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<Graduate School of Applied Chemical> Prof. Minoru INABA, Takayuki DOI Electrochemical Laboratory http://istc.doshisha.ac.jp/en/course/chemistry/laboratories/labo_40.html Research Topics
Efficient production of nitrogen trifluoride using molten salt electrolysis Development of methods of electrolytic production of organic fluorides using ambient temperature
molten salt Development of silicon carbide surface etching methods using nitrogen trifluoride plasma Development of water electrolysis methods in harmony with the Lake Biwa environment Analysis of electrode reactions in lithium-ion batteries Development of high-performance lithium-ion battery electrode materials Research on polymer electrolyte fuel cell degradation mechanisms Development of high-active platinum core-shell catalysts used in polymer electrolyte fuel cells Development of anion exchange membrane fuel cells Development of ammonia-based solid oxide fuel cells
Research Contents
Production of functional inorganic gases using molten salt electrolysis and their application
Fluorine compounds marked the start of the development of functional materials, and one of our main areas of research is the production and application of inorganic fluorides, especially nitrogen trifluoride, that are used in large volumes in the electronics industry. Molten salt electrolysis method that was developed at this laboratory is the main production method used in Japan, but there are still some issues concerned with its use, including one major drawback-anode dissolution of nickel electrodes. To solve this issue, we are conducting fundamental research on the development of metal electrodes resistant to corrosion even in fluoride baths. For example, the priorities are assay of the coating produced on nickel anode surfaces and analysis of its mechanism of electrical conduction, and preparation and characterization of novel nickel-based alloys by means of doping with carbon, lithium or rare earth metals. We have also started work on the development of a production process for perfluorotrimethylamine. A second major line of research is the development and surface treatment of new materials. Specifically, we are developing novel production methods using plasma polymerization for carbon film used in lithium secondