACT
Nowadays, the increase in the demand of nutraceutical and pharmaceutical products of natural origin has led to the search of sources of bioactive products. In this sense, the agro-food sector of Castilla La Mancha offers the possibility to obtain these products from low-value materials or residues, allowing both to satisfy the current need of natural products and promote a key economic sector of the region. Special interest has been paid to compounds with antioxidant and anti-inflammatory potential for the treatment of skin-related diseases such as atopic dermatitis, which affects approximately 20 % of the world's population. Several studies have shown the viability of the extraction of compounds with these properties from garlic, essential oil of different plants and residues of the wine industry [1].
Bioactive compounds are usually extracted with organic solvents. However, these methods have certain limitations such as high energy costs, high temperatures and low selectivity. For this reason, alternative methods are being studied, like supercritical fluid extraction (SFE) [2]. This technology is environmentally friendly and offers the
92
versatility needed to treat different raw materials. Carbon dioxide (CO2) is the most widely used supercritical fluid, as it is inert, non-toxic and allows extraction at lower temperatures and pressures.
Lavender essential oil has been extensively studied for its antioxidant and anti-inflammatory potential, which is attributed to one of its predominant compounds, linalool [3]. In this sense, the present work focuses on the supercritical extraction of this compound for its application in drugs and nutraceuticals for atopic dermatitis.
In order to obtain linalool, the equilibrium system of lavender essential oil with CO2 has to be studied [4], through the analysis of the influence of pressure and temperature, as well as the optimal conditions for supercritical extraction and isolation of this substance [5], which will be quantified by liquid and gas chromatography.
ACKNOWLEDGEMENTS Project: SBPLY/17/180501/000311 “Promoción del sector agroindustrial mediante tecnología supercrítica” Junta de Comunidades de Castilla- La Mancha.
REFERENCES
[1] D.A. Oliveira, A.A. Salvador, A. Smânia, E.F. Smânia, M. Maraschin, S. R. Ferreira, J. of Biotechnology, 164, 423-432, 2013.
[2] T. Fornari, G. Vicente, E. Vázquez, M.R. García-Risco, G. Reglero, J. of Chromatography A, 1250, 34-48, 2012.
[3] L.T. Danh, N.D.A. Triet, L.T.N. Han, J. Zhao, R. Mammucari, N. Foster, J. of Supercritical Fluids, 70, 27-34,2012.
[4] C. Guitiérrez, J.F. Rodríguez, I. Gracia, A. de Lucas, M.T. García, Ind. Eng. Chem. Res., 53(32), 12830-12838, 2014.
[5] Á. Martín, V. Silva, L. Perez, J. García Serna, M. Cocero, Chem. Eng. Technol., 30(6), 726–731, 2007.
93
EIFS 2020 PE05
Experimental optimization of sub- and supercritical carbon dioxide extractions of carotenoids from Dunaliella salina
Mónica Buenoa, Clementina Vitalia,b, J. David Sánchez-Martíneza, Rocío Gallegoa, Jose
A. Mendiolaa,*, Miguel Herreroa, Elena Ibáñeza a Laboratory of Foodomics, Institute of Food Science Research (CIAL, CSIC), Nicolas Cabrera
9, Madrid, 28049, Spain b Unity of Food Science and Nutrition, Faculty of Medicine - Campus Bio-Medico University of
Rome, via Álvaro del Portillo 21, 00128 Rome, Italy * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT There is an increasing demand for natural bioactive compounds able to provide health benefits. In this regard, microalgae are promising microorganisms that can play a key role in bio-based economy, since they may serve as a continuous and reliable source of safe natural products thanks to their variety of valuable bioactive compounds. Dunaliella salina is a green microalga that is able to accumulate relatively high amounts of β-carotene when grown under specific conditions. Although this compound is the main terpenoid in this class of microalgae, other carotenoids related to its biosynthetic pathway could be also of industrial interest. Carotenoids have health promoting properties such as anti-cancer, antioxidant or anti-diabetic [1], and furthermore when are extracted by compressed fluid technologies using green solvents these extracts are compliant with processes and regulations implemented in food, cosmetic and pharmaceutical sectors [2].
Graphical Abstract Image
D. salina
green extraction
characterization mathematical modeling
neuroprotective activities
94
In the present contribution, subcritical and supercritical CO2 conditions have been further studied in order to optimize the extraction yield, carotenoid recovery and purity of the extracts. An experimental design procedure was employed to investigate the effect of pressure and temperature variations ranging respectively from 250 to 400 bar and from 15 to 45 °C. Chemical characterization of the carotenoids extracts was carried out by HPLC-UV/Vis. Moreover, neuroprotective effect of extracts have been studied using antiacetylcholinesterase activity.
Twelve compounds were recognized as carotenoids and quantified. Nine of them were further identified as lutein, zeaxanthin, cryptoxanthin, 13-cis-β-carotene, all-trans-α-carotene, 9-cis-α-carotene, all-trans-β-carotene, 15-cis-β-carotene and 9-cis-β-carotene. Comparison with a conventional solvent extraction proved the investigated green method to be superior in terms of efficiency and purity. Based on the obtained data, three mathematical models were designed. The optimum conditions to maximize the extraction yield were calculated as 400 bar and 40.9 °C (12.8 % extract weight per initial algae weight). The most appropriate operating conditions to obtain the best extraction carotenoid recovery were assessed as 307.6 bar and 43 °C (38.2 mg of carotenoids/g algae). In addition, the best conditions to maximize the extract purity were predicted as 299.4 bar and 40.3°C (32.4 mg of carotenoids/100 mg extract). In addition, selective parameters have been described and discussed in the different extraction conditions studied. Interesting differences in the composition were found in terms of β-carotene isomeric relation, 9-cis/all-trans and carotenes/xanthophylls ratio.
In conclusion, green supercritical CO2 extraction are suitable for fast and efficient production of high-quality carotenoids extracts from D. salina microalga.
ACKNOWLEDGEMENTS Authors thank projects ABACUS (Algae for a Biomass Applied to the production of added value compoundS, grant agreement No 745668, funded by the Bio Based Industries Joint Undertaking under the European Union’s Horizon 2020 research and innovation programme) and AGL2017-89417-R (MINECO, Spain) for financial support. Authors also thank A4F – Algae for Future, Portugal, for supplying and assisting with algae biomass. C.V. acknowledges the Erasmus+ Program for the mobility grant. M.B. acknowledges MINECO for a “Juan de La Cierva-Formación” postdoctoral grant FJCI-2016-30902.
REFERENCES
[1] R. Gallego, L. Montero, A. Cifuentes, E. Ibáñez, M. Herrero, J. Analysis and Testing, 2, 109-123, 2018.
[2] R. Gallego, M. Bueno, M. Herrero, Trend Anal. Chem., 116, 198-213, 2019.
95
EIFS 2020 PE06
Effect of thermal pre-treatment on supercritical CO2 extraction of Castanea sativa burs
Beatriz Díaz-Reinosoa*, Paula Rodrígueza,b, Andrés Mourea,b, Herminia Domínguez,a, b
a CITI-Universidad de Vigo, Parque Tecnolóxico de Galicia, 32900 Ourense, España b Department of Chemical Engineering, University of Vigo (Campus Ourense), Edificio
Politécnico, As Lagoas, 32004 Ourense, Spain *[email protected]
GRAPHICAL ABSTRACT
ABSTRACT Castanea sativa Miller is a chestnut variety produced in temperate areas. The seasonal fruit is a nut, commonly named sweet chestnut or marron, which is collected in autumn and is used for different food purposes. Chestnut burs resulting from the fruit harvesting process are underutilized residues that could be used as renewable source of bioactive compounds with potential interesting applications in the pharmaceutical, food or cosmetics industries.
Different technologies have been studied for the extraction of chestnut burs, such as conventional solvents [1], microwave assisted extraction [2] or hydrothermal treatment [3]. Supercritical CO2 (sc-CO2) is widely known as an environment-friendly alternative for the extraction of bioactive compounds from natural sources. Sc-CO2 allows the extraction at milder operational conditions and offers several advantages including, low viscosity, high diffusivity, tunable solvating power with small changes in pressure and temperature and the easy separation of solvent from the final extract.
Supercritical fluid extraction is limited by the solute-solid matrix interactions, the diffusivity of the solute in the solid, solubility of the solute in the solvent and by the resistance to the external mass transfer. Internal resistance is usually the most important. Therefore, the previous mechanical, thermal, or biochemical conditioning of the solid has a significant influence on the final efficiency of the extraction process.
Thermal pretreatment of the solid could be employed to improve the efficiency of the extraction. Microwave heating increases the internal pressure of the cells promoting the
CO2
Yield
Time
MW effectPower, timePower, timeSC-CO2
CHESTNUT BURS
MICROWAVEPRETREATMENT
SUPERCRITICAL CO2 EXTRACTION
96
rupture of cell walls and enhances the penetration of the solvent into the interior structure of the plant. López-Hortas et al. [4] confirmed that after microwave assisted drying of brown seaweeds, the yields of the ethanolic extraction of the residual solids was significantly enhanced.
The aim of the work was to evaluate the effects of a microwave pretreatment on the supercritical extraction kinetics of chestnut burs.
The chestnut burs were treated in a domestic microwave under selected power and time conditions. Supercritical CO2 extraction was carried out in a Thar SFE-1000 equipment under previously optimized conditions leading (20 MPa and 45 ºC using 10 % ethanol as cosolvent). The collected extracts were used for determination of yields and for the characterization of phenolic content (Folin-Ciocalteu method) and antiradical properties. The model proposed by Sovová [5] was used to describe the experimental extraction curves.
ACKNOWLEDGEMENTS The authors are grateful for the financial support of the Ministry of Economy, Industry and Competitiveness of Spain (research project CTM2015-68503-R). PRS is also grateful for financial support from the Ministry of Economy, Industry and Competitiveness of Spain (FPI grant BES-2016-076840).
REFERENCES
[1] D. Pinto, F. Rodrigues, N. Braga, J. Santos, F.B. Pimentel, A. Palmeira-de.Oliveira, B.P.P. Oliveira, Food Funct., 8, 201-208, 2017.
[2] A. Fernandez-Agulló, M.S. Freire, G. Antorrena, J.A. Pereira, J. González-Álvarez, Sep. Sci. Technol., 49(2), 267-277, 2014.
[3] A. Moure, E. Conde, E. Falqué, H. Domínguez, J.C. Parajó, Rood Res. Int., 359-366, 2014.
[4] L. López-Hortas, M. Gely, E. Falqué, H. Domínguez, M.D. Torres, J. Food Eng., 261, 15–25, 2019.
[5] H. Sovová. J. Supercritic. Fluids, 33, 35-52, 2005.
97
EIFS 2020 PE07
Valorisation of tomato waste using supercritical fluid
technologies
Marta Marquesa,*, Alexandre Paivaa, Susana Barreirosa, Sandra Simõesb, Ana Costab, Marta Bentoc, Pedro Simõesa
a LAQV-REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal
b Research Institute for Medicines (iMed.ULisboa), Faculty of Pharmacy, University of Lisbon, 1649-003 Lisboa, Portugal
c Italagro - indústria de Transformação de Produtos Alimentares S.A., 2600-602 Castanheira do Ribatejo, Portugal * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT The industrial processing of tomatoes produces large amounts of solid wastes, where about 40% of the raw material is removed as waste [1-3]. Tomato waste consists mainly of seeds (rich in oil) and skins (rich in carotenoids such as lycopene). During the processing of tomatoes, a significant amount of carotenoids (mainly lycopene) is lost along with the seeds and skins.According to Al-Wandawi et al. (1985) [4], tomato waste contains three times more lycopene than the tomato products. Lycopene (C40H56) is a natural pigment responsible for the red colour in tomatoes and has been receiving attention due to its high antioxidant activity [2, 3, 5].
The presence of lycopene in tomato wastes increases its economic value since it can be extracted and used in food, cosmetics and pharmaceuticals [1, 3].
Supercritical fluid extraction (SFE) can be used as an alternative to the traditional extraction methods of carotenoids that use organic solvents [6]. Due to its low critical
SFE
20-50 MPa
40-60ºC
10-200 g/min
Lyophilized and milled tomato waste
Lyophilized tomato waste
or
Oil extract + lycopene
98
temperature (31.2ºC) and critical pressure (74 bar), carbon dioxide (CO2) is one of the most commonly used supercritical fluids.
The main objective of this work is the valorisation of tomato industry wastes, obtaining lycopene enriched extracts using supercritical carbon dioxide (ScCO2) extraction. The effect of different process parameters (temperature, pressure, particle size and flow rate) on the oil and lycopene extraction yields were studied.
The conventional method for the extraction of carotenoids tested was the Soxhlet extraction method. N-hexane was used as the solvent. Soxhlet extraction was performed to be later compared with the supercritical CO2 extraction (ScCO2) results. Soxhlet extraction yields varied between 7 to 14%.
ScCO2 extractions were performed at pressures from 200 to 500 bar, and temperatures from 40 to 60 ºC, using lyophilized tomato waste. Higher pressures, higher temperatures and lower particle sizes increased the yield of extraction of oil by ScCO2.
The extracts were analysed spectrophotometrically at 472 nm to rapidly estimate the concentration of lycopene. Lycopene yields ranging from 10 to 60 mg lycopene per 100g of dry material were obtained depending on the pressure/temperature conditions used. Lycopene extracts were further formulated in microemulsions with the aim of developing a topical dosage form, able to supplement the skin with lycopene and treat skin inflammatory disorders.
ACKNOWLEDGEMENTS This work was supported by the Associate Laboratory for Green Chemistry- LAQV which is financed by national funds from FCT/MCTES (UID/QUI/50006/2019) and by project grant number PTDC/SAU-SER/30197/2017.
REFERENCES
[1] E. Vági, B. Simándi, K. P. Vásárhelyiné, H. Daood, Á. Kéry, F. Doleschall, B. Nagy, J. of Supercritical Fluids, 218-226, 2007.
[2] B.P. Nobre, A.F. Palavra, F.L.P. Pessoa, R.L. Mendes, Food Chemistry, 680-685, 2009.
[3] U. Topal, M. Sasaki, M. Goto, K. Hayakawa, J. of agricultural and food chemistry, 5604-5610, 2006.
[4] H. Al-Wandawi, M. Abdul-Rahman, K. Al-Shaikhly, J. of agricultural and food chemistry, 804-807, 1985.
[5] E. Sabio, M. Lozano, V. Montero de Espinosa, R.L. Mendes, A.P. Pereira, A.F. Palavra, J.A. Coelho, Industrial & Engineering Chemistry Research, 6641-6646, 2003.
[6] T. Baysal, S. Ersus, D.A.J. Starnabs, J. of agricultural and food chemistry, 5507-5511, 2000.
99
EIFS 2020 PE08
Sequential extraction (scCO2 + pressurized ethanol) of
Paulownia flowers to obtain phenolic/antioxidants compounds
Paula Rodríguez-Seoanea*, Herminio de Sousab, Marisa C. Gasparb, Mara E. M. Bragab, Herminia Domíngueza*
a Department of Chemical Engineering, University of Vigo (Campus Ourense), Edificio Politécnico, As Lagoas, 32004 Ourense, Spain
b CIEPQPF, Department of Chemical Engineering, Faculty of Sciences and Technology University of Coimbra, Rua Sílvio Lima, Polo II, Portugal
* [email protected]; [email protected]
GRAPHICAL ABSTRACT
ABSTRACT The genus of Paulownia is native to China and stands out for being composed of fast-growing tree species, and it has great value in the wood industry. However, interest in knowing the compounds present in leaves, flowers and fruits is increasing. It is well known that traditional Chinese medicine used these parts of the plant for the treatment of diseases [1, 2].
Nowadays, natural compounds from different plant species are studied as a source of ingredients and additives for functional foods and nutraceuticals [3]. In species of this genus, some of these bioactive compounds as flavonoids, lignans, phenolic glycosides, quinones, terpenoids, glycerides, phenolic acids, have already been identified [4, 5]. In recent studies, extractions with supercritical carbon dioxide (scCO2) in combination with ethanol (etOH) have been carried out to extract phenolic compounds [6].
100
The aim of this work is focused on the fractionation and identification of phenolic compounds present in Paulownia flowers by sequential extraction using supercritical carbon dioxide (first step) and pressurized ethanol (second step).
The extraction is carried out at 35ºC and 45°C, and 150 and 250 bar with a constant average flow rate of 0.50L/min of CO2 and 1.5 ml/min of ethanol. The feasibility of sequential extraction was evaluated by evaluating the kinetics of an extraction process consisting on two stages. In addition, a single pressurized extraction with ethanol was performed as control. Identification of the volatile compounds present in the extract was addressed by GC-MS technology, and heavier compounds were identified by HPLC-UV comparing with standards and literature information.
The extraction yield of 1st step was around 2-10 %, and in the range 13-19 % for the 2nd step. These values were highly dependent on the operational conditions. The characterization of the extracts is being carried out.
ACKNOWLEDGEMENTS The authors are grateful for the financial support of the Ministry of Economy, Industry and Competitiveness of Spain (research project CTM2015-68503-R). PRS is also grateful for financial support from the Ministry of Economy, Industry and Competitiveness of Spain (FPI grant BES-2016-076840). This work was also financially supported by COMPETE 2020, Fundação para a Ciência e Tecnologia (FCT, Portugal), through the Project PEst-C/EQB/UI0102/2019.
REFERENCES
[1] C.-L. Cheng, X.-H. Jia, C.-M. Xiao, Phytochemistry Reviews, 18(3), 549-570, 2019.
[2] Á.M. Móricz, P.G. Ott, M. Knaś, (...), T. Kowalska, M. Sajewicz, Journal of Liquid Chromatography and Related Technologies, 42(9-10), 282-289, 2019.
[3] K. Smejkal, P. Holubova, A. Zima, J. Muselik, M. Dvorska, Molecules, 12(6), 1210-1219, 2007.
[4] B. Dai, Z. Hu, H. Li, C. Yan, L. Zhang, Journal of Chromatography B: Analytical Technologies in the Biomedical and Life Sciences, 978-979, 54-6, 2015.
[5] K. Schneiderová, K. Šmejkal, Phytochemistry Reviews, 14(5), 799-83, 2015.
[6] I.J. Seabra, M.E.M. Braga, R.A. Oliveira, H.C. De Sousa, Journal of CO2 Utilization, 34, 375-385, 2019.
101
EIFS 2020 PE09
Sequential extraction of oxindole alkaloids from Uncaria
tomentosa leaves by pressurized solvents
José R. S. Botelho, Hermínio C. de Sousa, Mara E. M. Braga* CIEPQPF, Department of Chemical Engineering, FCTUC, University of Coimbra, Coimbra,
3030-790, Portugal1 * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT Pentacyclic and tetracyclic oxindolic alkaloids are the main alkaloids present in Uncaria tomentosa or cat’s claw. Cat's claw has been studied and most of the studies highlight mytraphylline as the major alkaloid in the stem bark extract, which is usually a reference in the relation of this plant to the therapeutic effects such as inflammatory processes, hypertension, cancer, Alzheimer's and Parkinson's diseases, hypertension and depression [1]. The main objective of this work to study at extraction of U. tomentosa leaves studying the process variables temperature, pressure and solvent density in obtaining enriched extracts in different concentrations of rhynchophylline, mytraphylline and isomytraphylline by pressurized green solvents sequentially: acetone (1st step) and mixture of ethanol/CO2 (2nd step).
The extractions were performed in an apparatus described by Gañán et al. 2016 [2] and were performed in a sequential order: 1st step: acetone at 328 K and 15 MPa, static period of 1 h, dynamic period of 6 h, and flow rate of 3.76×10-5 kg/s; 2nd step: ethanol+CO2 (25%, m/m), 313 and 333 K and 16-38 MPa, static period of 1 h, dynamic period of 8 h, total flow rate of ~5.6×10-5 kg/s.
102
In the first step, pressurized liquid acetone was used to remove phenolic compounds, chlorophylls and concentrate the oxindole alkaloids in the plant matrix (data were observed in thin layer chromatography and are not shown in this work). Rhynchophylline, mytraphylline and isomytraphylline were identified according to HPLC method from Montoro et al. 2004 [3] in ethanol+CO2 extracts. The rhynchophylline and isomytraphylline contents varied according to the operational conditions of extraction, however the literature reports that mytraphylline is the major oxindole alkaloid prensent in U. tomentosa. rhynchophylline, mytraphylline and isomytraphylline were not observed in the extract obtained by pressurized liquid acetone. The extract obtained at 313 K and 16 MPa presented rhynchophylline content 1.5 times more than isomytraphylline and 5 times more than mytraphylline. Whereas the extract obtained at 333 K and 38 MPa showed isomytraphylline content 1.5 times more than rhynchophylline and 5 times more than mytraphylline. These results show that the pressure and temperature were directly related to the selectivity of the gas-expanded ethanol in relation to these alkaloids. In addition, the contents of isomytraphylline may indicate greater selectivity of the gas-expanded ethanol for this compound and/or isomerization of mytraphylline [4] has occurred due to the extraction process conditions. More than 95% of the alkaloids present in the product marketed in Western Europe of cat's claw are pentacyclic alkaloids as mytraphylline [5]. Therefore, the operational conditions presented in this work make it possible to obtain different extracts enriched in rhynchophylline and isomytraphylline from a single batch of U. tomentosa leaves extraction.
This work presents the process variables optimization for obtaining extracts enriched in the tetracyclic oxindole alkaloid rhynchophylline and the pentacyclic isomytraphylline and mytraphylline. Moreover, the process of this work used green solvents and the results showed that leaves can also be used as a source of these alkaloids.
ACKNOWLEDGEMENTS This work was financially supported by COMPETE 2020, Fundação para a Ciência e Tecnologia (FCT, Portugal), through the Projects FCT-MEC (PEst-C/EQB/UI0102/2013, Est-C/EQB/UI0102/2018 and PEst-C/EQB/UI0102/2019). M. E. M. Braga acknowledges FCT for the financial support (SFRH/BPD/101048/2014) and J.R.S. Botelho acknowledges CNPq–Brazil for PhD fellowship (203210/2014-0-GDE).
REFERENCES
[1] Q. Zhang, J.J. Zhao, J. Xu, F. Feng, W. Qu., J. Ethnopharmacology, 173, 48-80, 2015.
[2] N.A. Gañán, A.M.A. Dias, F. Bombaldi, J.A. Zygadlo, E.A. Brignole, H.C. de Sousa, M.E.M. Braga, Sep. and Purif. Tech., 165, 199-207, 2016.
[3] P. Montoro, V. Carbone, J. de D. Z. Quiroz, F. De Simone, C. Pizza, Phytochem. Anal., 15, 55-64, 2004.
[4] G. Laus, J. Chem. Soc., Perkin Trans., 2, 315-317, 1998.
[5] B. Falkiewicz, J. Łukasiak, Case Rep. Clin. Pract. Rev., 2(4), 305-316, 2001.
103
EIFS 2020 PE10
Enriched oil in DHA omega-3 fatty acid by optimized supercritical fluid extraction of Aurantiochytrium sp.
microalgae
Inês Ferreiraa, M.M.R. de Meloa, M. Sapatinhab, J. Pinheiroc, M.F.L. Lemosc, N.M. Bandarrab, I. Batistab, M.C. Paulod, J. Coutinhod, J.A. Saraivae, I. Portugala, C.M. Silvaa
* a CICECO – Aveiro Institute of Materials, Department of Chemistry, University of Aveiro,
Campus Universitário de Santiago, 3810-193 Aveiro, Portugal. b Division of Aquaculture and Upgrading, Portuguese Institute of the Sea and Atmosphere, Rua
Alfredo Magalhães Ramalho, 6, 1495-006 Lisboa, Portugal. c MARE Marine and Environmental Sciences Centre, School of Tourism and Maritime
Technology, Polytechnic Institute of Leiria, 2520-641 Peniche, Portugal. d DEPSIEXTRACTA Tecnologias e Biológicas, Lda., Zona Industrial do Monte da Barca rua H,
lote 62, 2100-057 Coruche, Portugal. e QOPNA & LAQV-REQUIMTE, Department of Chemistry, University of Aveiro, 3810-193
Aveiro, Portugal. * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT The dependence on fish to assure the world scale supply of omega-3 (ω-3) polyunsaturated fatty acids (PUFA) imposes several challenges, starting with the decrease of fish stocks, but also seasonal variations, unpleasant organoleptic features, or oxidative stability issues. The microalgae thraustochytrid Aurantiochytrium sp. [1] is an alternative marine source that can yield lipophilic extracts with 50 wt.% of PUFA, of which more than 90 % corresponds to docosahexaenoic acid (DHA, 22:6n-3), from the ω-3 family [2]. This research covers the optimization of supercritical fluid extraction (SFE) conditions to maximize the total extraction yield (𝜂𝜂Total), DHA content (𝐶𝐶DHA), total
104
phenolics content (𝑇𝑇𝑇𝑇𝐶𝐶), and antioxidant activity (𝐴𝐴𝐴𝐴𝐶𝐶) of the extracts produced from Aurantiochytrium sp. biomass. The maximum and minimum experimental results were 𝜂𝜂Total = 2.1 and 13.4 wt.%, 𝐶𝐶DHA = 27.3 and 39.3 wt.%, 𝑇𝑇𝑇𝑇𝐶𝐶 = 1.19 and 2.24 mgGAE gextract−1 , and 𝐴𝐴𝐴𝐴𝐶𝐶 = 0.3 and 1.4 mgTEAC gextract−1 . Under the studied experimental conditions, increasing pressure up to 300 bar is the optimum to rise both 𝜂𝜂Total and 𝐶𝐶DHA. Under optimized conditions, supercritical extracts exhibited a DHA content several times above those of fish oil and of the best alternative microalgae species found in the literature [3-4].
ACKNOWLEDGEMENTS This work was funded by the project “Valorização dos subprodutos do processo biotecnológico de produção de esqualeno e DHA pela microalga Aurantiochytrium sp.” (AlgaValue) (ref. 17680), and within the scope of the project CICECO Aveiro Institute of Materials, FCT Ref. UID/CTM/50011/2019 and strategic program of MARE (MARE - UID/MAR/04292/2013), financed by national funds through the FCT/MCTES. Authors also thank the funding from Project AgroForWealth (CENTRO-01-0145-FEDER- 000001), funded by Centro2020, through FEDER and PT2020 and University of Aveiro and FCT/MCT for the financial support for the QOPNA research Unit (FCT UID/QUI/00062/2019) through national founds and, where applicable, co-financed by the FEDER, within the PT2020 Partnership Agreement. The project was also partially funded by the Integrated Programme of SR&TD “SmartBioR” (reference Centro-01-0145-FEDER-000018) cofunded by Centro 2020 program, Portugal2020, European Union, through the European Regional Development Fund.
REFERENCES
[1] A. Zinnai, C. Sanmartin, I. Taglieri, G. Andrich, F. Venturi, Journal of Supercritical Fluids, 116, 126–131, 2016.
[2] V. Manikan, M.S. Kalil, A.A. Hamid, Scientific Reports, 5, 8611, 2015.
[3] V.J.M. Furlan, V. Maus, I. Batista, N.M. Bandarra, Brazilian Journal of Microbiology, 48, 359–365, 2017.
[4] E. Ryckebosch, C. Bruneel, R. Termote-Verhalle, K. Goiris, K. Muylaert, I. Foubert, Food Chemistry, 160, 393–400, 2014.
105
EIFS 2020 PE11
Silybum marianum extracts obtained by conventional and supercritical fluid extraction techniques
Ivana Lukica,*, Stoja Milovanovica, Milica Panticb, Vanja Tadicc
a University of Belgrade, Faculty of Technology and Metallurgy, Karnegijeva 4, 11120 Belgrade, Serbia
b University of Maribor, Laboratory for Separation Processes and Product Design, Faculty of Chemistry and Chemical Engineering, Smetanova 17, 2000 Maribor, Slovenia
c Institute for Medical Plant Research “Dr Josif Pancic”, Tadeusa Koscuska 1, 11000 Belgrade, Serbia
GRAPHICAL ABSTRACT
ABSTRACT Silybum marianum (Asteraceae) seeds and its extracts contain unsaturated fatty acids, vitamin E and flavonoids [1]. Its main compound silymarin is attributed for treatment of cancer, liver, kidney, cardiac, and brain disease [1, 2]. The aim of the present work is to compare extracts obtained by conventional and supercritical fluid extraction techniques considering extraction yield and composition of obtained extracts.
Silybum marianum seeds were grinded and sieved to obtain particles with diameter of ~0.4 mm. Obtained material was placed in a Soxhlet apparatus for conventional extraction. Silybum marianum seeds extracts were obtained during 4 h extraction process using ethanol or n-hexane as solvent. After evaporation of the ethanol or n-hexane, extraction yields were 17% and 25%, respectively. For supercritical fluid extraction (SFE), grinded seeds were exposed to supercritical CO2 at 30 MPa and 40 ºC with or
106
without ethanol as a co-solvent. After around 6 h, result of SFE is extraction yield of 21% without co-solvent addition and 18% with co-solvent addition. In both cases, use of ethanol lead to decrease in an amount of obtained extract. Chemical composition of obtained extracts was analyzed and compared.
ACKNOWLEDGEMENTS Financial support of this work from the Ministry of Education, Science and Technological Development of the Republic of Serbia (Project III45017 and III45001) is gratefully acknowledged. Work carried out in the frame of the COST-Action "Green Chemical Engineering Network towards upscaling sustainable processes" (GREENERING, ref. CA18224) funded by the European Commission.
REFERENCES
[1] N.B. Rahal, F.J. Barba, D. Barth, I. Chevalot, Food and Chemical Toxicology, Vol. 83, 275-282, 2015.
[2] H.T. Celik, M. Gürü, J. of Supercritical Fluids, Vol. 100, 105–109, 2015.
107
EIFS 2020 PE12
Colombian coffee silverskin as source of bioactive extracts
A.M. Escamilla-Santosa, A.D.P. Sánchez-Camargob, M. Martínez-Rodríguezc, G. Alvarez-Riverad, S.R.S. Ferreirab, A. Cifuentesd, E. Ibáñezd, F. Parada-Alfonsoa,* a Departamento de Química y Programa de Maestría en Ciencias-Química, Facultad de
Ciencias, Universidad Nacional de Colombia-Sede Bogotá, Bogotá D.C., Colombia b Departamento de Engenharia Química e Engenharia de Alimentos, Universidade
Federal de Santa Catarina, CP 88040-900, Florianópolis, Brasil c Programa de Maestría en Ciencia y Tecnología de Alimentos, Facultad de Ciencias Agrarias,
Universidad Nacional de Colombia-Sede Bogotá, Bogotá D.C., Colombia d Laboratory of Foodomics, Institute of Food Science Research, CIAL, CEI-UAM+CSIC,
Nicolás Cabrera 9, 28049 Madrid, Spain * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT The coffee industry is one of the most relevant in Colombia in terms of economic development and export earnings [1]. However, this industry is a great waste generator, since about 90% by dry weight of coffee bean becomes unused by-products [2]. Coffee silverskin-CS is a by-product from roasted coffee bean, which has been reported with a valuable proximal composition and important bioactive compounds to be extracted [1]. In this work the lipid fraction-LF and the polar fraction-PF were obtained employing SFE and PLE, respectively. On the one hand, supercritical CO2 at 30 MPa and 45 ºC was used for obtaining LF, and the extraction yield was assessed. On the other hand, for PF, the effect of two pressurized liquid extraction (PLE) factors, temperature of extraction (50,
108
100, and 150 ºC) and solvent composition (0, 50, and 100% EtOH: H2O mixtures) were assessed using a 32 factorial experimental design. Extracts were obtained using PLE static extraction mode (10 MPa, 20 min). Yield, total phenolic content-TPC, total flavonoid content-TFC and antioxidant activity (by TEAC and EC50 methods) were selected as response variables. After the multiple response optimization, n-times extraction cycles (of 20 min) at the best conditions were carried out and yield, TPC and TFC were measured.
Results showed that the SFE extraction yield for LF was 3.6%, whereas the PLE extraction yields for PF were between 5 to 35% (obtained to 50 ºC-50% EtOH and 150 ºC-50% EtOH, respectively). Regards to TPC for PF, values of 54.38 to 109.34 mg Galic Acid equiv. (GAE)/g extract (50 ºC - 100% H2O and 150 ºC - 100 % EtOH, respectively) were found. TFC achieved concentrations between 6.85 to 17.92 mg Quercetin Equiv. (QE)/g extract (150 ºC - 100% H2O and 50 ºC-100 % EtOH). The antioxidant activity values by TEAC method were 0.16 to 1.11 mmol Trolox/g extract (50 ºC - 100% H2O and 150º C – 50 % EtOH) and by DPPH radical were EC50 83.39 to 21.89 µg/mL (50 ºC - 100 % H2O and 100 ºC-100 % EtOH, respectively). The optimal extraction conditions found were 150 ºC and 100% EtOH. At such conditions, remarkable values of 18.20 %, 109.34 mg GAE/g extract, 15.50 mg QE/g extract, 0.99 mmol Trolox/g extract, and EC50 of 26.72 µg/mL of the aforementioned responses variables, were obtained. Temperature was the most important extraction factor in all the responses studied. In addition, four extraction cycles (80 min in total) were enough to exhaust the CS sample. PLE applied to CS is a promising route to enhance the coffee production chain, providing an alternative of valorization to obtain antioxidant extracts.
ACKNOWLEDGEMENTS
The authors thanks to La Tostadora S.A.S.-Café de la Fonda®- (Bogotá-Colombia) for providing the CS sample. A.D.P.-S.-C and S.R.S.F would like acknowledge to the PrINT project/CAPES (Universidade Federal de Santa Catarina) and, F. P-A. to the Direccion de Relaciones Exteriores-DRE at Universidad Nacional de Colombia by respectively supports.
REFERENCES
[1] A. Iriondo-DeHond, N. Aparicio García, B. Fernandez-Gomez, E. Guisantes-Batan, F. Velázquez Escobar, G.P. Blanch, M.I. San Andres, S. Sanchez-Fortun, M.D. del Castillo, Innovative Food Science and Emerging Technologies 51, 194-204, 2019.
[2] M.D. del Castillo, A. Iriondo-DeHond, N. Martinez-Saez, B. Fernandez-Gomez, M. Iriondo-DeHond, J.-R. Zhou, in: Ch.M. Galanakis (Ed.), Handbook of Coffee Processing By-Products. Sustainable Applications, 1st Ed., Academic Press, London, UK, pp. 171-194.
109
EIFS 2020 PE13
Valorisation of agro industrial by-products for obtaining bioactive extracts using SFE and PLE: Colombia as case
study
D. Ballesteros-Vivasa, A.D.P. Sánchez-Camargoa, J.P. Ortega-Barbosab, S.J. Morantes Medinac, H.A. Martínez-Corread, A.M. Hurtado-Benavidese, L.I. Rodríguez Varelaf, F.
Parada-Alfonsoa,*
a Dpto. Química, Facultad de Ciencias, Universidad Nacional de Colombia, Bogotá D.C., Colombia
b Sociedad Colombiana de Ciencias Químicas, Bogotá D.C., Colombia c Unidad de Investigación Básica Oral-UIBO, Universidad El Bosque, Bogotá D.C., Colombia
d Facultad de Ingeniería y Administración, Universidad Nacional de Colombia, Palmira, Colombia
e Facultad de ingeniería Agroindustrial, Universidad de Nariño, Pasto, Colombia f Dpto Ing. Quím.-Ambiental, Fac. Ingeniería, Universidad Nal. de Colombia-Bogotá D.C.,
Colombia * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT
Supercritical fluid extraction (SFE) and Pressurized liquid extraction (PLE) have been recently used as extraction techniques in Colombia for academic and industrial purposes. Those green extraction techniques have been employed to obtain bioactive extracts from agro-industrial food by-products with economic interest. Banana passion fruit seeds, golden berry calyx, mango peels, mango seed kernel, passion fruit seeds, soursop seeds, tamarillo peels have been some the studied agro-industrial food by-products. Several bioactivities have been assessed on the obtained extracts, such as larvicidal activity (against Culex quinquefasciatus), in vitro antioxidant activity (TPC, TFC, DPPH, ABTS, FRAP), protective effect against edible oil oxidation, antiproliferative activity against cancer cell lines (oral or colon cell lines). The authors present a review of research works
110
developed between 2010 and 2019 about the use of compressed fluids to obtain bioactive extracts from Colombian agro-industrial food by-products for pharmaceutical and functional food applications as a strategy for their economical valorisation. DEDICATED TO: The authors dedicate this work to agricultural engineer Carlos Mario López. The young man was murdered at 31th October/2019 (Caloto-Cauca, Colombia) doing his job as agricultural engineer. He trusted in the rural development as the driving force for change and transformation for the Colombian nation. Carlos Mario believed and committed to Colombian peace process.
111
EIFS 2020 PE14
Evaluation of the antibacterial activity of Rosmarinus essential oil (Rosmarinus officinalis) obtained by supercritical fluids extraction against bacterial microbiota of rainbow trout
(Oncorhynchus mykiss) Zully Suarez-Montenegroa,b,*, F. Argote-Vegaa, E. Arteaga-Cabreraa,, A. López-Suáreza,
A. Hurtado-Benavidesa, M. Quiroz-Cabreraa, A. Cifuentesb, E. Ibañezb. a Laboratory of Tecnologías Emergentes en Agroindustria, University of Nariño, Colombia
b Laboratory of Foodomics, Institute of Research in Food Science (CIAL), Madrid, Spain * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT The department of Nariño (Colombia) stands out for being one of the largest producers of rainbow trout in Colombia where it reports an increase of 320.1 tons in 2008 to a production of 493 tons/year in 2011. This activity is focused mainly in Guamués lake, and it carried out in artisanal way and little technology generating a huge risk for the consumer because of low quality and safety of the product obtained, thereby affecting public health. However, this activity has great relevance for the population of the region at an economic and social level because it involves 3550 fish farms [1].
The plants produce compounds with antimicrobial properties that can be used to avoid different foodborne diseases that cause complications for the health of people [2]. In order to find alternatives for conservation based on natural ingredients and reduce the use of
Guamués lake, Nariño (Col)
112
food chemical additives, the main objective of this research was to evaluate in vitro antibacterial activity of Rosmarinus essential oil (Rosmarinus officinalis), obtained by a green technology of Supercritical Fluid Extraction (SFE) in rainbow trout fillets.
The results showed that pressure and temperature play a significant rol (p<0.05) in the extraction process, obtaining the highest yield (2,42%) at 60°C and 300 Bar. The chemical composition of Rosmarinus essential oil identified that the main compound was camphor (21.3-26.95%), followed by trans-caryophyllene (15-22.8%) and eucalyptol (5.5-13.85%). Then, a microemulsion was performed for different concentrations of the essential oil to get a standardized one [3], and the optimum parameters were: heating 60°C, ratio 1:2 oil with Tween 20 as emulsifying agent and 34,2 minutes of agitation.
The antimicrobial activity was determined by the Minimum Inhibitory Concentration (MIC) and Minimum Bactericidal Concentration (MBC) against a group of phatogenic bacteria isolated from the rainbow trout microbiota, as a Staphylococcus aureus, Bacillus cereus and Listeria monocytogenes. Using the method of microdilution in colorimetric broth per Elisa box [4], it was demonstrated that Rosmarinus essential oil has no effect antibacterial on Bacillus cereus but it has antibacterial activity against Listeria monocytogenes and Staphylococcus aureus with a MIC of 32 and 48 μL of oil per mL of emulsion respectively, representing an alternative for the antibacterial control and foodborne diseases [5]. ACKNOWLEDGEMENTS This work was supported by the project 1297 of Research System of University of Nariño (Colombia). T.E.A. group would like to acknowledge the Laboratory of Foodomics (Spain) for financial support.
REFERENCES [1] M.C. Merino, S.P. Bonilla, F. Bages, A. Flores-Nava. Diagnóstico del estado de la Acuicultura en Colombia, Plan Nacional de Desarrollo de la Acuicultura Sostenible en Colombia AUNAP – FAO, 2013. [2] N. Adrar, N. Oukil, F. Bedjou, Industrial Crops and Products, 88, 112–119, 2016. [3] D.J. McClements, Soft Matter, 8, 1719–1729, 2012. [4] G. Abate, R.N. Mshana, H. Miorner, Int. J. Tuberc. Lung Dis., 2(12), 1011-1016, 1998. [5] M.A. Olivares-Cruz, A. López-Malo, Temas Selectos de Ingeniería de Alimentos, 7-1, 78–86, 2013.
113
EIFS 2020 PE16
Subcritical water fractionation of proteins and free amino acids from Brewer’s Spent Grain (BSG)
Patricia Alonso-Riaño*, Esther Trigueros, María Teresa Sanz, Sagrario Beltrán,
Cipriano Ramos, Óscar Benito-Román University of Burgos, Biotechnology and Food Science Dept. Chemical Engineering Division
Pza. Misael Bañuelos s/n 09001 Burgos (Spain) * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT
Brewer’s spent grain (BSG) has been traditionally used only in animal feed despite its high nutritional value, with a protein content of ~20% in dry weight basis [1]. This work is part of a wider project for a complete biomass valorization by using pressurized fluids, namely SC-CO2 to recover the lipophilic fraction and water. In this work we proposed the use of subcritical water at 50 bar and 4 ml/min in a semicontinuous reactor at different temperatures (125 to 185ºC) to extract and hydrolyze BSG proteins. Figure1 shows protein and amino acid values on SubCW extracts accumulated after 240 minutes of
extraction. The highest protein content, 15.6 g/100g BSG, dry, was obtained at 185ºC. On
Figure1. Effect of temperature on SWF extracts of BSG.♦125ºC, ■145ºC,▲160ºC, ○185ºC. A) Protein as 6.25·%N.
0
5
10
15
20
0 30 60 90 120 150 180 210 240
% P
rote
in (%
)
Time, minutes
0
20
40
60
80
100
0 30 60 90 120 150 180 210 240
µmol
aa/
g B
SG, d
ry
Time, minutes
A) B)
114
the other hand, the highest free amino acid content in extracts, 77 µmol aa/g BSG, dry, was achieved at 160ºC due to amino acid decomposition at this operation conditions. This trend has been also observed in the literature for SCWF of oyster at 150 ºC [2]. Free amino acid formed during BSG protein hydrolysis in SubCW are listed in Table 1 together with the amino acid composition of the BSG protein fraction.
Table 1. Amino acid profile of BSG and BSG hydrolysates obtained at different SCWF temperatures.
Essential amino acids (EAA). Values are expressed as mean ± SD and in mg/100 g BSG, dry
Conditions HIS ISO LEU LYS MET PHE THR VAL EAA BSG 379 ± 57 1422 ± 2 1541 ± 38 1475 ± 9 335 ± 20 1121 ± 77 887 ± 45 3147 ± 209 10308 ± 239
125 26.6 ± 0.6 13.5 ± 0.3 25.2 ± 0.1 37.7 ± 0.2 4.4 ± 0.3 26.3 ± 0.2 13.1 ± 0.1 28.2 ± 0.3 175 ± 0.7
145 33.7 ± 0.3 20.9 ± 0.1 41.6 ± 0.2 131.2 ± 3.5 15.7 ± 0.1 34.5 ± 0.3 18.6 ± 0.2 38.9 ± 0.4 336 ± 4
160 19.7 ± 0.8 25.4 ± 0.2 46.7 ± 0.2 87.5 ± 3.8 25.5 ± 0.2 30.4 ± 0.3 19.3 ± 0.2 62.7 ± 0.4 317 ± 4
185 26.7 ± 0.7 34.5 ± 0.2 59.8 ± 0.2 39.4 ± 2.6 4.3 ± 0.1 33.7 ± 1.1 17.7 ± 0.5 117.8 ± 2.1 334 ± 4
Non-essential amino acids (NEAA)
Conditions ALA ASP GLU GLY PRO SER TRP TYR NEAA
BSG 827 ± 87 1422 ± 134 3898 ± 691 741 ± 21 1716 ± 91 926 ± 18 80.7 ± 1.7 421 ± 81 10598 ± 724
125 44.8 ± 0.2 51.2 ± 0.2 114.3 ± 1 15.3 ± 0.1 34.9 ± 0.2 35.5 ± 0.4 4.8 ± 0.1 39.8 ± 0.3 340.4 ± 1.2
145 58.3 ± 0.1 182.9 ± 0.1 75..3 ± 0.6 26.1 ± 0.1 42.4 ± 0.1 48.5± 0.3 6.4 ± 0.1 53.2 ± 0.5 496 ± 2
160 66.8 ± 0.2 232.8 ± 3.2 49.2 ± 0.9 39.5 ± 0.2 44.8 ± 0.3 49.4± 0.5 2.7 ± 0.1 47 ± 0.7 617± 5
185 89.4 ± 0.4 92.3 ± 1 28.8 ± 1.2 78.6 ± 0.8 4.7.9 ± 0.1 30.2 ± 1.4 0.4 ± 0.1 58.1 ± 1.9 430.1 ± 3
Results appears to show a trend related to the hydrophobicity of each group of amino acid since an increase in temperature improves the yield of aliphatic amino acids extraction, while the highest yield for charged amino acids, was reached at 145ºC, and neutral amino acids with a polar side chain, had the highest yield at 160ºC. This agrees with the fact that aliphatic amino acids are stable at higher temperatures. The decrease of water polarity with temperature may favor the affinity for these amino acids due to their hydrophobic character. In addition, small aliphatic amino acids are formed during the decomposition of the other amino acids [3].
BSG offers a great potential as raw material to obtain protein hydrolyzates and amino acids due to its high protein content (~20%) and the elevated rate of EAA. Despite different amino acids has found to be a key parameter on the yield obtained for each amino acid as function of operating temperature. Results obtained in this work suggest that SCWF of BSG is able to recover and hydrolyze BSG proteins. ACKNOWLEDGEMENTS To JCyl and ERDF for financial support of project BU301P18. To Hiperbaric, S.A. for financial support of Project BIOLIGNO. To JCyL and ESF for the predoctoral contracts of E. Trigueros and P. Alonso-Riaño and for the contracts of D. Benito-Bedoya and D. M. Aymara-Caiza through the YEI program.
REFERENCES [1] K.M. Lynch, E. J. Steffen, E. K. J. Institute of Brewing, 122, 553–568, 2016. [2] H.J. Lee, P.S. Saravana, Y.N. Cho, M. Haq, B.S. Chun, Journal of Supercritical Fluids, 141, 120-127, 2018. [3] A.C. Noell, A.M. Fisher, K.F. Francis, S. Sherrit, Electrophoresis, 39, 2854–2863, 2018.
115
EIFS 2020 PE17
The supercritical water approach in valorization of high lignin content biomass
Tijana Adamovica,*, Maria Jose Coceroa
a BioecoUva Research Institute. High Presurre Proceses Group, University of Valladolid, Valladold,
Spain * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT Lignocellulosic biomass is the most abundant biomass form, composed of the three main fractions, hemicellulose, cellulose, and lignin while those fractions are build up from different units, cellulose from C6 sugars, hemicellulose mainly from C5 sugars and lignin from aromatic compounds. Defatted grape seed is a lignocellulosic type of biomass composed of more than 50% of lignin vs 15 % of carbohydrates and thus a great feedstock for lignin and aromatic compounds contained in the lignin structure.
Supercritical Water Technology offers many opportunities to overcome drawbacks of conventional technics used in biomass fractionation, such as long reaction time and accumulation of organic residue, allowing much faster reaction rate and use of water as a green solvent compared to organics [1].
116
Defatted grape seeds firstly were hydrothermally treated to extract hemicellulose fraction and possibly bonded phenolic compounds. After hemicellulose extraction remained solid stayed rich in lignin (around 70 %) and cellulose fraction (around 25 %). This solid was further subjected to supercritical water hydrolysis. For this purpose, a continues pilot plant with a sudden expansion microreactor was used. The grape seed suspension was pumped up to 26 MPa and instantaneously heated to 385 ºC by mixing with SCW steam. The design of the plan allows instantaneously cooling and therefore reaction termination by depressurizing the product through a high-temperature needle valve. After the reaction two sample phases were obtained, liquid phase reach in sugars and aromatic compounds and solid-phase reach in lignin.
Graph 1. shows preliminary results based on the supercritical water hydrolysis of grape seeds that were not previously hydrothermally extracted, as the yield of sugars in the liquid phase vs reaction time, which was measured as the function of reactor volume and total flow. High recovery of total sugars (up to 70 %) was obtained, already for a very short reaction time of 210 ms. Further, the amount of sugars was gradually decreased due to degradation and then increased again that could be due to possible lignin depolymerization that allows the new amount of sugars to be accessible to supercritical water, as the lignin could act as a barrier to supercritical water for hydrolysis of label fractions. The composition of solid-phase showed that the amount of lignin in solid-phase firstly increase, but then started to decrease again due to already mentioned possible depolymerization. Those results will be compared with the results of biomass that was previously hydrothermally extracted as would be expected that hydrothermal treatment can improve sample porosity and decrease cellulose crystallinity, allowing in that way, apart of hemicellulose recovery by hydrothermal pretreatment, higher recovery of C6 sugars by supercritical water hydrolysis and possibly of aromatic compounds due to lignin depolymerization.
Graph 1. Sugar yield in the liquid phase vs reaction time
ACKNOWLEDGEMENTS
Authors thank to Ministerio de Ciencia, Investigacion y Universidades and FEDER program for the project CTQ 2016-79777. T.A. Thanks to FPI- UVA Santander PhD Grant.
REFERENCES [1] M. J. Cocero, Á. Cabeza, N. Abad, T. Adamovic, L. Vaquerizo, C. M. Martínez, M. V. Pazo-Cepeda, The Journal of Supercritical Fluids, 133, 550-565, 2018.
4045505560657075
0 200 400 600 800 1000
Suga
r yie
ld (%
,w/w
)
Reaction time (ms)
117
EIFS 2020 PE18
Integral valorization of agro-food biomass through pressurized fluids. Case study: Brewery Spent Grain (BSG)
Maria Teresa T. Sanz, Patricia Alonso-Riaño, Esther Trigueros, M. Kashaninejad, D.M.
Aymara, Oscar Benito-Román, M.O. Ruiz, I. Escudero, J. M. Benito and Sagrario Beltrán*
Department of Biotechnology and Food Science (Chemical Engineering Division) University of Burgos, 09001 Burgos, Spain
GRAPHICAL ABSTRACT
ABSTRACT The biorefinery concept involves the valorization and conversion of biomass into different bioproducts, including energy, materials and chemicals that can replace products derived from fossil carbon sources. The integral valorization of biomass requires the extraction and fractionation of the different constituents thereof, extractables, lipids, proteins and structural components such as cellulose, hemicellulose and lignin. In this work, the use of emerging and clean technologies for the integral valorization of different types of biomass is proposed. First, the use supercritical CO2 (SCCO2) extraction is proposed for recovering the lipid fraction and ultrasonic assisted extraction to recover the hydrophilic fraction, to subsequently perform a fractionation and hydrolysis of the residual biomass using pressurized liquid water.
Several types of biomass are being studied, both second and third generation. Among second generation biomass, the brewery spent grain (BSG), which accounts for 85% of the by-products generated in beer processing [1], has been selected as case study of this communication.
The extraction of the lipid fraction with SCCO2 has been carried out in a 26.5 mL capacity extractor at different pressures (20-40 MPa) and temperatures (40-80 °C). The lipid fraction obtained has been characterized by determining its lipid profile and antioxidant capacity.
118
The experiments of fractionation and hydrolysis in subcritical water (scW) have been carried out in a semi-continuous reactor, varying the extraction temperature. The different fractions obtained have been characterized by HPLC with two series detectors, UVD and RID, to determine the content in monomeric sugars and oligomers. Protein, free amino acids, total polyphenols and total organic carbon have been also determined.
The composition of the BSG according to the biomass characterization protocols of NREL [2] was 21.1 % arabinoxylans, 25.6 % glucanes, 5.1 % soluble lignin, 10.5 % insoluble lignin, 1.2 % ashes, 16.7 % proteins, 5.6 % lipids and 14.4 % extractables. Worth noting the presence of insoluble lignin as well as the high content of arabinoxylans and glucanes, 10% of which were residual starch.
The extraction curves obtained when studying the extraction of the lipid fraction of BSG with SCCO2, showed that the extraction rate and the extraction yield increased with increasing temperature and pressure, with the major fatty acid being linoleic acid.
Regarding fractionation of the carbohydrate fraction, we have observed that, as temperature increases, hydrolysis increases. Figure 1a shows the sugars yield, including monomeric sugars and oligomers. Degradation of sugars due to the high residence times produces acids (Fig. 1b), hydroxymethylfurfural (HMF) and furfural (Fig. 1c).
Figure 1. Fractionation in scW at T = 185 °C (a) total sugars yield (b,c) degradation products
The treatment of biomass by scW, allows also recovering the entire protein fraction by increasing the temperature up to around 185ºC. In addition, partial hydrolysis of the protein fraction occurs, obtaining as major free aminoacids valine, aspartic acid, alanine and glycine.
We can conclude that the fractionation of BSG through emerging and clean technologies allows an integral recovery of BSG, obtaining extracts with high antioxidant capacity. Pressurized water hydrolysis allows the recovery and fractionation of the carbohydrate and protein fraction.
ACKNOWLEDGEMENTS To JCyL and ERDF for financial support of project BU301P18. To Hiperbaric, S.A. for financial support of Project BIOLIGNO. To JCyL and ESF for the predoctoral contracts of E. Trigueros and P. Alonso-Riaño and for the contracts of Davinia Benito-Bedoya and Daysi M. Aymara-Caiza through the YEI program.
REFERENCES [1] S.I. Mussatto, G. Dragone, I.C. Roberto, J. Cereal Sci., 43, 1-14, 2006. [2] LAP-002 NREL Determination Analytical Procedure, 2004.
119
EIFS 2020 PE19
Supercritical fluid extraction of triterpenoids of the lupane type from Acacia dealbata bark biomass
Vítor H. Rodriguesa,*, Inês Portugala, Carlos M. Silvaa
a Department of Chemistry, CICECO – Aveiro Institute of Materials, University of Aveiro, Campus Universitário de Santiago 3810-193. Aveiro, Portugal
GRAPHICAL ABSTRACT
ABSTRACT Acacia dealbata is a species of the genus Acacia, native from Australia, that has been introduced in the central coastal region of Portugal during the 19th and 20th century for ornamental, wood supply, dunes erosion protection and pine forests protection purposes [1]. Currently, it is considered an aggressive invader, appearing in every province of mainland Portugal, occupying (the genus Acacia) a total area of around 8 thousand hectares [2]. To control its reproduction, Acacia trees are periodically removed, producing considerable amounts of biomass. From a previous work [3], several triterpenes were firstly identified in the biomass of this species, namely lupeol and lupenone, which have been recognized for their bioactive properties, such as anti-inflammatory, anti-virus, anti-diabetes, anti-cancer, among others [4,5].
The bark of A. dealbata was extracted by the conventional Soxhlet method, using dichloromethane, ethanol, methanol, n-hexane, petroleum ether, ethyl acetate and
120
isopropanol as solvents for 6 h. The supercritical fluid extractions (SFE) were performed at different pressures (200-300 bar), temperatures (40-80 °C) and with the employment of ethanol and ethyl acetate as CO2 modifiers. The CO2 flow rate was maintained at 12 g min-1 and the extractions lasted 6 h. The yields of extraction were measured, and the extracts were analysed by gas chromatography coupled to mass spectrometry (GC-MS).
The total yields of extraction ranged from 1.08 wt.% to 21.87 wt.% for SC-CO2 (200 bar and 40 °C) and methanol (Soxhlet), respectively. The best SFE assay yielded 2.11 wt.% (300 bar, 80 C, 5 wt.% ethanol), a comparable value to the least polar solvents by Soxhlet (dichloromethane, n-hexane and petroleum ether).
Several compounds of the lupane type were identified, namely, lupenone, lupadienyl acetate, lupenyl acetate and lupeyl acetate (LA). The latter was the main compound present in the bark. In the case of SFE, the maximum LA yield reached the Soxhlet reference value for several assays, while the concentration in the first moments of the extraction surpassed that of the Soxhlet, showing the specificity of SFE for the extraction of triterpenoids.
Overall, this work provides arguments for further SFE research on A. dealbata biomass, disclosing a possible valorisation route for the agro-industrial sector, under the biorefinery scope. ACKNOWLEDGEMENTS This work was carried out under the Project inpactus – innovative products and technologies from eucalyptus, Project N.º 21874 funded by Portugal 2020 through European Regional Development Fund (ERDF) in the frame of COMPETE 2020 nº246/AXIS II/2017.
REFERENCES
[1] C.A. Kull, C.M. Shackleton, P.J. Cunningham, C. Ducatillon, J.-M. Dufour-Dror, K.J. Esler, J.B. Friday, A.C. Gouveia, A.R. Griffin, E. Marchante, S.J. Midgley, A. Pauchard, H. Rangan, D.M. Richardson, T. Rinaudo, J. Tassin, L.S. Urgenson, G.P. von Maltitz, R.D. Zenni, M.J. Zylstra, , Divers. Distrib. 17 (2011) 822–836.
[2] S. Ferreira, E. Monteiro, P. Brito, C. Vilarinho, Renew. Sustain. Energy Rev. 78 (2017) 1221–1235.
[3] F.B.M. Pereira, F.M.J. Domingues, A.M.S. Silva, Nat. Prod. Lett. 8 (1996) 97–103.
[4] F. Xu, X. Huang, H. Wu, X. Wang, Biomed. Pharmacother. 103 (2018) 198–203.
[5] M. Salee, Cancer Lett. 285 (2009) 109–115.
121
Poster Sessions
122
123
EIFS 2020 PR01
Direct hydrothermal conversion of CO2 capture on aqueous solutions of alkanolamines into formic acid and methane
Laura Quintana Gómeza, Ángel Martín Martíneza, M. Dolores Bermejo Rodaa,*
a BioEcoUVa. Instituto de Investigación en Bioeconomía. Grupo de Procesos a Alta Presión. Dpto. Ing. Química y TMA. Universidad de Valladolid
GRAPHICAL ABSTRACT
ABSTRACT
As it is well-known, the huge combustion of fossil fuels in modern societies has broken the natural balance of the carbon cycle and thus, CO2 concentration in the atmosphere has increased from approximately 278 ppm in ca. 1750 to more than 400 ppm in 2019 [1, 2]. Therefore, due to its abundance and lack of toxicity, CO2 has gained great attention as a potential raw material for the synthesis of chemicals and fuels [3]. One of the most popular alternatives to transform CO2 is its catalytic hydrogenation, however this technique involves the addition of gaseous H2 which is produced from fossil fuels, such as the steam methane reforming (SMR) [4]. Moreover, the use of H2 present other disadvantages such as high production costs and dangerous flammability and compressibility [5]. Therefore, the in-situ generation of H2 by reduction of water would represent a great advantage. Furthermore, nowadays the most developed technology to capture CO2 is its chemical absorption by aqueous solutions of alkanolamines. The direct conversion of the captured CO2 into useful chemicals would reduce the high costs associated with the capture process, particularly the desorption of CO2 and the regeneration of the amine [6]. This work reports initial proof-of-concept studies on the
124
direct hydrothermal reduction of CO2 absorbed on aqueous amine solutions in the absence of the addition of gas phase H2.
In this research, CO2 absorbed on monoethanolamine (MEA) was used as the starting material for the synthesis of formic acid and methane. The hydrothermal reaction of CO2 requires the addition of a reductant to the in-situ production of H2. In this work, the role as reductants of Zn and Al were evaluated. The performance of hydrogenation catalysts, including Raney Ni, Pd supported on carbon, Fe3O4, Fe2O3 and Ni powder was also explored. Moreover, the effect of the reaction temperature on the product distribution was also investigated. Results revealed that Raney Ni catalyst was very selective to the production of CH4, reaching a yield of ca. 25 % on carbon basis. The yield to CH4 using Ni powder as catalysts was approximately 7 % on carbon basis, while with the other catalysts tested no methane was produced. Although the product distribution with both iron oxides was very similar, Fe3O4 produced higher yields of formic acid than Fe2O3. These results demonstrated the feasibility of the hydrothermal conversion of CO2 into value-added chemicals and the potential of this technology for the design of integrated CO2 capture and utilization systems.
ACKNOWLEDGEMENTS Authors acknowledge Junta de Castilla y León for funding this research through the project VA24P18. LQG also thanks Junta de Castilla y León for her postdoctoral contract and MDB also thanks Ministerio de Economía y Empresa for her Ramón y Cajal contract.
REFERENCES
[1] T. Stocker, G.K. Plattner, M. Tignor, S. Allen, J. Boschung, A. Nauels, Y. Xia, V. Bex, P.M. Midgley, IPPC 2013, Cambridge University Press, Cambridge, 2013.
[2] CO2.earth, https://es.co2.earth/, Accessed October 21, 2019.
[3] T. Sakakura, J.C. Choi, H. Yasuda, Chemical Reviews, 107(6), 2365-2387, 2007.
[4] B. Michalkiewicz, Z.C. Koren, Journal of Porous Materials, 22, 635-646, 2015.
[5] G. Centi, E.A. Quadrelli, S. Perathoner, Energy & Environmental Science, 6, 1711-1731, 2013.
[6] Y.E. Kim, J.A. Lim, S.K. Jeong, Y.I. Yoo, S.T. Bae, S.C. Nam, Bulletin of the Korean Chemical Society, 34, 783-787, 2013.
125
EIFS 2020 PR02
Hydroxyl-functionalised ionic liquids in the synthesis of cyclic carbonates from high-pressure CO2
A.B. Paninho,a A. Forte,a M.E. Zakrzewskaa,b, K.T. Mahmudov,b,c
A.J.L. Pombeiro,b M.F.C. Guedes da Silva,b M. Nunes da Ponte,a Luís C. Branco,a Ana V. M. Nunesa*
a LAQV, REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia,
Universidade Nova de Lisboa, 2829-516 Caparica, Portugal b Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av.
Rovisco Pais, 1049–001 Lisbon, Portugal c Department of Chemistry, Baku State University, Z. Xalilov Str. 23, Az 1148 Baku, Azerbaijan
GRAPHICAL ABSTRACT
ABSTRACT Carbon capture and utilization (CCU) is a rapidly growing research area. It explores the utilization of carbon dioxide (CO2) as a C1 building block as alternative to fossil-based resources, bringing carbon back into the value chain and therefore contributing to a circular economy [1]. Concerns related with increasing CO2 emissions and high levels of atmospheric concentrations are the major driving force behind scientific global efforts to address this issue. In this context, the production of cyclic carbonates is one of the most promising applications of CO2 as a carbon feedstock into a large-scale utilization. Indeed, cyclic carbonates may find applications as polar aprotic solvents, electrolytes for lithium batteries, chemical intermediates and precursors for polymers and fuels [1].
126
One of the most attractive routes to produce cyclic carbonates is the atom economic coupling reaction between CO2 and highly energetic epoxides. Binary catalytic systems composed of homogeneous metal complexes together with ionic liquids, namely quaternary ammonium halides, have been successfully used [2,3]. In this work the synergetic catalytic effect of several hydroxyl-functionalised quaternary ammonium salts was studied in the coupling reaction between CO2 and propylene oxide. Quaternary ammonium salts bearing different alkyl chains and hydroxyl groups were synthesized and tested as catalysts. Reactions were performed in a visual stainless-steel cell at 60ºC and high pressure CO2 [4-6]. Propylene carbonate was quantitatively analysed by 1H-NMR spectroscopy. Results obtained highlight the importance of exploring simultaneously both electrostatic and hydrogen bonding effect in order to increase ionic liquids catalytic activity. ACKNOWLEDGEMENTS This work was supported by FCT/MEC through project PTDC/EQU-EPQ/31926/2017, by the Associate Laboratory for Green Chemistry LAQV and Centro de Química Estrutural CQE, which are financed by national funds from FCT/MEC (UID/QUI/50006/2019 and programme 2020-2023). A.V.M. Nunes is thankful to FCT/MEC for contract IF/01374/2014. A.B. Paninho is thankful to FCT/MEC for the Post-doctoral fellowship PD/BD/52497/2014. NMR spectrometers at FCT NOVA are part of Rede Nacional de RMN (PTNMR), supported by Fundação para a Ciência e Tecnologia (ROTEIRO/0031/2013 - PINFRA/22161/2016) and (co-financed by FEDER through COMPETE 2020, POCI, and PORL and FCT through PIDDAC).
REFERENCES [1] A.S. Reis Machado, A.V.M. Nunes, M. Nunes da Ponte, J. Supercrit. Fluids 2018, 134, 150-156. [2] M. North, R. Pasquale, C. Young, Green Chem 2010, 12, 1514-1539. [3] C. Martin, G. Fiorani, A.W. Kleij, ACS Catal. 2016, 5, 1353-1370. [4] C.A. Montoya, A.B. Paninho, P.M. Felix, M.E. Zakrzewska, J. Vital, V. Najdanovic-Visak, A.V.M. Nunes, J. Supercrit. Fluid 2015, 100, 155-159. [5] C.A. Montoya, C.F. Gomez, A.B. Paninho, A.V.M. Nunes, K.T. Mahmudov, V. Najdanovic-Visak, L. Martins, M. da Silva, A.J.L. Pombeiro, M. Nunes da Ponte, J.Catal. 2016, 335, 135-140. [6] A.B. Paninho, A.L.R. Ventura, L.C. Branco, A.J.L. Pombeiro, M.F.C. Guedes da Silva, M. Nunes da Ponte, K.T. Mahmudov, A.V.M. Nunes, J Supercrit Fluid 2018, 132, 71-75.
127
Poster Sessions
128
129
EIFS 2020 PT01
The effect of the three phase relative permeability model in low salinity water alternating supercritical CO2 injection
Silvio A. B. Vieira de Meloa,b,*, Arley S. Carvalhala, Gloria M.N. Costaa
a Programa de Pós-Graduação em Engenharia Industrial, Universidade Federal da Bahia, Salvador, BA, Brasil
b Centro Interdisciplinar de Energia e Ambiente, Universidade Federal da Bahia, Salvador, BA, Brasil
GRAPHICAL ABSTRACT
ABSTRACT The Brazilian Pre-Salt fields, today responsible for most of the country’s oil production, have a very high CO2 content (20%-44% molar) [1]. In order to avoid atmospheric release of CO2, reinjection into the oil reservoir must be done and the associated effects should be well addressed. The minimum pressure needed to achieve miscible conditions for oil-CO2 mixtures in reservoir is typically above the critical pressure of CO2. Reservoir temperature is also typically above the critical temperature of CO2. In this work, simulations of supercritical CO2 injection in a petroleum reservoir is performed and compared to low salinity water alternating CO2 injection (CO2LSWAG). As this technique inherently includes three-phase flow, a key step in the simulation is modeling the three-phase relative permeability. This property is defined as the ratio between the effective permeability of a fluid phase in the reservoir and the absolute permeability of the porous media. However, experimental measuring of three-phase relative permeability is a troublesome task. Therefore, a usual practice is to predict it from two phase relative permeability data. In this work, four of the most used correlations were compared to evaluate their effect on oil recovery [2-4]. In the beginning of the simulation period, when the oil saturation and consequently the oil relative permeability are high, the three-phase relative permeability model choice has low impact on oil recovery. However, as the
130
difference in the predicted oil relative permeability becomes higher for lower oil saturation, a significant difference in oil recovery is observed at the end of the simulation period. Different scenarios were simulated to assert the conditions in which this property is more important. The difference in the predicted oil recovery is higher when the alternation of the injected fluid is more frequently carried out. This difference also increases when the ratio between the flow rates of the injected fluids is unity. It was observed that the choice of the model may lead to a difference of up to 4.5% in ultimate oil recovery, a substantial value, comparable to differences related with uncertainties of the CO2 content in the reservoir [5].
ACKNOWLEDGEMENTS The authors acknowledge the support of the Agência Nacional de Petróleo, Gás Natural e Biocombustíveis (ANP) and the Petrogal Brasil S.A. related to the grant from the R&D investment rule.
REFERENCES [1] M.A. Pasqualette, M. J. Rempto, J.N.E. Carneiro, R. Fonseca, J.R.P. Ciambelli, S.T. Johansen, B.T. Løvfall, Paper OTC-28093-MS presented at the Offshore Technology Conference Brasil held in Rio de Janeiro, Brazil, 24-26 October 2017. [2] H.L. Stone, Journal of Petroleum Technology, Vol. 249, 214-218, 1970. [3] H.L. Stone, Journal of Canadian Petroleum Technology, Vol. 12, 53-61, 1973. [4] L.E. Baker, SPE/DOE Paper 17369, presented at the 6th Symposium on Enhanced Oil Recovery, Tulsa, Oklahoma, April 17-20, 1988. [5] A.S. Carvalhal, G.M.N. Costa, S.A.B. Vieira de Melo, SPE Paper 196684-MS presented at the SPE Reservoir Characterization and Simulation Conference and Exhibition held in Abu Dhabi, UAE, 17-19 September 2019.
131
EIFS 2020 PT02
Study of volumetric behavior during asphaltene precipitation due to supercritical CO2 injection using PC-SAFT EoS
Silvio A. B. Vieira de Meloa,b,*, Fabio P. Nascimentoa, Gloria M. N. Costaa
a Programa de Pós-Graduação em Engenharia Industrial, Universidade Federal da Bahia, Salvador, BA, Brasil
b Centro Interdisciplinar de Energia e Ambiente, Universidade Federal da Bahia, Salvador, BA, Brasil
GRAPHICAL ABSTRACT
ABSTRACT Asphaltene is an ill-defined polydisperse mixture and the heaviest part of petroleum [1]. During oil recovery from the reservoir, asphaltenes may precipitate due to changes in the temperature, pressure and composition of the fluid and can plug reservoir wells and production lines [1,2]. Injection of supercritical CO2 is the most-common approach for enhanced oil recovery (EOR), but it may trigger asphaltene precipitation due to composition changes [3]. Hence, predicting the onset of asphaltene precipitation is extremely important. The Perturbed Chain-Statistical Associating Fluid Theory (PC-SAFT) [4] equation of state (EoS) has been widely used in the literature to model the asphaltene precipitation [1,3].
As discussed by Yang et al. [5], asphaltene initially precipitates as a second liquid asphaltene-rich phase. According to Pedersen et al. [6], starting from a single-phase liquid state, as pressure is reduced the asphaltene onset pressure (AOP) is the pressure at which
132
it becomes thermodynamically favorable for the oil to split into two phases (asphaltene-rich and asphaltene-lean phases) rather than remaining as a single-phase. At constant temperature, the total volume of the asphaltene-lean and asphaltene-rich phases below the AOP is lower than the volume the oil would have as a single phase. Therefore, a successful asphaltene model must account for this volumetric behavior.
In this work, the capability of PC-SAFT EoS to predict the volumetric behavior during asphaltene precipitation was evaluated. Four oils with data available in the literature [7] were studied following the characterization procedure proposed by Punnapala and Vargas [8]. The aromaticity of the (A+R) fraction [8] was adjusted using experimental data of bubble pressure while the aromaticity of asphaltene was fitted based on experimental AOP data. The volumetric behavior in the AOP was calculated with the PC-SAFT EoS at different compositions of supercritical CO2, for each oil. Above the AOP, an oil is in a single phase and the results were calculated considering the global composition. Bellow the AOP, each oil splits in two phases. Thus, a liquid-liquid PT-Flash [6] was first performed and the resulting phase compositions were used for density calculation. For all evaluated oils the PC-SAFT EoS correctly predicts a slight change in the slope of the PV (pressure-volume) curve for pressures below the AOP.
ACKNOWLEDGEMENTS The authors acknowledge the support of Agência Nacional de Petroleo, Gás Natural e Biocombustíveis (ANP) and Petrogal Brasil S.A., related to the grant from the R&D investment rule.
REFERENCES
[1] A. Arya, X. Liang, N. von Solms, G. M. Kontogeorgis, Energy & Fuels, Vol. 30, 6835-6851, 2016.
[2] G. M. Kontogeorgis, G. K. Folas, Thermodynamic models for industrial applications: from classical and advanced mixing rules to association theories, 1st Ed., John Wiley & Sons, West Sussex, United Kingdom, pp. 422-424, 2010.
[3] F. P. Nascimento, G. M. N. Costa, S. A. B. Vieira de Melo, Fluid Phase Equilibria, Vol. 494, 74-92, 2019.
[4] J. Gross, G. Sadowski, Industrial & Engineering Chemistry Research, Vol. 40(4), 1244-1260, 2001.
[5] Y. Yang, W. Chaisoontornyotin, M. P. Hoepfner, Langmuir, Vol. 34, 10371-10380, 2018.
[6] K. S. Pedersen, P. L. Christensen, J. A. Shaikh, Phase Behavior of Petroleum Reservoir Fluids, 2 Ed., CRC Press, Boca Raton, Florida, pp. 144-150 and 306-312, 2015.
[7] W. A. Fouad, M. I. L. Abutaqiya, K. Mogensen, Y. F. Yap, A. Goharzadeh, F. M. Vargas, L. F. Vega, Energy & Fuels, Vol. 32, 8318-8328, 2018.
[8] S. Punnapala, F. M. Vargas, Fuel, Vol. 108, 417-429, 2013.
133
EIFS 2020 PT03
Estimation of multicomponent diffusivities in supercritical and liquid mixtures
Bruno Zêzere, João Iglésias, Inês Portugal, José R. B. Gomes, Carlos M. Silva* Department of Chemistry, CICECO, University of Aveiro, Aveiro, 38100-193, Portugal
GRAPHICAL ABSTRACT
ABSTRACT
Transport properties such as molecular diffusion coefficients (D12) are of chief importance for accurate modeling and equipment design of processes involving mass transfer like supercritical fluid extraction (SFE). The use of supercritical CO2 with a co-solvent has been increasing since it enables fine tuning the affinity of the solvent mixture to specific solutes. Hence there is a need for D12 of a solute in solvent mixtures [1]. Currently, the experimental data for multicomponent systems, both supercritical and liquid, are scarce. Moreover, there is an absence of accurate models for these cases [2].
One relevant model for diffusivity estimation is that of Liu-Silva-Macedo [3-5], originally developed for self-diffusion coefficients and later extended to binary tracer diffusion (TLSM) by Liu and coworkers [3,5] and to multicomponent Lennard-Jones (LJ) intradiffusivities by Merzliak and Pfenning (LSM-MP) [3,6].
In this work an improved predictive model and a 1-parameter correlation are proposed to calculate tracer diffusivities of solutes in multicomponent supercritical or liquid mixtures, based on the work of Merzliak and Pfenning [3,6]. In this research an extensive database containing 1457 experimental points was used to optimize the model parameters. This
134
database spans across 131 ternary systems, namely 90 liquid systems and 41 supercritical systems retrieved from the literature.
The resulting predictive and 1-parameter correlation of the New-LSM model demonstrate an improved performance over the LSM-MP model. The predictive form of the New-LSM model showed an average absolute relative deviation (AARD) of 9.64 % and the 1-parameter correlation achieved 4.11 %, while the original LSM-MP model scores a grand AARD of 35.93 %.
Furthermore, the predictive Wilke-Chang equation [7] and the 2-parameter correlation of Dymond–Hildebrand–Batschinski (DHB) [3,8] were tested using the same experimental database. The former achieves relative deviations of 15.47 % while the later provides a lower error of 8.05 %.
Overall the New-LSM predictive model shows an improved performance over the predictive models of Wilke-Chang and LSM-MP, while the 1-parameter correlation shows better performance than all the tested models
ACKNOWLEDGEMENTS This work was developed in the scope of the project CICECO-Aveiro Institute of Materials (Ref. FCT UID/CTM/50011/2019), financed by National Funds through the FCT/MEC and when applicable co-financed by FEDER under the PT2020 Partnership Agreement. Bruno Zêzere thanks FCT for PhD grant SFRH/BD/137751/2018.
REFERENCES [1] M. M. R. De Melo, A. J. D. Silvestre, C. M. Silva, J. of Supercrit. Fluid., 92, 115–176, 2014; [2] B. Zêzere, A. L. Magalhães, I. Portugal, C. M. Silva, J. of Supercrit. Fluid, 133, 297–308, 2018; [3] H. Liu, C. M. Silva, in Á. Mulero (Eds.), Lecture Notes in Physics 753 Theory and Simulation of Hard-Sphere Fluids and Related Systems, Springer, Berlin/Heidelberg, pp. 37–109, 2008; [4] H.Q. Liu, C.M. Silva, E.A. Macedo, Ind. Eng. Chem. Res., 36, 246-252, 1997; [5] A.L. Magalhães, S.P. Cardoso, B.R. Figueiredo, F.A. Da Silva, C.M. Silva, Ind. Eng. Chem. Res., 49, 7697– 7700, 2010; [6] T. Merzliak, A. Pfennig, Mol. Simul. 30, 459–468, 2004; [7] C.R. Wilke, P. Chang, A.I.Ch.E. J., 264–270. 1995; [8] Dymond, J. H., J. Chem. Phys., 60, 969–973, 1974.
135
EIFS 2020 PT04
Molecular dynamics simulation of diffusion coefficients in supercritical carbon dioxide
João Iglésias, Bruno Zêzere, Inês Portugal, José R. B. Gomes, Carlos Manuel Silva*
Department of Chemistry, CICECO, University of Aveiro, Aveiro, 38100-193, Portugal
GRAPHICAL ABSTRACT
ABSTRACT
Over the past years the interest in bioactive compounds from natural sources has been increasing together with the need to substitute conventional harmful organic solvents applied in solid-liquid extractions by greener alternatives. Therefore it is also necessary to investigate and determine equilibrium and transport properties of such greener systems, from which the tracer diffusion coefficients (𝐷𝐷12) can be emphasized [1]. This property is of chief importance for design and optimization of equipment and processes involving mass transfer phenomena like supercritical fluid extraction (SFE) [2]. The SFE is being widely studied for the extraction of bioactive compounds like squalene, the solute focused in this work, which can be obtained from vegetable matrixes with supercritical CO2 (SC-CO2) [3-4]. Research on hypothetical fluid models is particularly useful to understand the effect of molecular interactions upon their macroscopic properties. Comparing experimental data with calculated values on the basis of model fluids allows us to assess the extent to which a hypothetical system approximates the real one. Molecular dynamics (MD) simulation
136
is a widespread and potential approach that can be used to obtain such information/properties [2]. In this work, classical MD simulations using GROMACS [5] were employed to compute tracer diffusion coefficients (𝐷𝐷12) of squalene in SC-CO2. The results were compared with experimental data retrieved from the literature. The main trends were analyzed and discussed taking into account the most relevant theories of transport properties. ACKNOWLEDGEMENTS This work was developed in the scope of the project CICECO-Aveiro Institute of Materials (Ref. FCT UID/CTM/50011/2019), financed by National Funds through the FCT/MEC and when applicable co-financed by FEDER under the PT2020 Partnership Agreement. Bruno Zêzere thanks FCT for PhD grant SFRH/BD/137751/2018.
REFERENCES
[1] B. Zêzere, J. M. Silva, I. Portugal, J. R. B. Gomes, C. M. Silva, Sep. Purif. Technol., 234, 116046, 2020 ;
[2] H. Liu, C. M. Silva, in Á. Mulero (Eds.), Lecture Notes in Physics 753 Theory and Simulation of Hard-Sphere Fluids and Related Systems, Springer, Berlin/Heidelberg, pp. 37–109, 2008;
[3] M. M. R. De Melo, A. J. D. Silvestre, C. M. Silva, J. of Supercrit. Fluid., 92, 115–176, 2014;
[4] T. Rosales-Garcia, C. Jimenez-Martinez, G. Davila-Ortiz, Int. J. Environ. Agric. Biotechnol., 2, 1662-1670, 2017;
[5] E. Lindahl, M.J. Abraham, B. Hess, D. van der Spoel, GROMACS 2019.2 Source code, 2019.
137
EIFS 2020 PT05
Experimental measurements of diffusion coefficients in compressed liquids and supercritical fluids
Carlos Manuel Silva*, Bruno Zêzere, José R. B. Gomes, Inês Portugal
Department of Chemistry, CICECO, University of Aveiro, Aveiro, 38100-193, Portugal
GRAPHICAL ABSTRACT
ABSTRACT Eucalyptol is a high value monocyclic monoterpene possessing antioxidant features beneficial to human health [1]. Among others, it exhibits substantial antibacterial activity [2] and is present in medicinal drugs used as a remedy for symptoms of the common cold and other respiratory infections [1]. Furthermore, eucalyptol has some applications in the cosmetic industry and is used for food and beverage flavoring [3].
Over the last years demand of consumers for natural food and products, such as natural bioactive compounds like eucalyptol, has been increasing leading to a higher interest of both Industry and Academia for fruits and vegetables as a potential source. Extraction processes and equipment must be designed to achieve the large-scale production of natural bioactive compounds from such sources. Hence specific transport properties of bioactive compounds in solvents of interest must be known [4].
In this work, the diffusion coefficients (D12) of eucalyptol in supercritical fluids and in compressed liquids were experimentally determined. The measurements were carried out using “green solvents” [5], namely liquid ethanol and supercritical CO2 (SC-CO2) modified with ethanol, using one of the most well known chromatographic technics, the
138
chromatographic peak broadening (CPB) method [6]. The dependencies on temperature, pressure, density and Stokes-Einstein coordinates were analysed. Furthermore, the new experimental data were modelled using well-known equations, namely: the two hydrodynamic equations of Hayduk-Minhas [7] and Wilke-Chang [7-8]; the free-volume correlation of Dymond-Hildebrand-Batschinski (DHB) [9]; the hybrid model of Tracer Liu-Silva-Macedo (TLSM) and one of its correlations (TLSMd) [10]; and two of the empirical correlations of Magalhães et al [11].
ACKNOWLEDGEMENTS This work was developed in the scope of the project CICECO-Aveiro Institute of Materials (Ref. FCT UID/CTM/50011/2019), financed by National Funds through the FCT/MEC and when applicable co-financed by FEDER under the PT2020 Partnership Agreement. Bruno Zêzere thanks FCT for PhD grant SFRH/BD/137751/2018.
REFERENCES
[1] A.I. Caceres, B. Liu, S.V. Jabba, S. Achanta, J.B. Morris, S.-E., Br. J. Pharmacol., 174, 867-879, 2017;
[2] R. Moghimi, A. Aliahmadi, H. Rafati, Ultrason. Sonochem., 35, 415-421, 2017;
[3] M. Eggersdorfer, Terpenes in Ullmann’s, 6th ed., Ludwigs, 2002;
[4] R. Taylor, R. Krishna, Multicomponent mass transfer, Wiley Series in Chemical Engineering, John Wiley & Sons, Inc., New York, 1993;
[5] D. Prat, J. Hayler, A. Wells, Green Chem., 16, 4546-4551, 2014;
[6] T. Funazukuti, C.Y. Kong, S. Kagei. J. Chromatogr. A., 1037, 411-429, 2004;
[7] R.C. Reid, J.M. Prausnitz, B.E. Poling, The Properties of Gases & Liquids, 5th Ed., McGraw-Hill International Editions, New York, pp 11.1-11.55, 2001;
[8] C.R. Wilke, P. Chang, A.I.Ch.E. J., 264–270. 1995;
[9] Dymond, J. H., J. Chem. Phys., 60, 969–973, 1974;
[10] H.Q. Liu, C.M. Silva, E.A. Macedo, Ind. Eng. Chem. Res., 36, 246-252, 1997; [11] A.L. Magalhães, P.F. Lito, F.A. Da Silva, C.M. Silva, J. Supercrit. Fluids, 76, 94-144, 2013.
139
EIFS 2020 PT06
Prediction of diffusivities in supercritical carbon dioxide using machine learning models
José P.S. Aniceto*, Bruno Zêzere, Carlos M. Silva
CICECO, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT The knowledge of transport properties is required for the design, simulation and scale-up of separations and chemical reactions. In the case of the molecular diffusion coefficient, D12, it is fundamental to estimate dispersion coefficients, convective mass transfer coefficients, and catalysts efficiency factors [1]. Many such processes make use of supercritical carbon dioxide (SC-CO2) as it enables fine tuning the affinity of the solvent mixture to specific solutes [2]. Since experimental D12 data in SC-CO2 is not widely available, there is a significant demand for accurate models capable of providing reliable D12 estimations [3].
Currently, the Wilke-Chang equation [4], which is a modification of the Stokes–Einstein equation, is the most well-known and most used model to calculate solute diffusivities in SC-CO2. Recently, Artificial Intelligence models have been applied to the prediction of diffusivities of gases at atmospheric pressure [5] and binary diffusion coefficients of liquids [6].
140
In this work we applied machine learning algorithms to develop predictive models to estimate diffusivities of solutes in supercritical carbon dioxide. A large database of experimental data containing 21 properties for 174 solutes and 4917 data points (covering small and large molecules) was used in the training of the machine learning models. The database was randomly split 70/30 % into training and testing sets, respectively.
Three machine learning models were evaluated: a K-Nearest Neighbors model, a Decision Tree algorithm, and an Ensemble Method (Random Forest). The results were compared with a simple multi-linear regression and with the Wilke-Chang equation [4].
The best results were found using the Random Forest algorithm which showed an average absolute relative deviation (AARD) of 4.11 % (see Graphical Abstract) for the 1476 points in the test set (not used in model training). Fitting error was 2.13 %. This model has six parameters including temperature, pressure, density, solute molar mass, solute critical pressure and solute acentric factor. The K-Nearest Neighbors and Decision Tree models presented overall results between 4.8 % and 5.5 %.
By comparison the multi-linear regression obtained an AARD of 15.86 % and the Wilke-Chang equation resulted in an AARD of 12.41 % for the same test set.
ACKNOWLEDGEMENTS This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020 & UIDP/50011/2020, financed by national funds through the FCT/MEC and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement. Bruno Zêzere thanks FCT for PhD grant SFRH/BD/137751/2018.
REFERENCES
[1] Eduardo L.G. Oliveira, Armando J.D. Silvestre, and Carlos M. Silva. Review of kinetic models for supercritical fluid extraction. Chem. Eng. Res. Des., 89(7A):1104–1117, 2011.
[2] M.M.R. De Melo, A.J.D. Silvestre, C.M.Silva, J. Supercrit. Fluid., 92, 115–176, 2014.
[3] H. Liu, C.M. Silva, in Á. Mulero (Eds.), Lecture Notes in Physics 753 Theory and Simulation of Hard-Sphere Fluids and Related Systems, Springer, Berlin/Heidelberg, pp. 37–109, 2008.
[4] C.R. Wilke, P. Chang, A.I.Ch.E. J., 264–270. 1995.
[5] R. Eslamloueyan, M.H. Khademi, A neural network-based method for estimation of binary gas diffusivity, Chemom. Intell. Lab. Syst. 104 (2010) 195–204.
[6] R. Beigzadeh, M. Rahimi, S.R. Shabanian, Developing a feed forward neural network multilayer model for prediction of binary diffusion coefficient in liquids, Fluid Phase Equilib. 331 (2012) 48–57.
141
Poster Sessions
142
143
EIFS 2020 PM01
Modelling the in vitro release of Gemcitabine impregnated foams by high-pressure CO2
Irene Álvarez a, *, C. Gutiérrez a, A. de Lucas a, Ignacio Gracia a, Juan F. Rodríguez a,
M. Teresa García a a Institute of Chemical and environmental Technology (ITQUIMA). University of Castilla-La
Mancha. Avda. Camilo José Cela s/n, 13071 Ciudad Real, Spain. * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT Controlled release systems are formed by a polymer and a drug, which is released into the body in a pre-designed form. At present, one of the most widely used techniques in the synthesis of these systems is supercritical foaming and impregnation because it can be carried out in a single step [1, 2]. In particular, the use of supercritical carbon dioxide is suitable because its critical point is easy to reach, it is non-toxic, flammable and does not leave residues after its elimination.
During the foaming process, gas sorption in the polymer matrix results in a decrease in the glass transition temperature of the polymer, enhancing diffusion and facilitating a homogeneous impregnation of the drug in the interior of the polymer scaffolds [3]. This sorption leads to the nucleation of the bubbles. The formation and growth of the cells takes place during the depressurization stage as thermodynamic instability is produced. This growth finishes when the polymer returns to the glassy state [4]. Usually, polymer foaming is carried out at high temperature, but the use of polymeric solutions allows working at lower temperature.
In this work, Gemcitabine impregnation has been performed on PLGA microcellular scaffolds obtained from polymeric solutions of ethyl lactate. For this purpose, the effect of working pressure, temperature and the ratio between monomers of the polymer on the internal structure of the foams. In addition, this study was conducted for three initial drug loading in the polymeric matrix. Thermogravimetric Analysis (TGA), Fourier-Transform
144
Infrared Spectroscopy (FTIR) and Energy Dispersive Spectroscopy (EDS) analysis were accomplished to determine if Gemcitabine was impregnated and evenly distributed throughout the interior of the foam. Finally, the in vitro release profile was also studied and fitted to a mathematical model. In this model it was considered that the release process was divided into three different steps controlled by the external diffusion in the first place, by the internal transfer of mass in the second and then by the degradation of the polymer.
ACKNOWLEDGEMENTS The Spanish Ministry of Science and Innovation (CTQ2016-79811-P) and Junta de Castilla-La Mancha (PEII-2014-052-P), in part financed by the European Regional Development Fund (ERDF), have funded this work.
REFERENCES [1] R. Campardelli, P. Franco, E. Reverchon, I. De Marco, The Journal of Supercritical Fluids, 146, 47-54, 2019.
[2] L.I. Cabezas, I. Gracia, A. De Lucas, J.F. Rodríguez, Industrial and Engineering Chemistry Research, 53, 15374-15382, 2014.
[3] I. Álvarez, C. Gutiérrez, A. de Lucas, J.F. Rodríguez, M.T. García, The Journal of Supercritical Fluids, 104637, 2019.
[4] C. Gutiérrez, J.F. Rodríguez, I. Gracia, A. de Lucas, M.T. García, Chemical Engineering and Technology, 37, 1845-1853, 2014.
145
EIFS 2020 PM02
Supercritical impregnation of bioactive extracts in alginate wound dressing
Elisabeth Gómez-Cepero, M. Teresa Fernández-Ponce, Cristina Cejudo, Lourdes Casas,
Casimiro Mantell, Enrique Martínez de la Ossa, Clara Pereyra* a Chemical Engineering and Food Technology Department, Science Faculty, University of
Cádiz * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT The Mangifera Indica tree, commonly known as mango, has great potential as an alternative source of natural compounds with high bioactivity. The production of this plant generates considerable agro-industrial waste throughout the entire production chain. These wastes, specifically the leaves, are a very important source of bioactive compounds of high added value, and therefore, the recovery of these wastes can be important in various sectors such as pharmaceutical, cosmetic, food, etc [1-5].
This work focuses on the extraction of bioactive compounds present in mango leaf extracts, for subsequent supercritical impregnation in calcium-sodium alginate dressings for pharmaceutical purposes.
The extraction technique used is the improved extraction and is carried out for two hours at 200 bar pressure and 80 ⁰C of temperature with CO2 + 50% ethanol as solvent. The bioactivity of the extract obtained was evaluated by antioxidant, antidiabetic and antimicrobial activity against S. aureus. [6-10].
Subsequently, the extract was impregnated in calcium-sodium alginate dressings by supercritical CO2, at different conditions of pressure (200, 300 and 400 bar) and temperature (35 and 55 ⁰C). The impregnated dressings were studied to assess whether they maintained the extract's functionality. The results showed that the best impregnation conditions are at 200 bar and 55 ⁰C and that the dressings continue to maintain the antioxidant, antidiabetic and antimicrobial properties of the extract, demonstrating that
146
the dressing is capable of retaining the bioactive compounds of the leaf extract, after the impregnation process with supercritical CO2. These results guaranty the possible to develop new products with biomedical applications using this methodology.
ACKNOWLEDGEMENTS We gratefully acknowledge the Spanish Ministry of Science and Technology (Project CTQ2017-86661-R) and European Regional Development Funds (UNCA10-1E-1125 and 18INIA1103. 2011) for the financial support.
REFERENCES
[1] C.M. Ajila, K.A. Naidu, S.G. Bhat, U.J.S. Prasada Rao, Food Chemistry, 105, 982–988, 2007.
[2] J. Pan, X. Yi, S. Zhang, J. Cheng, Y. Wang, C. Liu, X. He, Bioactive phenolics from mango leaves (Mangifera indica L.). Industrial Crops and Products, 2018.
[3] M.T. Fernández-Ponce, E. Medina-Ruiz, L. Casas, C. Mantell, E. J. Martínez de la Ossa-Fernández, Development of cotton fabric impregnated with antioxidant mango polyphenols by means of supercritical fluids. Journal of Supercritical Fluids, 2018.
[4] M.T. Fernández-Ponce, B. Razi Parjikolaei, H. Nasri Lari, L. Casas, C. Mantell, E.J. Marínez de la Ossa, Chemical Engineering Journal, 299, 420-430, 2016.
[5] M.T. Fernández-Ponce, L. Casas, C. Mantell, E.M. de la Ossa, Innovative Food Science and Emerging Technologies, 29, 94–106, 2015.
[6] W. Brand-Williams, M. E. Cuvelier, C. Berset, Use of a free radical method to evaluate antioxidant activity, LWT - Food Science and Technology, 1995.
[7] R. Scherer, H. T. Godoy, Food Chemistry 112(3), 654–658, 2009.
[8] Pistia-Brueggeman & Hollingsworth, ChemInform Abstract: A Preparation and Screening Strategy for Glycosidase Inhibitors. ChemInform, 33(5), 2010.
[9] J. Gabrielson, M. Hart, A. Jarelo, I. Ku, D. Mckenzie, R. Mo, Journal of Microbiol. Methods 50, 63–73, 2002.
[10] S.H. Moussa, A.A. Tayel, A.A. Al-hassan, A. Farouk, Tetrazolium / Formazan Test as an Efficient Method to Determine Fungal Chitosan Antimicrobial Activity, Journal of Mycology, 2013.
147
EIFS 2020 PM03
Nanolubricants based on silane-coated nanoparticles using supercritical CO2
Fátima Mariñoa, Víctor Santos-Rosalesb, Carlos A. García-Gonzálezb, Josefa Fernándeza*, Enriqueta R. Lópeza
a Laboratorio de Propiedades Termofísicas, Grupo NaFoMat, Departamento de Física Aplicada, Facultad de Física, Agrupación Estratégica de Materiales (AeMAT), Universidade de
Santiago de Compostela, 15782, Santiago de Compostela, Spain b Departamento de Farmacología, Farmacia y Tecnología Farmacéutica, I+D Farma group
(GI-1645), Facultad de Farmacia, Agrupación Estratégica de Materiales (AeMAT) and Health Research Institute of Santiago de Compostela (IDIS), Universidade de Santiago de Compostela
15782, Santiago de Compostela, Spain * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT About 23% (119 EJ) of the world’s total energy consumption is spent in overcoming friction and to remanufacture worn parts and spare equipment due to wear and wear-related failures [1]. Nanolubricants, i.e. nanoparticles dispersions in lubricants, have shown great potential due to the friction and wear reductions [2]. Different nanoparticles have been used, such as inorganic nanoparticles or carbon-based materials [3]. However, the dispersion of nanoparticles in base oils is not always stable, this could lead to damage in the machinery, by additives loss or efficiency reduction of the lubricant. Nanoparticles aggregation also limits the lubricating performance. Several methods have been developed to improve dispersion stability among which stand out nanoparticles surface modification [4]. Surface modification consists in the functionalization of the nanoparticles with dispersants or other organic molecules with functional groups that can
148
react with the nanoparticles. In a recent review [4] it has been concluded that the surface silanization has a clear advantage because of its higher grafting density and versatility.
In this work, magnesium oxide (MgO) and graphene nanoplatelets (GnP) were functionalized with octyltriethoxysilane using supercritical CO2 as processing medium, applying two different reaction conditions to compare the stability of nanoparticles varying the coating density [5,6]. Silanized nanoparticles were characterized using IR and X-ray diffraction techniques to verify the synthetic method. In addition, dispersions of the silanized nanoparticles, in a polyalphaolefin PAO40 and in a mineral oil which belongs to the G-III group according to the API classification were prepared in order to study their stability through visual and refractometric methods and their friction and wear reducing capabilities.
ACKNOWLEDGEMENTS Authors acknowledge Repsol for providing us the PAO40 and G-III samples. This work was supported by Agencia Estatal Investigación (AEI), MINECO, MCIUN, and the ERDF program through the RTI2018-094131-A-I00 and ENE2017-86425-C2-2-R projects, by Xunta de Galicia (ED431E 2018/08, ED431F 2016/010, GRC ED431C 2016/008 and GRC ED431C 2016/001). C.A.G.-G. acknowledges to MINECO for a Ramón y Cajal Fellowship (RYC2014-15239). V.S.-R. acknowledges to Xunta de Galicia (Consellería de Cultura, Educación e Ordenación Universitaria) for a predoctoral research fellowship (ED481A-2018/014).
REFERENCES
[1] K. Holmberg, A. Erdemir, Friction, 5, 263-284, 2017.
[2] W. Dai, B. Kheireddin, H. Gao, H. Liang, Tribology International, 102, 88-98, 2016.
[3] G. Paul, H. Hirani, T. Kuila, N.C. Murmu, Nanoscale, 11, 3458-3483, 2019.
[4] Y. Chen, P. Renner, H. Liang, Lubricants, 7, 7, 2019.
[5] C.A. García-González, J. Saurina, J.A. Ayllón, C. Domingo, J. Phys. Chem. C, 113, 13780–13786, 2009.
[6] C.A. García-González, J. Fraile, A. López-Periago, J. Saurina. C. Domingo, Ind. Eng. Chem. Res., 48, 9952–9960, 2009.
149
EIFS 2020 PM04
Green revalorization strategy following an adsorbent-assisted supercritical CO2 extraction of terpenoids from olive leaves.
Evaluation of the neuroprotective effects of the obtained extracts
Zully Suárez-Montenegroa*, Mónica Buenoa, Gerardo Álvarez-Riveraa, Jose A.
Mendiolaa, Alejandro Cifuentesa, Elena Ibáñeza a Laboratory of Foodomics, Institute of Research in Food Science (CIAL), Madrid, España
GRAPHICAL ABSTRACT
ABSTRACT Alzheimer´s disease (AD) is one of the main neurodegenerative disorders affecting elderly. Thus far, the pathophysiology of AD is not completely clear, and there is not an effective treatment for this disease yet. AD is a complex neurological pathology associated with multiple factors, some of them are related with the cholinergic activity and the increase in oxidative stress. Acetylcholinesterase (AChE) is one of the enzymes responsible for the development of some AD symptoms [1]. The main physiological function of AChE is the splitting of acetylcholine (ACh), a mediator of cholinergic synapses, during the transduction of nerve impulses [2]. Moreover, oxidative damage occurs as a result of excessive free radical production and the formation of Reactive Oxygen Species (ROS) [3] involved in disease-related neurodegeneration. Therefore, one of the promising therapeutic strategies is the inhibition of AChE and the reduction of the neurological effects caused by oxidative stress.
150
Olive leaf is an important agricultural residue in Spain and other olive oil producing countries, resulting from the pruning of olive trees and the cleaning of the olives before oil production. This residue is a promising natural source of bioactive compounds such as terpenoids. This by-product can provide all kinds of terpenoid structures, ranging from C10-C40. Triterpenoids derived from oleanane and ursane have been reported to have anti-neurodegenerative activity [4].
Therefore, this work was oriented towards the valorization of olive leaves through integrated supercritical fluid extraction (SFE) and on-line adsorption process, using supercritical carbon dioxide as solvent, in order to obtain different families of bioactive terpenoids with neuroprotective activity, as a therapeutic approach in delaying the detrimental effects of AD.
The extraction procedure was performed at 300 bar and 60°C during different times ranging from 0 to 120 min, followed by an adsorption step with different adsorbents materials, such as silica gel, molecular sieves and aluminum oxide, among others. Then, SFE extracts obtained at different times, and the compounds recovered from the adsorbents were characterized by gas chromatography - mass spectrometry (GC-MS-QTOF). Results showed that molecular sieves have the highest adsorption capacity, whereas silica gel produced extracts with different abundance of target terpenoids, thus providing extracts with diverse anti-cholinergic and antioxidant activities.
In conclusion, obtained results guide us to propose a silica gel adsorbent-assisted SFE strategy to obtain selective terpenoids rich extracts from olive leaves. Furthermore, new compounds with potential AChE inhibitory and antioxidant activities have been identified.
ACKNOWLEDGEMENTS This work was supported by the project AGL2017-89417-R (MINECO, Spain). Z.S.M. would like to acknowledge the University of Nariño (Colombia) for financial support. M.B. and G. A-R acknowledge MINECO for the “Juan de La Cierva-Formación” postdoctoral grants FJCI-2016-30902 and FJCI-2015-25504, respectively.
REFERENCES
[1] P. De Jager, L. Ma, Y. McCabe, C. Xu, J. Vardarajan, B.N. Felsky, D. Bennett, Scientific Data, 5, 1–13, 2018.
[2] G.M. Chuiko, V.A. Podgornaya, Y.Y. Zhelnin, Biochemistry and Molecular Biology, 135, 55–61, 2003. [3] S.C._Bondy, A. Campbell, (eds.), Inflammation, Aging, and Oxidative Stress, Springer International Publishing, Switzerland, pp. 95-97, 2016. [4] P. Ruszkowski, T. Bobkiewicz-Kozlowska, Mini. Rev. Org. Chem., 11, 37-315, 2014.
151
EIFS 2020 PM05
Strategies for the processing of medicated scaffolds for bone repair by supercritical foaming
Ana Iglesias-Mejutoa,*, Víctor Santos-Rosalesa, Carmen Álvarez-Lorenzoa, Philip
Jaegerb, José Luis Gómez-Amozaa, Carlos A. García-Gonzáleza a* Department of Pharmacology, Pharmacy and Pharmaceutical Technology, I+D Farma group (GI-1645), Faculty of Pharmacy, Agrupación Estratégica de Materiales (AeMAT) and Health
Research Institute of Santiago de Compostela (IDIS), Universidade de Santiago de Compostela, E-15782 Santiago de Compostela, Spain.
b Eurotechnica GmbH, An den Stücken 55, D-22941 Bargteheide, Germany. * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT
The current increase in the life expectancy makes diseases and disorders associated with age like bone pathologies more prevalent and urges the research in new bone repair strategies (1). Biopolymeric scaffolds are an alternative bone repair material to biological grafts able to promote bone healing in situations where self-regeneration is compromised. These synthetic porous structures act as provisional mechanical supports and serve as a 3D-template for cell colonization and subsequent tissue ingrowth (1,2).
Bioactive compounds can be incorporated to scaffolds for local administration to favor the effectiveness of bone healing. Current scaffold processing techniques have severe limitations to incorporate bioactive compounds to scaffold structure. Usually, these methods need organic solvents, high temperatures or multi-step processing which might originate cytotoxicity problems, premature drug degradation and long processing times
152
(1). Supercritical foaming of polymeric scaffolds emerge as the unique green technology and one-step method to generate highly porous scaffolds loaded with bioactive agents and with high incorporation yields (1,2). The supercritical foaming liquefies the polymer at temperatures below its melting point and allows its processing at mild conditions that are compatible with thermally sensitive bioactive compounds like dexamethasone (a glucocorticoid with an osteogenic differentiation action) or ketoprofen (an anti-inflammatory drug).
In this work, we generate poly(ε-caprolactone) (PCL) scaffolds with attractive morphological properties. Scaffolds with biodegradation rates in the range from weeks to months and suitable for bone repair applications were prepared by supercritical foaming (37ºC, 140 bar). The resulting scaffolds have high porosities (60- 70%) with pore sizes between 100 and 200 μm, a smooth surface and low-to-medium interconnectivity. The pore surface roughness and pore interconnectivity can be increased during foaming process with the use of aerogel microparticles in the scaffold formulations. The intrinsic lightweight of aerogels (85–95% porosity) also contributed to the increase in the porosity of the scaffolds and pore size, obtaining macropores in the 100–300 μm range. Finally, in vivo test (Sprague-Dawley rats) highlighted the bone regeneration capacity (39% of bone repair at 14 weeks post-implantation) of PCL scaffolds loaded with aerogel microparticles and dexamethasone obtained by supercritical foaming.
ACKNOWLEDGEMENTS Work supported by Xunta de Galicia [ED431F 2016/010 & ED431C 2016/008], MCIUN [RTI2018-094131-A-I00], Agrupación Estratégica de Materiales [AeMAT-BIOMEDCO2, ED431E 2018/08], Agencia Estatal de Investigación [AEI] and FEDER funds. C.A.G.-G. acknowledges to MINECO for a Ramón y Cajal Fellowship [RYC2014-15239]. Work carried out in the frame of the COST Action CA18125 “Advanced Engineering and Research of aeroGels for Environment and Life Sciences” (AERoGELS) and funded by the European Commission.
REFERENCES
[1] L. Goimil, M.E.M. Braga, A.M.A. Dias, J.L. Gómez-Amoza, A. Concheiro, C. Alvarez-Lorenzo, H.C. De Sousa, C.A. García-González, Journal of CO2 Utilization, 18, 237-249, 2017.
[2] L. Goimil, V. Santos-Rosales, A. Delgado, C. Évora, R. Reyes, A.A. Lozano-Pérez, S.D. Aznar-Cervantes, J.L. Cenis, J.L. Gómez-Amoza, A. Concheiro, C. Álvarez-Lorenzo, C.A. García-González, Journal of CO2 Utilization, 31, 51-64, 2019.
153
EIFS 2020 PM06
Aerogels made of graphene oxide and metal-organic frameworks for gas separation
Alejandro Borrás,
a A. Rosado,
a J. Navarro,
b Julio Fraile,
a J. G. Planas,
a Ana M. López-
Periagoa, Concepción Domingo,a Amirali Yazdi
a
a Materials Science Institute of Barcelona (ICMAB-CSIC), Campus UAB s/n, Bellaterra, 08193, Spain
b Departamento de Química Inorgánica Universidad de Granada, Av. Fuentenueva s/n, Granada, 18071, Spain
GRAPHICAL ABSTRACT
ABSTRACT
Gelation of metal-organic frameworks (MOFs) under specific synthetic conditions opens up a new pathway to fabricate hierarchically porous MOF monoliths, which could be implemented directly into adsorptive applications. However, due to the complexity of MOFs synthetic conditions, fabrication of different types of MOFs into a form of a monolith might be difficult. Additionally, the combination of graphene-based materials and MOFs as a composite have received tremendous attention in the past years due to their superior physiochemical properties in comparison to the parent materials [1]. However, the development of monolithic structures in the form of an aerogel for these multifunctional materials has not been explored thoroughly. Here in, we report a novel and green general method using super critical carbon dioxide (scCO2) [2] to fabricate hybrid aerogels containing HKUST-1 or ZIF-8 MOFs and graphene oxide. Furthermore, we extend the method to fabricate aerogels inside columns for gas separation purposes. Two main procedures have been developed to fabricate these aerogels:
154
(i) Direct mixing, in which the first step consists of dispersing via sonication the pre-synthetized MOF nanoparticles into an alcoholic dispersion of GO, and then applying the scCO2 treatment for aerogel formation. (ii) In-situ growth, in which the nano-MOF crystals are grown from the precursors in the presence of dispersed GO, and then gelled and dried in scCO2. Obtained systems are described by using typical solid characterization techniques (XRD, FTIR, XPS, EDS, etc.). Low temperature N2 adsorption/desorption analysis indicates a mesoporous matrix with microporous porosity given by the added MOF. scCO2 drying methodology enables the fabrication of aerogels of GO@MOF inside a column for gas separation applications. As a proof-of-concept, the system GO@HKUST-1 was further studied for CO2/N2 separation. GO@HKUST-1 one-pot column with 75 wt.% MOF content demonstrated a breakthrough time of 12.5 min g-1 for N2/CO2 separation (CO2 uptake of 1.37 mmol g-1) and the separation properties were almost not altered after seven cycles.
ACKNOWLEDGMENTS Spanish National Plan of Research CTQ2017-83632, Severo Ochoa Program for Centers of Excellence in R&D (SEV-2015-0496) and ELENA project (Exploring the Limits of the Uniqueness of Hierarchical Hybrid Adsorbents for Energy Applications). REFERENCES [1] Y. Zheng, S. Zheng, H. Xue, H. Pang, Adv. Funct. Mater. 2018, 28 (47), 1804950 [2] A. Borrás, G. Gonçalves, G. Marbán, S. Sandoval, S. Pinto, P.A.A.P: Marques, J. Fraile, G. Tobias, A.M. López-Periago, C. Domingo, Chem. Eur. J. 2018, 24 (59), 15903-15911.
155
EIFS 2020 PM07
The role alginate-nanohydroxyapatite hydrogel on osteogenic response activation of mesenchymal cells
Joana Barrosa, Maria Pia Ferraz c, Joana Azeredo b, M. H. Fernandes d,e, P. S. Gomes d,e,
Fernando J. Monteiro a
a I3S – Instituto de Investigação e Inovação em Saúde, Universidade do Porto, INEB – Instituto de Engenharia Biomédica, FEUP – Faculdade de Engenharia, Universidade do Porto,
Portugal; b Laboratório de Investigação em Biofilmes Rosário Oliveira, Center of Biological Engineering,
University of Minho, Braga, Portugal; c FP-ENAS/CEBIMED –Energy, Environment and Health Research Unit/Biomedical Research
Center, University Fernando Pessoa, FCS-Faculdade de Ciências da Saúde, Universidade Fernando Pessoa, Porto, Portugal;
d Laboratory for Bone Metabolism and Regeneration – Faculty of Dental Medicine, U. Porto—Porto, Portugal;
e REQUIMTE/LAQV - U. Porto – Porto, Portugal. * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT Ceramic/polymer-based composites have emerged as potential biomaterials to fill, replace, repair or regenerate injured or diseased bone, due to their outstanding features in terms of biocompatibility, bioactivity, osteogenicity, injectability, and biodegradability [1, 2]. This functional synergism could improve both the physico-chemical and biological properties of the composite, consequently enhancing bone regeneration [1, 2]. However, these properties depend on the amount of ceramic component present in the polymer-based composite, since the amount of ceramic can modulate cellular behavior, through different signaling pathways, and consequently influence the bone mineralization process and bonding to the surrounding tissues [2]. In this study, different nanohydroxyapatite concentrations (0, 30, 50 and 70 %) were entrapped into alginate hydrogel, and their role on biological response was evaluated trough cytocompatibility and osteogenic activation.
156
All used composites showed sustained cell viability, without affecting the cellular and mitochondrial morphology and structure over 21 days of culture. However, cell proliferation was affected by nanohydroxyapatite content. Alginate hydrogel with nanohydroxyapatite at 30% promoted increased cell proliferation when compared to those with higher nanoHA content (50 and 70%), underlining the importance of nanoHA content for the bioactivity of the composite. The osteogenic response was also affected by the nanohydroxyapatite content. The composites with the lowest nanohydroxyapatite concentration induced significant expression of Runx2, the main transcriptional factor of osteoblastic differentiation. Besides, they also increased the expression of Col1a1 and BGLAP to similar levels to those attained in cells exposed to osteogenic medium, supporting the osteogenic activation. The results showed that the nanohydroxyapatite content had a crucial role in the biological response of the composite. Moreover, among the composites studied, the alginate hydrogel with 30% nanohydroxyapatite showed to maximize the osteoblastic cells’ proliferation and osteogenic activation, which could contribute to improved bone regeneration.
ACKNOWLEDGEMENTS This work was financed by FEDER – Fundo Europeu de Desenvolvimento Regional funds through the COMPETE 2020 – Operacional Programme for Competitiveness and Internationalisation (POCI), Portugal 2020, by Portuguese funds through FCT/MCTES in the framework of the project “institute for Research and Innovation in Health Sciences (POCI-01-0145-FEDER-007274), by Project Biotherapies (NORTE-01-0145-FEDER-000012) and by Joana Barrosʼ PhD grant (SFRH/BD/102148/2014).
REFERENCES
[1] M. Nabavinia, A.B. Khoshfetrat, H. Naderi-Meshkin, Material Science and Engineering C, 97, 67-77. 2019.
[2] J. Barros, M.P. Ferraz, J. Azeredo, M.H. Fernandes, P.G. Gomes, F.J. Monteiro, Material Science and Engineering C, 105, 109985, 2019.
[3] S. Eosoly, N.E. Vrana, S. Lohfeld, M. Hindie, Material Science and Engineering C, 32, 2250-2257, 2012.
157
EIFS 2020 PM08
Preparation of advanced drug delivery systems containing gold nanoparticles using supercritical CO2
Albertina Cabañasa,*, Jonathan Bermúdezb, M.J. Tenorio a,c, Eduardo Sáncheza, Isaac
A. Cuadraa, Concepción Pandoa, Diego Felipe Tiradob, Lourdes Calvob a Physical Chemistry Dep., b Chemical Engineering and Materials Dep., Universidad
Complutense de Madrid, 28040 Madrid
cCurrent address: Chemical, Energy and Mechanical Technology Dep., Universidad Rey Juan Carlos, Madrid, Spain
GRAPHICAL ABSTRACT
ABSTRACT The design of multifunctional drug formulations with high bioavailability is a key aspect in pharmaceuticals development. In this communication, the preparation of advanced drug delivery systems including Au nanoparticles (NPs) using supercritical CO2 is proposed. Gold has low inherent toxicity and high biocompatibility. [1] Furthermore gold NPs absorb radiation due to the plasmon resonance phenomena, causing local heating of the material. This fact has been exploited in cancer therapies to induce cell death (photothermia) [2] and it can be also used in advanced drug delivery formulations. For example, in systems formed by an Active Pharmaceutical Ingredient (API), Au NPs and a temperature sensitive polymer, local heating induced by light can trigger the release of the API.
Materials were prepared following two different techniques: (i) Impregnation using scCO2 as the solvent and (ii) the Supercritical AntiSolvent Technique (SAS) using CO2 as an antisolvent.
158
AuCl4·3H2O dissolved in ethanol + CO2 mixtures was used as precursor. First, the solubility of the precursor and its stability in the mixture was assessed using a high-pressure variable volume view cell following the procedure previously described.[3] The salt (y= 1.3 10-4) was dissolved at 40ºC and 8.6 MPa in a 20% mol ethanol + CO2 mixture. At this concentration, the precursor started to decompose at 60ºC yielding Au metal NPs.
AuCl4·3H2O was used to impregnate a mesoporous SiO2 SBA-15 support in the ethanol + CO2 mixture at 40 ºC and 9.5 MPa. Previously, the silica surface was functionalized with thiol groups in supercritical CO2.[4] The metal precursor decomposed insitu at 80ºC yielding Au NPs (7 nm wide) within the support pores.
Furthermore, the preparation of polymeric particles containing Au NPs was attempted by SAS. An ethanol solution of Eudragit L100 (Poly(methacylic acid-co-methyl methacrylate) 1:1) and the metal salt was precipitated by SAS at 40-60ºC and 10.0-15.0 MPa. The metal decomposed during the precipitation process and was incorporated into the polymeric particles. At 40ºC and 150 bar, polymer NPs of ca. 190 nm containing ca. 3% Au mass (EDX) were obtained. Precipitation process was affected by the Au NPs. This is the first time that the reactive precipitation of the gold precursor has been attempted by SAS.
These composite materials could be loaded in a further step with other APIs becoming advanced drug delivery systems. The examples provided illustrate the versatility of the supercritical fluid technologies in the preparation of drug formulations.
ACKNOWLEDGEMENTS We acknowledge financial support from the Spanish Ministry of Economy and Competitiveness (MICINN), research projects MAT2017-84385-R.
REFERENCES
[1] A. K. Khan, R. Rashid, G. Murtaza, A. Zahra Tropical Journal of Pharmaceutical Research, 13, 1169-1177, 2014.
[2] Yao, L. Zhang, J. Wang, Y. He, J. Xin, S. Wang, H. Xu and Z. Zhang, Journal of Nanomaterials, Article ID 5497136, 2016.
[3] E. Pérez, A. Cabañas, Y. Sánchez-Vicente, J.A.R. Renuncio, C. Pando, The Journal of Supercritical Fluids, 46(3), 238-244, 2008.
[4] M.J. Tenorio, C. Carnerero, M.J. Torralvo, C. Pando, A. Cabañas, Microporous and Mesoporous Materials, 256 (15), 147-154, 2018.
159
EIFS 2020 PM09
Searching a way of controlling the Pine Wood Nematode insect vector using PCL based matrices obtained by
supercritical CO2 foaming
João Leocádioa, Marisa C. Gaspara, Fernando Bernardoa, Pedro Navesb, Edmundo Sousab,
Hermínio C. de Sousaa, Mara E. M. Bragaa* a Chemical Process Engineering and Forest Products Research Centre (CIEPQPF),
Department of Chemical Engineering, University of Coimbra, 3030-790 Coimbra, Portugal b Unidade Estratégica de Investigação e Serviços de Sistemas Agrários e Florestais e Sanidade
Vegetal, Instituto Nacional de Investigação Agrária e Veterinária (INIAV), Quinta do Marquês, 2780-159, Oeiras, Portugal
GRAPHICAL ABSTRACT
ABSTRACT Triggered by the pine wood nematode (PWN), Bursaphelenchus xylophilus, pine wilt disease (PWD) leads to death of different pine species translating into significant ecological and economic losses. This invader organism is currently widespread in several regions of the world, including Portugal and Spain, where it essentially colonizes Pinus pinaster. Its dispersion is due to insect vectors of the genus Monochamus and, in these countries, M. galloprovincialis is the only identified species transmitting the PWN. Therefore, it is important to monitor and control these beetles to prevent the infection of healthy trees. In this sense, baited traps containing phytochemicals and/or aggregation pheromones have been used to capture these insects, but those products still present some limitations [1]. To overcome issues related to the effectiveness, duration of action and ease of application the main aim of this study is the development of formulations based
160
on the biodegradable polymer poly(e-caprolactone) (PCL) containing attractive compounds to PWN insect vectors, processed by supercritical CO2 (scCO2) foaming. To select attractive compounds, wind tunnel (200 × 80 cm) assays, at constant wind speed of 40m.s-1, using both male and female insects in sexual maturation phase were conducted, revealing positive responses to α/β-pinene, δ-3-carene and β-caryophyllene. Thus, we firstly incorporated α-pinene as a model molecule in PCL in order to define the process conditions. Three different pressures were applied (133, 164 and 212 bar) at 40ºC for two and a half hours before pressure quench at 10 bar/min. After this first step, previously obtained scCO2 P. pinaster extracts already analyzed were enriched with the attractive compounds (α/β-pinene, δ-3-carene and β-caryophyllene) to be then incorporated in the porous matrices. Those extracts revealed the presence of abietadiene, which may probably be due to a defensive response [2]. Furthermore, those extracts exhibited acetylcholinesterase (AChE) inhibitory activity, corresponding to a possible nematicidal/insecticidal potential [3]. All the resulting monoliths were evaluated in terms of their volatiles release and impregnation capability by gravimetric assays and gas chromatography by solid-phase microextraction (SPME-GC-FID/MS) using a wind tunnel. Regarding the first study with α-pinene, analogous mass loss of the monoliths was noticeable up to seven days. After 30 days, the tested monoliths had already released more than 90% of the initial loading. Despite that, even at a lower rate, monoliths with α-pinene released beyond 100 days, noticing the aroma and mass loss. To improve and avoid burst effect on the initial release profile we tested two different approaches: inclusion of sawdust (40%, w/w), and coating of monoliths using a cellulose membrane. An increasing of α-pinene loading was obtained by incorporation of sawdust, and a linear profile was achieved using cellulose membranes as a barrier. The enriched pine extracts with α/β-pinene, δ-3-carene and β-caryophyllene are currently being tested in a wind tunnel, and further assays with insects will be performed.
ACKNOWLEDGEMENTS This work was financially supported by COMPETE 2020, Fundação para a Ciência e Tecnologia (FCT, Portugal), through the Project ECOVECTOR - POCI-01-0145-FEDER-016820; Programa de Atividades Conjuntas (PAC) MultiBiorefinery - POCI-01-0145-FEDER-016403; and FCT-MEC (PEst-C/EQB/UI0102/2013, Est-C/EQB/UI0102/2018 and PEst-C/EQB/UI0102/2019). M. E. M. Braga acknowledges FCT for the financial support through the Post-Doctoral FCT fellowship (SFRH/BPD/101048/2014) and M. C. Gaspar acknowledges FCT for the financial support through the Scientific Employment Stimulus 2017 (CEECIND/00527/2017), and post-doctoral fellowship from MultiBiorefinery project.
REFERENCES
[1] P. Naves, L. Bonifácio, E. de Sousa, The Pine Wood Nematode and its local vectors in the Mediterranean Basin BT - Insects and Diseases of Mediterranean Forest Systems, T. D. Paine and F. Lieutier, Eds. Springer International Publishing, Cham, Switzerland, pp. 329–378, 2016.
[2] M.C. Gaspar, H.C. de Sousa, I.J. Seabra, M.E.M. Braga. Environmentally-safe scCO2 P. pinaster branches extracts: composition and properties. Submitted in the revised format to the Journal of CO2 utilization (JCOU_2019_254).
[3] Y. Xia, Y. Qi, X. Yu, B. Wang, R. Cao, D. Jiang, European Journal of Plant Pathology, 153(1), 239–250, 2019.
161
EIFS 2020 PM10
Supercritical CO2 impregnation of PLA/PCL film with carvacrol for food active packaging
Ivana Lukica,*, Jelena Vulicb, Stoja Milovanovica, Jasna Ivanovica
a University of Belgrade, Faculty of Technology and Metallurgy, Karnegijeva 4, 11000 Belgrade, Serbia
b University of Novi Sad, Faculty of Technology, Bulevar Cara Lazara 1, 21000 Novi Sad, Serbia
GRAPHICAL ABSTRACT
ABSTRACT Food active packaging is an innovative approach which aims to extend shelf-life by improving safety of food products while maintaining their quality [1]. Active packaging systems are based on materials in which active substances with antimicrobial and/or antioxidant properties are incorporated into the polymer matrix, with the tendency to follow the trend towards natural-based and eco-friendly alternatives. Carvacrol, phenolic monoterpene present in oregano and thyme essential oils, is already well known for its strong antimicrobial and antioxidant activity [2]. Blending of two biodegradable polymers, poly(lactic acid) (PLA) and poly(ε-caprolactone) (PCL) enables formation of new biomaterials with improved mechanical, thermal and biodegradation properties [3].
Present study was aimed to produce biodegradable film with antioxidant activity for active food packaging. Films of PLA with 5wt% of PCL (denoted as PLA-5) prepared by solvent casting method were loaded with carvacrol (C) using supercritical CO2 at temperature of 40 °C and pressure of 10 MPa. Morphological, structural and mechanical
162
properties of the obtained PLA-5/C film containing 21.83% of carvacrol were investigated. Antioxidant activity of prepared film was evaluated using 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical scavenging and reducing power assays, and the total polyphenolic content was determined. Kinetics of carvacrol release from PLA-5 film was investigated. The slow release of active component (49.03% of initially loaded in the film) into distilled water over longer time (6 weeks) was observed. Film with the homogeneous distribution of active component within the polymer was produced, which was confirmed using gravimetric, UV-Vis and HPLC methods. FTIR analysis revealed that carvacrol interacted with polymer matrix through intermolecular hydrogen bonds between their terminal hydroxyl group and carbonyl groups of the ester moieties of both PLA and PCL [3]. Supercritical CO2 impregnation process enabled preparation of PLA-5 film with homogeneous distribution, good antioxidant activity and improved flexibility and elasticity.
ACKNOWLEDGEMENTS Financial support of the Ministry of Education, Science and Technological Development of the Republic of Serbia (Project III45017 and III45001) is gratefully acknowledged. Work carried is out in the frame of the COST-Action "Green Chemical Engineering Network towards upscaling sustainable processes" (GREENERING, ref. CA18224) funded by the European Commission.
REFERENCES
[1] C. Vilela, M. Kurek, Z. Hayouka, B. Röcker, S. Yildirim, M.D.C. Antunes, J. Nilsen-Nygaard, M.K. Pettersen, C.S.R. Freire, Trends in Food Science & Technology, 80, 212–222, 2018.
[2] M. Ramos, A. Jiménez, M. Peltzer, M.C. Garrigós, Journal of Food Engineering, 109, 513–519, 2012.
[3] S. Milovanovic, G.Hollermann, C. Errenst, J. Pajnik, S. Frerich, S. Kroll, K. Rezwan, J.Ivanovic, Food Research International, 107, 486–495, 2018.
163
EIFS 2020 PM11
Inactivation of Salmonella Enteritidis in liquid whole egg with supercritical carbon dioxide in isolation and in combination
with cinnamaldehyde
María Teresa Valverdea, Diego F. Tiradob, Amaury Taboada-Rodrígueza, Fulgencio Marín-Iniestaa, Lourdes Calvob, *
a Grupo Biotecnología de Alimentos, Facultad de Veterinaria, Universidad de Murcia, Campus de Espinardo, CP 30100 Murcia, España
b Departamento de Ingeniería Química, Facultad de Químicas, Universidad Complutense de Madrid, 28040 Madrid, Spain
GRAPHICAL ABSTRACT
ABSTRACT Egg products are widely used by the food service industry and commercial food manufacturers because of its convenience and ease of handling and storage as compared to shell eggs. However, these products are responsible for many foodborne illnesses, mainly caused by Salmonella enterica, constituting a significant health risk and a source of high economic losses. Consequently, the European Regulation is very stringent, so it requires the absence of Salmonella in 25 g o ml of liquid whole egg (LWE). For this reason, pasteurized liquid egg products have replaced raw eggs in restaurants and other collective caterers. Commonly, LWE pasteurization is achieved by thermal treatment at 61 ºC for a minimum of 2.5 min. However, this standard treatment might not be completely effective in eliminating Salmonella. Therefore, some providers use chemical preservatives to prevent the survival of biocontamination after pasteurization. It is also usually recommended to consume the product within 3 days from the opening of the package. In a previous work, we explored the use of essential oils (EOs) as alternative to the chemical preservatives as these natural compounds are generally recognized as safe (GRAS). The growth/survival of S. enteriditis was studied by quantitative and presence/absence tests during the storage of the product at 4 ºC (simulating refrigeration conditions). The cinnamon bark EO showed the strongest antimicrobial activity. Its action was attributed mainly to its high content (67 %) of cinnamaldehyde (CNM). Thus, the
It is possible to inactivate Salmonella in whole liquid egg by the application of high pressure CO2 combined with cinnamaldehyde.
1
10
100
1000
10000
100000
0 20 40 60 80 100 120 140 160 180
CFU
/ml
Time (h)
N0
HPCD
HPCD+1000 ppm CNM
HPCD+2500 ppm CNM
HPCD+4000 ppm CNM
164
addition of this pure compound was further investigated. Concentrations of 6000 ppm were enough to reduce a S. Enteriditis population of 106 colony forming units (CFU) per mL to undetectable levels. The CNM addition did not significantly affect the pH or the ºBrix of egg products, but the smell and the color were very perceptible [1]. On the other hand, the use of high-pressure CO2 effectively killed Salmonella typhimurium spiked in egg yolk (>100%) at 13.7 MPa and 35 ºC for 2 h. However, it was not effective in LWE [2] probably due to the protective effect of its high fat content (about 15%).
This work explores the use of high-pressure carbon dioxide (HPCD) for the inactivation of Salmonella enterica serovar Enteritidis alone and in combination with cinnamaldehyde at lower concentrations than those previously explored. We pursued to reduce the sensory impact of the pure CNM as well as a synergetic effect of the two technologies to provide a non-thermal method for the sterilization of LWE. The assays were carried out with continuous CO2 flow over the samples at 10 MPa, 45º C, and 20 minutes of exposure time. The effect of CNM concentration on the survival of Salmonella was followed during storage at 4º C for 7 days. The results are shown in the Graphical Abstract figure.
Treatment with CO2 alone caused the immediate death of 97.4 % (equivalent to 1.6 logs) of the initial Salmonella contamination (6.8 104 CFU/mL). In samples contaminated with 1.2 106 CFU/mL, the reduction was 2.2 logs (results not shown). This reduction could be enough for the practice as contamination by Salmonella in real samples is at most of the order of 101-102 CFU/mL; although it is not sufficient for the sterilization standards that require at least 6 logs reduction. On the other hand, it seems that the Salmonella cells were damaged, since 100 % of them were death after 7 days of storage. Refrigeration by itself caused the slow death of Salmonella, as can be seen in the curve corresponding to the control sample (N0) but the inactivation rate of the HPCD treated samples was faster.
The use of CNM showed additional inactivation effect, but significant differences were not detected till the concentration of CNM increased up to 4000 ppm. Thus, with this compound added to the LWE previous the HPCD treatment, the Salmonella was totally inactivated at 48 h in cold storage. At this same time, 98.9 % of the Salmonella population was inactivated by solely the CO2. Another very interesting aspect of this investigation is that no recovery of Salmonella was detected after any of the treatments.
After the CO2 release, the pH of the samples did not vary. In the samples added with CNM, the smell to “cinnamon” was perceptible but not unpleasant. Anyway, the LWE is above all used to make bakery products, so this odour could be even wanted. Additionally, the LWE is also very diluted in the pastry masses.
ACKNOWLEDGEMENTS This research was financed by the Spanish Ministry of Science and Innovation (MICINN), project ref. CTQ2010-18537 and by the project FEI17/32 of the UCM.
REFERENCES [1] M.T. Valverde, R. Cava-Roda, L. Calvo, F. Marín-Iniesta, European Food Research and Technology, 240(5), 961-968, 2015. [2] C.I. Wei, M.O. Balaban, S.Y. Fernando, A.J. Peplow, Journal of Food Protection, 54(3), 189-193, 1991.
165
EIFS 2020 PM12
Inactivation of Legionella in aqueous media by supercritical CO2
D. Martín, Maria Teresa Valverde, Diego F. Tirado, Lourdes Calvo*
Department of Chemical and Materials Engineering, Universidad Complutense de Madrid, Avda. Complutense s/n 28040 Madrid, Spain
GRAPHICAL ABSTRACT
ABSTRACT Legionellosis is a set of infections caused by Legionella pneumophila and related to Legionella bacteria. The severity of legionellosis ranges from a mild febrile illness (Pontiac fever) to a life-threatening form of pneumonia (Legionnaires' disease) that can affect anyone, but primarily affects those who are susceptible due to age, disease, immunosuppression, or other risk factors, such as smoking. Water is the main natural reservoir of Legionella. Therefore, Legionella can be found in many aquatic environments, both natural and artificial such as cooling towers, water systems in hotels, health-care facilities, hotels and ships, fountains natural spas, hot tubs and swimming pools [1].
Once an outbreak of Legionella is detected, action must be taken immediately. The sterilization methods commonly employed are the application of heat above 70 °C for at least 3 h or the addition of chlorine under specific pH conditions. In the latter case, it is common the need to use bio-dispersants to facilitate the attack of chlorine, as well as anticorrosives to prevent damage to the installations [2]. These techniques are applied after the contamination is produced. In this work, the inactivation of Legionella in aqueous media using supercritical carbon dioxide (sc-CO2) was investigated as a pre-treatment of the water.
-5.0
-4.5
-4.0
-3.5
-3.0
-2.50 5 10 15 20 25 30
Deg
ree
of in
activ
atio
n
lo
g (N
/N0)
Treatment time (min)
Inactivation kinetics of Legionella in water by CO2 at 26 ºC and 10 MPa
166
First, tests were performed in discontinuous operation, at pressures from 10 MPa to 35 MPa, temperatures from room (about 26 ºC) to 50 ºC, and treatment times up to 30 min. The results were compared with those obtained with only heat. The increased pressure improved the inactivation of Legionella, probably due to better dispersion and dissolution of sc-CO2 in the aqueous medium. However, it was not necessary to exceed 20 MPa. In the chemical industry, the most problematic installations are cooling towers (27 % of legionellosis cases). The temperature that the water can acquire in this equipment oscillates between 22 °C and 35 ºC (in summer), the ideal temperature for the growth of Legionella. The treatment with sc-CO2 in this temperature range, which would imply not having to provide heat, was effective, causing the total inactivation of Legionella, if the pressure was 20 MPa and the treatment time was 30 min.
For a given temperature, treatment with sc-CO2 was always much more effective than thermal treatment, confirming the separate antimicrobial capacity of sc-CO2. However, it is an implicit requirement of this treatment to work at high pressures.
Inactivation kinetics was studied at mild conditions of 26 ºC and 10 MPa (see Figure in graphical abstract). The kinetic curve had two distinct stages. The first one corresponding to a constant inactivation degree of almost -3 log-cycles that was related to the effect of the pressurization at the immediate contact with sc-CO2. The second one from 15 min on, corresponds to a faster straight-line inactivation kinetics that was related to the cellular penetration of the sc-CO2 and the subsequent many intracellular alterations caused [3]. The inactivation constants of the second decreasing period (k = 0.17 min-1 and D = 5.6 min) were of the order of magnitude to those reported at close conditions for other gram-negative bacteria as Salmonella typhimurium, k = 0.21 min-1 at 35 ºC and 15 MPa [4] and Escherichia Coli, D = 7.31 min at 26 ºC and 6 MPa [5].
For future application as water treatment, continuous processing is necessary. Thus, water contaminated with Legionella was treated in spiral coils of different length in direct co-current contact with sc-CO2. Holding times of few minutes were necessary for the total inactivation of Legionella at temperatures below 35 ºC at 10 MPa. The depressurization of the outlet mixture allowed the separation of the sterile water from the gaseous CO2. At higher scale, CO2 could be recycled with minimum pumping if water was separated at 5 MPa - 6 MPa in a flash tank as it is done today the separation of the extract in other sc-CO2 processes.
ACKNOWLEDGEMENTS This research was financed with the project FEI17/32 of the Univ. Complutense de Madrid.
REFERENCES
[1] J.E. McDade, Emerg. Infect. Dis., Vol. 14, 1006a – 1006, 2008. [2] Asociación Española de Abastecimientos de agua y saneamiento, Manual de la Cloración, 1–32, 1984. [3] L. García-González, A.H. Geeraerd, S. Spilimbergo, K. Elst, L. Van Ginneken, J. Debevere, J.F. Van
Impe, F. Devlieghere, J. Food Microbiol., Vol. 117, 1-28, 2007. [4] O. Erkmen, H. Karaman, J. Food Eng., Vol. 50, 25-28, 2001. [5] T. Parton, N. Elvassore, A. Bertucco, G. Bertolini, J. Supflu, Vol. 40, 490-496, 2007.
167
Poster Sessions
168
169
EIFS 2020 PP01 Solid lipid microparticles (SLMPs) for the local delivery of an
anaesthetic agent
Clara López Iglesiasa,*, Cristina Quílezb, Joana Barrosc, Enriqueta R. Lópezd, D. Velascob, José L. Jorcanob, Fernando J. Monteiroc, Carmen Alvarez-Lorenzoa, Josefa
Fernándezd, Carlos A. García-Gonzáleza a Department of Pharmacology, Pharmacy and Pharmaceutical Technology, I+D Farma group (GI-1645), Faculty of Pharmacy, Agrupación Estratégica de Materiales (AeMAT) and Health
Research Institute of Santiago de Compostela (IDIS), Universidade de Santiago de Compostela, E-15782 Santiago de Compostela, Spain
b Department of Bioengineering and Aerospace Engineering, Universidad Carlos III de Madrid (UC3M), Madrid, Spain
c I3S - Instituto de Investigação e Inovação em Saúde, Universidade do Porto, INEB – Instituto de Engenharia Biomédica, FEUP – Faculdade de Engenharia, Universidade do Porto,
Portugal d Laboratorio de Propiedades Termofísicas, Grupo NaFoMat, Departamento de Física
Aplicada, Facultad de Física, Agrupación Estratégica de Materiales (AeMAT), Universidade de Santiago de Compostela, 15782, Santiago de Compostela, Spain
GRAPHICAL ABSTRACT
ABSTRACT Some strategies for the treatment of wounds involve the use of active wound dressings that deliver bioactive agents to treat wound complications. For example, the local delivery of anaesthetics has been proposed to treat wound pain in chronic and post-surgical wounds [1]. The use of microparticles for local drug delivery is of special interest since they present high surface area and low toxicity, and they do not cross biological barriers,
170
allowing a sustained release of the bioactive agents [2]. In particular, microparticles made of lipid materials are suitable for wound delivery due to their high biocompatibility and similarity with natural components of the skin, stability upon storage and ease of processing at a large scale.
PGSS (Particles from Gas-Saturated Solutions) technique is based on the use of supercritical CO2 as a plasticizer and pressurizing agent for the atomization of particles [3]. This supercritical technology is a solvent-free and one-step process consisting on the melting of a substance (or mixture of substances) in the presence of pressurized CO2, which has a plasticizer effect and reduces the normal melting point of the mixture. Then, the reactor is depressurized by opening a valve, the mixture passes through a nozzle of a determined diameter and the fast depressurization causes the precipitation of the solution in the form of solid microparticles.
In this work, the PGSS technique was used to produce SLMPs of glyceryl monostearate (GMS) loaded with an anaesthetic agent that also presents some antimicrobial properties, lidocaine hydrochloride (LID). The melting point depression of GMS in the presence of compressed CO2 was studied using a view cell. The influence of the most relevant parameters (P and T) in the final shape and size of the particles was studied using scanning electron microscopy (SEM) and image analysis to visualize the particles and determine the particle size distribution. The SLMPs were characterized in terms of physicochemical properties (ATR-IR), drug content and release behavior. The antimicrobial properties (MIC and MBC) of LID were studied against relevant bacteria in wound infections. The permeability of the SLMPs through bioengineered skin equivalents was also tested in Franz cells to study in vitro any potential penetration through epidermal and dermal tissue.
ACKNOWLEDGEMENTS Work supported by Xunta de Galicia [ED431F 2016/010, ED431C 2016/008 & GRC ED431C 2016/001], MCIUN [RTI2018-094131-A-I00], Agrupación Estratégica de Materiales [AeMAT-BIOMEDCO2, ED431E 2018/08], Agencia Estatal de Investigación [AEI] and FEDER funds. C.A.G.-G. acknowledges to MINECO for a Ramón y Cajal Fellowship [RYC2014-15239].
REFERENCES [1] S. Ranjan, F. Fontana, H. Ullah, J. Hirvonen, H.A. Santos, Ther. Deliv., 7, 711-732, 2016. [2] D.S. Kohane, Biotechnol. Bioeng., 96, 203-209, 2007. [3] C.A. García-González, A. Argemí, A.R. Sampaio de Sousa, C.M.M. Duarte, J. Saurina, C. Domingo, J. Supercrit. Fluids, 54, 342-347, 2010.
171
EIFS 2020 PP02
Supercritical Antisolvent Precipitation of Ca/Mg acetate as precursor for Ca/Mg Oxide
Luis C. S. Nobrea,*, Paula Teixeiraa, Carla I.C. Pinheiroa, António M. F. Palavraa, Mário
J. F. Calveteb, Carlos A. Nieto de Castroa, Beatriz P. Nobrea a Centro de Química Estrutural, Instituto Superior Técnico e Faculdade de Ciências da
Universidade de Lisboa. 1049-001 Lisboa, Portugal b Centro de Química de Coimbra, Departamento de Química, Faculdade de Ciência e
Tecnologia da Universidade de Coimbra, 3004-535 Coimbra, Portugal * [email protected]
GRAPHICAL ABSTRACT
ABSTRACT Nowadays developing solutions for carbon dioxide capture is extremely important. There are already presented in the literature various materials and techniques capable of capturing this gas [1]. A suitable and appropriate alternative the is Calcium Looping technology that use calcium oxide [2], which can be obtained from various renewable sources, mainly by the calcination of eggshells or marble residues, since these are mainly composed of calcium carbonate. However, for the use of this type of solid materials it is important to produce them homogeneously and to guarantee a maximum possible surface area. One technique that has proven to be an added value in this regard is Supercritical Antisolvent (SAS) precipitation [3]. With this technique, and by varying the operating conditions it is possible to obtain both different particle sizes and particle size distributions as well as different morphologies. Nobre et al (2019) have already successfully micronized calcium acetate from eggshells using SAS process [4]. The aim of this work is to study the possibility of using the SAS process to micronize calcium and magnesium acetate, from dolomite residues, a naturally occurring calcium and
172
magnesium carbonate. The product obtained from the precipitation will be characterized by SEM analysis, FTIR spectroscopy and its surface areas, as well as its capacity for carbon dioxide capture.
ACKNOWLEDGEMENTS Luis C. S. Nobre thanks FCT (Fundação para a Ciência e Tecnologia – Portugal) for the PhD grant (ref. PD/BD/133309/2017) and the financial support from UID/QUI/00100/2013.
REFERENCES
[1] E.I. Koytsoumpa, C. Bergins, E. Kakaras, J. Supercrit. Fluids, 132, 3–16, 2018.
[2] T. Witoon, Ceram. Int., 37, 3291–3298, 2011.
[3] Knez, E. Markočič, M. Leitgeb, M. Primožič, M. Knez Hrnčič, M. Škerget, Energy. 77, 235–243, 2014.
[4] L.C.S. Nobre, S. Santos, A.M.F. Palavra, M.J.F. Calvete, C.A. Nieto de Castro, B.P. Nobre, Micronization of Calcium Acetate: an effective way to produce quality catalysts by Supercritical Antisolvent Precipitation., in: 17th Eur. Meet. Supercrit. Fluids, B. Abstr., 2019: pp. 193–194.
173
EIFS 2020 PP03
Using Supercritical Fluid Technology to generate novel cocrystals of poorly soluble drugs
Barry Long, Kevin M. Ryan, Luis Padrela*
SSPC Research Centre, Department of Chemical Sciences, Bernal Institute, University of Limerick, Limerick, Ireland
GRAPHICAL ABSTRACT
ABSTRACT About 40% of drugs with market approval and nearly 90% of molecules in the discovery pipeline are poorly water-soluble [1, 2]. Solid state, drug purity and crystal size distribution are key control objectives of pharmaceutical crystallization processes. These outputs directly influence the drug product quality including solubility and rheological behavior during downstream processing [3].
Supercritical fluid methodologies have attracted interest due to their potential to control the crystalline form and size of pharmaceutical substances, improving the bioavailability of poorly soluble drugs [3-6]. These techniques provide a unique environment for different molecular recognition events to occur, which may induce the formation of particular cocrystals, polymorphs or amorphous materials in the micron and nano-sized range, that cannot be reproduced by other techniques [6, 7].
This work describes the generation of several newly reported cocrystals of a poorly soluble API. Due to the API extremely poor solubility, these cocrystals cannot be produced using conventional techniques (e.g. solution crystallization, slurry recrystallization, and spray drying). By employing a Cocrystallisation with Supercritical Solvent (CSS) method, it was possible to generate materials with improved dissolution profiles in the form of cocrystals.8 This technique has many advantages over most conventional techniques as there is no requirement for organic solvent use during processing. As a result, this factor also eliminates the need for time consuming post-
174
processing steps such as filtration and drying unit operations. Furthermore, this technique (CSS) is considered to be a relatively straight forward technique to scale, providing an opportunity for a new method to be employed for the large-scale production of pharmaceutical compounds. A thorough screening, using multiple coformers, was completed using supercritical CO2 as a solvent and the results (cocrystal purity, dissolution rate) were compared to mechanochemical techniques such as neat and liquid assisted grinding. In these experiments, several new cocrystals were produced and characterized by PXRD, FTIR, and DSC techniques. The compressibility and flowability of these new cocrystals were studied and compared to raw forms of this API in crystalline and amorphous forms.
ACKNOWLEDGEMENTS This publication has emanated from research conducted with the financial support of the Synthesis and Solid State Pharmaceutical Centre, funded by Science Foundation Ireland under Grant Number 12RC/2275 and 15/US-C2C/I3133, as well as support from the Bernal Institute.
REFERENCES
[1] T. Loftsson, M.E. Brewster, Journal of Pharmacy and Pharmacology, 62(11), 1607-1621, 2010.
[2] M. Rodriguez-Aller, D. Guillarme, J.-L. Veuthey, R. Gurny, Journal of Drug Delivery Science and Technology, 30, 342-351, 2015.
[3] B. Long, G.M. Walker, K.M. Ryan, L. Padrela, L., Controlling Polymorphism of Carbamazepine Nanoparticles in a Continuous Supercritical-CO2-Assisted Spray Drying Process, Crystal Growth & Design, 2019.
[4] L. Padrela, M.A. Rodrigues, A. Duarte, A.M.A. Dias, M.E.M. Braga, H.C. de Sousa, Advanced Drug Delivery Reviews, 131, 22-78, 2018.
[5] L. Padrela, B. Castro-Dominguez, A. Ziaee, B. Long, K.M. Ryan, G. Walker, E. O'Reilly, CrystEngComm, 21(18), 2845-2848, 2019.
[6] L. Padrela, J. Zeglinski, K.M. Ryan, Crystal Growth & Design, 17(9), 4544-4553, 2017.
[7] B. Long, K.M. Ryan, L. Padrela, European Journal of Pharmaceutical Sciences, 137, 104971, 2019.
[8] L. Padrela, M.A. Rodrigues, J. Tiago, S.P. Velaga, H.A. Matos, E.G. de Azevedo, Crystal Growth & Design, 15(7), 3175-3181, 2015.
175
EIFS 2020 PP04
Microencapsulation of supercritical CO2 extracted rice bran oil in pea proteins
Óscar Benito-Román*, Teresa Sanz, Sagrario Beltrán
Department of Biotechnology and Food Science (Chemical Engineering Section), Faculty of Sciences. University of Burgos. Plaza Misael Bañuelos s/n, 09001 Burgos, Spain
GRAPHICAL ABSTRACT
ABSTRACT Rice bran oil is a source of bioactive molecules such as sterols, tocols, -oryzanols and unsaturated fatty acids [1,2]. In this work, the encapsulation of rice bran oil extracted using supercritical CO2 under the conditions optimized by Benito-Román et al. [3] has been studied.
Microencapsulation processes are sequential and involve the emulsion formation and then, the emulsion drying. In a first stage, the emulsification process by high pressure homogenization was studied and optimized. High pressure homogenization, also known as microfluidization, is a high energy emulsification method affected by several parameters: pressure and number of homogenization cycles (together determine the energy input), the carrier material, the carrier to core ratio, and the solids content in the emulsion. Microfluization also exhibits an important advantage: the industrial application due to flexibility to control the emulsion droplet size (EDS) and the ability to produce emulsions from a variety of materials [4]. Among the different encapsulation materials, vegetable proteins are trendy, due to their properties and the possibility to be used in pharma, cosmetics and food industries [5]. More specifically, pea proteins present the most interesting properties such as emulsifying easiness, high nutritional value and non-
176
allergenic characteristics [6]. For these reasons, and the wall forming properties pea proteins have, key in microencapsulation processes, they were used in this work. The effect of working pressure (60-150 MPa), composition of the carrier (mixtures of pea protein isolate (PPI) and maltodextrin (MD), (from 50 to 90% of PPI) and carrier to oil ratio (COR) (from 2 to 4) on the emulsion droplet size (EDS) was studied, using the response surface methodology. The number of passes through the homogenization chamber was previously determined and set in 7. The experimental work, revealed that in order to minimize the EDS, moderate pressures (114 MPa), a carrier composed mainly by PPI (64%) and carrier to oil ratios around 3.2 are required. Important interactions between the experimental factors were also observed.
In the second stage, the emulsion obtained in the optimal conditions (EDS=189±3nm) was dried using different technologies: spray-drying (Buchi B-290 mini Spray-dryer, inlet temperature 155 ºC, outlet temperature 92-96 ºC and emulsion flow rate of 3 g/min); PGSS-drying (apparatus extensively described by Melgosa et al. [7], being the main working conditionsgas to product ratio (GPR) equal to 30 g/g temperature and pressure in the static mixer of 105 ºC and 10 MPa, respectively) and freeze drying (Labconco Freeze Dry System, 0.15 mbar for, at least, 48 h). All of them were suitable to get dry powders, spray drying provided high encapsulation efficiencies (around 73%) and monomodal powders (around 18 µm), whereas PGSS drying provided lower encapsulation efficiencies (around 52%) but perfect spheres with lower particle size (around 11 µm). Freeze drying yielded powders with almost complete encapsulation efficiencies, and higher stability when stored at 4 ºC, since spray-dried and PGSS-dried powders increased the amount of free oil after two weeks of storage.
ACKNOWLEDGEMENTS To JCyL and ERDF for financial support of project BU301P18 and OBR’s post-doctoral contract and to JCyL and ESF for D. M. Aymara-Caiza’s contract through the YEI program.
REFERENCES
[1] M. Friedman, J. Agric. Food Chem., 61, 10626–10641, 2013.
[2] K. Gul, B. Yousuf, A.K. Singh, P. Singh, A.A. Wani, Bioact. Carbohydrates Diet. Fibre, 6, 24–30, 2015.
[3] O. Benito-Román, S. Varona, M.T. Sanz, S. Beltrán, J. Ind. Eng. Chem., 80, 273-282, 2019.
[4] S.M. Jafari, Y. He, B. Bhandari, Eur. Food Res. Technol., 225, 733–741, 2007.
[5] C.E. Gumus, E.A. Decker, D.J. McClements, Food Res. Int., 100, 175–185, 2017.
[6] T. Moreno, E. de Paz, I. Navarro, S. Rodríguez-Rojo, A. Matías, C. Duarte, M. Sanz-Buenhombre, M.J. Cocero, Food Bioprocess Technol., 9, 2046–2058, 2016.
[7] R. Melgosa, Ó. Benito-Román, M.T. Sanz, E. de Paz, S. Beltrán, Food Chem., 270, 138–148, 2019.
177
Participants list
Albertina Cabañas Separation Processes and Materials Preparation following Green Chemistry Principles and using Supercritical Fluids Universidad Complutense de Madrid Dpr Química-Física, Facultad de C.C. Químicas, Universidad Complutense de Madrid Avda. Complutense s/n 28040 Madrid España [email protected]
Alejandro Borrás Caballero Supercritical Fluids and Functional Materials Institut de Ciència de Materials de Barcelona (ICMAB-CSIC) Campus UAB s/n 08193 Cerdanyola del Vallès Spain [email protected]
Alexandre Paiva Biocatalysis & Bioenergy LAQV / FCT-UNL Lab. 427, Dep. Química, Campus da Caparica 2829-516 Caparica Portugal [email protected]
Alvaro Reyes ARCAMO CONTROLS Pol. Ind. Riu Clar, C/ del Coure – Parcela 167 43006 Tarragona Spain [email protected]
Ana Iglesias I+D Farma USC Faculty of Pharmacy, University of de Santiago de Compostela 15782 Santiago de Compostela Spain [email protected]
178
Ana N. Nunes Nutraceuticals and Bioactives Process Technology lab iBET Av. República, Qta. do Marquês, Estação Agronómica Nacional 2780-157 Oeiras Portugal [email protected]
Ana Nunes CO2 Conversion and Utilization Group LAQV-REQUIMTE/ FCT-NOVA Largo da Torre 2829-516 Caparica Portugal [email protected]
Ana Leite Oliveira CBQF - Centre for Biotechnology and Fine Chemistry Universidade Católica Portuguesa Universidade Católica Portuguesa, Rua Diogo Botelho, 1327 4169-005 Porto Portugal [email protected]
Ana Matias Northern Swan Portugal Rua Filipe Folque nº 2 3ºDto, Northern Swan Company 1100-050 Lisbon Portugal [email protected]
Ana Rita C. Duarte Des Solve FCT-UNL Campus de Caparica 2829-516 Caparica Portugal [email protected]
Angel Concheiro I+DFarma Universidade de Santiago de Compostela Facultad de Farmacia 15782 Santiago de Compostela Spain [email protected]
179
Ángel Martín Martínez BioEcoUVa Universidad de Valladolid Dpto Ing. Química y TMA, Residencia Universitaria Alfonso VIII, RTeal de Burgos s/n 47011 Valladolid Spain [email protected]
Ariana Farias Melo CO2 Enhanced Oil Recovery UFBA Salvador Brazil [email protected]
Barry Long SSPC University of Limerick MS1-013-015, MSSI Building University of Limerick V94 T9PX Limerick Ireland [email protected]
Beatriz Díaz-Reinoso CITI University of Vigo Avda. Galicia 2, Parque Tecnolóxico de Galicia, San Cibrao das Viñas 32900 Ourense Spain [email protected]
Bruno Zêzere CICECO - Aveiro Institute of Materials Universidade de Aveiro Campus Universitário de Santiago 3810-193 Aveiro Portugal [email protected]
Carlos Silva CICECO - Aveiro Institute of Materials University of Aveiro Campus Universitário de Santiago 3810-193 Aveiro Portugal [email protected]
180
Carlos A. García González I+D Farma group Universidade de Santiago de Compostela Depto. Farmacología, Farmacia y Tecnología Farmacéutica, Facultad de Farmacia, Campus Vida E-15782 Santiago de Compostela Spain [email protected]
Carmen Alvarez-Lorenzo I+DFarma Universidade de Santiago de Compostela Facultad de Farmacia 15782 Santiago de Compostela Spain [email protected]
Celia Martínez ARCAMO CONTROLS Pol. Ind. Riu Clar, C/ del Coure – Parcela 167 43006 Tarragona Spain [email protected]
Clara López-Iglesias I+D Farma GI-1645 Universidade Santiago de Compostela Dept. Tecnología Farmacéutica, Facultade de Farmacia, Campus Vida s/n 15782 Santiago de Compostela Spain [email protected]
Clara María Pereyra López Análisis y diseño de procesos con fluidos supercríticos Universidad de Cádiz Facultad de Ciencias. Avda. Saharaui s/n 11510 Puerto Real España [email protected]
Concepción Domingo Supercritical Fluids and Functional Materials ICMAB-CSIC Campus UAB s/n 08193 Bellaterra Spain [email protected]
181
Cristiana Sofia Amaral Bento CIEPQPF, DEQ-FCTUC University of Coimbra Avenida Paulo VI, Nº 50, 3ºEsq 2040-325 Rio Maior Portugal [email protected]
David Piña Muñoz NANOMOL ICMAB-CSIC Carrer dels Til·lers s/n, Campus de la UAB, Carrer dels Til·lers 08193 Bellaterra (Barcelona) Spain [email protected]
Diana Troconis Productos de Instrumentación, S.A. Calle Montejo nº 11, Nave 9 28021 Madrid Spain [email protected]
Diego Valor Análisis y diseño de procesos con fluidos supercríticos | TEP-128 | UCA Universidad de Cádiz Facultad de Ciencias Campus Universitario Río San Pedro s/n 11510 Puerto Real España [email protected]
Elena Ibáñez Foodomics CSIC-CIAL (Instituto de Investigación en Ciencias de la Alimentación) C/ Nicolás cabrera, 9 28049 Madrid Spain [email protected]
Elvira Casas Sanz Department of Supercritical Fluids-Altex AINIA Parque Tecnológico de Valencia. C/ Benjamín Franklin 5-11 46980 Paterna Spain [email protected]
182
Emre Demirkaya High Pressure Process Group Universidad de Valladolid Escuela de Ingenierias Industriales, Sede Mergelina, Dpto. Ingenieria Quimica y Tecnologia del Medio ambiente, Universidad de Valladolid 47011 Valladolid España [email protected]
Encarnación Cruz Sánchez-Alarcos Laboratorio de Operaciones Básicas y Tecnología de Polímeros Universidad de Castilla - La Mancha Avda. Camilo José Cela 12 13071 Ciudad Real Spain [email protected]
Esther Trigueros Andrés Biotechnology and Food Science Dept., Chemical Engineering Division Burgos University Pza. Misael Bañuelos s/n 09001 BURGOS ESPAÑA [email protected]
Eva Tejedor Calvo Department of Production and Characterization of Novel Foods (INGREEN) Institute of Food Science Research –CIAL Calle Nicolás Cabrera 9 28049 Madrid Spain [email protected]
Fabián Parada-Alfonso Grupo de Investigación en Química de Alimentos (UNC) y FOODOMICS (CIAL) Universidad Nacional de Colombia (UNC) y CIAL/CSIC-UAM (CIAL) Av Cra 30 No. 45-00, Dpto. Química, Facultad de Ciencias, Universidad Nacional de Colombia 111321 Bogotá D.C. Colombia [email protected]
Fátima Mariño Thermophysical Properties Laboratory, NaFoMat Group University of Santiago de Compostela Facultad de Física, Campus Vida, Santiago de Compostela 15782 Santiago de Compostela España [email protected]
183
Gláucia Medeiros Burin Particles, Polymers and Biomaterials Technology (PPB) University of Coimbra Rua Silvio Lima, Polo II, Department of Chemical Engineering 3030-790 Coimbra Portugal [email protected]
Herminia Domínguez Biomasa y Desarrollo Sostenible Universidad de Vigo Facultad de Ciencias. Campus Ourense 32004 Ourense Spain [email protected]
Ignacio Gracia Fernandez TEQUIMA UCLM Adva Camilo Jose Cela, 12 13071 Ciudad Real España [email protected]
Inês Portugal CICECO - Aveiro Institute of Materials University of Aveiro Campus Universitário de Santiago 3810-193 Aveiro Portugal [email protected]
Inês Ferreira CICECO - Aveiro Institute of Materials Universidade de Aveiro Campus Universitário de Santiago 3810-193 Aveiro Portugal [email protected]
Inês Vasconcelos CBQF - centro de biotecnologia de química fina Universidade Católica Portuguesa Rua Mestre Joaquim Pereira Ramos 545 4435-492 Porto Portugal [email protected]
184
Irene Álvarez Lara Departamento de Ingeniería Química Universidad de Castilla-La Mancha Avenida Camilo José Cela s/n. ITQUIMA, Instituto de Tecnología Química y Medioambiental 13071 Ciudad Real España [email protected]
Isik Sena Akgun Energy Technologies and Supercritical Fluids Research Group KOÇ UNIVERSITY Koç University, Rumelifeneri Yolu 34350 ıstanbul Turkey [email protected]
Ivana Lukic Faculty of Technology and Metallurgy, Organic Chemical Technology Faculty of Technology and Metallurgy, University of Belgrade Karnegijeva 4 11000 Belgrade Serbia [email protected]
Jesús Manuel García Vargas TEQUIMA- Laboratorio de Operaciones Básicas y Tecnología de Polímeros Universidad de Castilla-La Mancha Avenida Camilo José Cela, 12 13071 Ciudad Real España [email protected]
Joana Barros Biocomposites Instituto de Investigação e Inovação em Saúde (i3S) R. Alfredo Allen 208, 4200-135 Porto Portugal [email protected]
João Carvalheira Paralab [email protected]
185
João Fernandes NATEX NATEX Prozesstechnologie GesmbH Werkstrasse 7 2630 Ternitz Austria [email protected]
João Iglésias CICECO - Aveiro Institute of Materials University of Aveiro Campus Universitário de Santiago 3810-193 Aveiro Portugal [email protected]
João Leocádio CIEPQPF – DEQ - FCTUC University of Coimbra Rua Sílvio Lima, Polo II, Pinhal de Marrocos 3030-790 Coimbra Portugal [email protected]
José Aniceto CICECO - Aveiro Institute of Materials University of Aveiro Campus Universitário de Santiago 3810-193 Aveiro Portugal [email protected]
José Coelho CIEQB/CQE Instituto Superior de Engenharia de Lisboa Rua Conselheiro Emidio Navarro, 1 1959-007 Lisboa Portugal [email protected]
Jose Antonio Mendiola Foodomics CSIC-CIAL (Instituto de Investigación en Ciencias de la Alimentación) C/ Nicolás Cabrera, 9 28049 Madrid Spain [email protected]
186
Jose Luis Gomez-Amoza I+DFarma Universidade de Santiago de Compostela Facultad de Farmacia 15782 Santiago de Compostela Spain [email protected]
Josefa Fernández Thermophysical Properties Laboratory, NaFoMat Group Universidad de Santiago de Compostela Facultad de Física, Campus Vida, Santiago de Compostela 15782 Santiago de Compostela España [email protected]
Juan Catalá Camargo Laboratorio de Operaciones Básicas y Tecnología de Polímeros Universidad de Castilla La Mancha Av/ Camilo José Cela 12, Edificio Enrique Costa 13071 Ciudad Real España [email protected]
Juan Castellanos Productos de Instrumentación, S.A. Calle Montejo nº 11, Nave 9 28021 Madrid Spain [email protected]
Juan Francisco Rodriguez Romero Departamento de Ingeniería Química. Instituto de Tecnología Química y Medioambiental Univesidad de Castilla La Mancha Avda. Camilo José Cela, s/n. 13071 Ciudad Real España [email protected]
Julio Fraile Supercritical Fluids and Functional Materials ICMAB-CSIC Campus UAB 08193 Bellaterra Spain [email protected]
187
Laura Quintana Gómez High Pressure Processes Group Universidad de Valladolid Dpto. Ing. Química y TMA. Escuela de Ingenierías Industriales (Sede Mergelina), Calle Dr. Mergelina 47011 Valladolid España [email protected]
Lourdes Vega Research and Innovation Center on CO2 and H2 (RICH Center) Khalifa University P O Box 127788 Abu Dhabi [email protected]
Lourdes Calvo-Garrido Department of Chemical Engineering Universidad Complutense de Madrid Avda. Séneca nº2 28040 Madrid Spain [email protected]
Luís Padrela SSPC University of Limerick MS1-013-015, MSSI Building University of Limerick V94 T9PX Limerick Ireland [email protected]
Luis Carlos Nobre Molecular and Engineering Thermodynamics - Centro de Química Estrutural Universidade de Lisboa Lab 11.06.14 Torre Sul Instituto Superior Técnico Av. Rovisco Pais 1 1049-001 Lisboa Portugal [email protected]
188
Mª Jesus Ramos Marcos Departamento de Ingeniería Química. Instituto de Tecnología Química y Medioambiental Universidad de Castilla La Mancha Avda. Camilo Jose Cela s/n 13170 Ciudad Real España [email protected]
Mª Teresa García González Departamento de Ingeniería Química. Instituto de Tecnología Química y Medioambiental Universidad de Castilla La Mancha Avda. Camilo José Cela, s/n. 13071 Ciudad Real España [email protected]
Manuel Nunes da Ponte LAQV, REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa [email protected] Portugal
Mara Elga Medeiros Braga CIEPQPF - DEQ- FCTUC Universidade de Coimbra Rua Silvio Lima s/nº, Pólo II, Pinhal de Marrocos 3030-790 Coimbra Portugal [email protected]
Marcelo Melo CICECO - Aveiro Institute of Materials University of Aveiro Universidade de Aveiro Campus Universitário de Santiago 3810 - 193 Aveiro Portugal [email protected]
María José Cocero Alonso BioecoUva Valladolid University EII Sede Mergelina 47011 Valladoloid Spain [email protected]
189
Mariana Landin I+D Farma Universidad de Santiago de Compostela Dpt. Farmacia y Tecnología Farmacéutica, Facultad de Farmacia, Campus Vida 15782 Santiago de Compostela España [email protected]
Marisa Costa Gaspar CIEPQPF - DEQ- FCTUC University of Coimbra Rua Sílvio Lima, Polo II, Pinhal de Marrocos 3030-790 Coimbra Portugal [email protected]
Marta Duarte CBQF - Centro de Biotecnologia e Química Fina Universidade Católica Portuguesa Rua do Chantre, nº 162 4465-780 Leça de Balio Portugal [email protected]
Marta Marques Biocatalysis and Bioenergy Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa Faculdade de Ciências e Tecnologia, Quinta da Torre, Campus Universitário 2829-516 Caparica Portugal [email protected]
Miguel Carvalho ARCAMO CONTROLS Pol. Ind. Riu Clar, C/ del Coure – Parcela 167 43006 Tarragona Spain [email protected]
Miguel Herrero Foodomics CSIC-CIAL (Instituto de Investigación en Ciencias de la Alimentación) C/ Nicolás cabrera, 9 28049 Madrid Spain [email protected]
190
Naiara Fernández Hernández Nutraceuticals & Bioactives Process Technology Instituto de Biologia Experimental y Tecnológica Avenida da Republica 2780-901 Oeiras Portugal [email protected]
Nora Ventosa Rull NANOMOL ICMAB-CSIC Carrer dels Til·lers s/n, Campus de la UAB. 08193 Bellaterra (Barcelona) Spain [email protected]
Pablo Arranz Productos de Instrumentación, S.A. Calle Montejo nº 11, Nave 9 28021 Madrid Spain [email protected]
Paula Rodríguez-Seoane Chemical Engineering- EQ-2 University of Vigo Department of Chemical Engineering. Faculty of Science. University of Vigo (Campus Ourense). As Lagoas S/N 32004, Ourense, Spain. 32004 Ourense Spain [email protected]
Pedro Simões LAQV Requimte FCT Universidade Nova de Lisboa Faculdade de Ciências e Tecnologia Campus da Caparica 2829-516 Caparica, Lisbon Portugal [email protected]
Rafael Villablanca Philip Jaeger Eurotechnica GmbH An den Stücken 55 22941 Barghteheide Germany [email protected]
191
Raquel Viveiros CleanMIPTech group LAQV-REQUIMTE, School of Sciences and Technology, NOVA University of Lisbon, Portugal Faculdade de Ciências e Tecnologia, Universidade NOVA de Lisboa Campus de Caparica 2829-516 Caparica, Almada Portugal [email protected]
Rocío Gallego Foodomics CSIC-CIAL (Instituto de Investigación en Ciencias de la Alimentación) C/ Nicolás Cabrera, 9 28049 Madrid Spain [email protected]
Rodrigo Melgosa Bioacatalysis and Bioenergy Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa Faculdade de Ciências e Tecnologia Quinta da Torre, Campus Universitário 2829-516 Caparica Portugal [email protected]
Roger Aragonés ARCAMO CONTROLS Pol. Ind. Riu Clar, C/ del Coure – Parcela 167 43006 Tarragona Spain [email protected]
Sagrario Beltrán Biotecnología Industrial y Medioambiental (BIOIND) Universidad de Burgos Facultad de Ciencias. Plaza Misael Bañuelos s/n 09001 Burgos España [email protected]
Selva Pereda Termodinámica de Procesos Planta Piloto de Ingeniería Química (PLAPIQUI - UNS -CONICET) Camino La Carrindanga km 7 8000 Bahia Blanca Agentina [email protected]
192
Silvio Vieira de Melo CO2 Enhanced Oil Recovery UFBA Rua Arisitides Novis, 2 40210-630 Salvador Brazil [email protected]
Sonia López Quijorna Laboratorio de Operaciones Básicas y Tecnología de Polímeros Universidad de Castilla-La Mancha Avda. Camilo José Cela,12 13071 Ciudad Real Spain [email protected]
Teresa Casimiro CleanMIPTech group LAQV-REQUIMTE, FCT/NOVA Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade NOVA de Lisboa, Campus de Caparica 2829-516 Caparica Portugal [email protected]
Vítor Hugo Rodrigues CICECO-Aveiro Institute of Materials University of Aveiro Campus Universitário de Santiago 3810-193 Aveiro Portugal [email protected]
Víctor Santos Rosales I+D Farma Group (GI-1645) Universidade Santiago de Compostela Dept. Tecnología Farmacéutica, Facultade de Farmacia, Campus Vida s/n 15782 Santiago de Compostela España [email protected]
Zully X. Suarez Montenegro Foodomics CSIC-CIAL (Instituto de Investigación en Ciencias de la Alimentación) C/ Nicolás Cabrera 9 28049 Madrid Spain [email protected]
193
Overall Conference Programme Tuesday, 18th February Wednesday, 19th February
8:30 Registration
9:00 Welcome/Opening Session 9:30 Plenary 1
(Chair: Carlos A. García-González) Plenary 3
(Chair: Luísa Durães) Session 1
(Co-chairs: Carlos Silva, Ignacio Gracia) Sesssion 5
(Co-chairs: Ana Rita Duarte, Lourdes Calvo) 10:20 O01 O13 10:40 O02 O14 11:00 O03 O15 11:20 Coffee break + Poster Session Coffee break + Poster Session 11:50 Session 2
(Co-chairs: Manuel N. da Ponte, Josefa Fernández)
Session 6 (Co-chairs: Sílvio V. Melo, Nora Ventosa)
Keynote 1 Keynote 2 12:20 O04 O16 12:40 O05 O17 13:00
Lunch Break Lunch Break
13:45 FLUCOMP meeting 14:30 Plenary 2
(Chair: Carlos García-González) Plenary 4
(Chair: Mara Braga) Session 3
(Co-chairs: Selva Pereda, Sagrario Beltrán) Session 7
(Co-chairs: Pedro Simões, Angel Martín) 15:20 O06 O18 15:40 O07 O19 16:00 O08 O20 16:20 Coffee break + Poster Session Coffee break + Poster Session 16:50 Session 4
(Co-chairs: José Coelho, Herminia Domínguez)
Session 8 (Co-chairs: Ana L. Oliveira, Concha
Domingo) O09 O21
17:10 O10 O22 17:30 O11 O23 17:50 O12 O24 18:10
Guided City Tour Closing Session
18:30 19:30
Tapas Dinner 20:00 Gala Dinner
Rooms: Plenary 1 and Plenary 3 – Salón de Actos Novoa Santos Other Plenaries and Oral sessions – Aula Castelao Poster sessions – corridor
EIFS 2020
Picture by Carmucha Remuñán López
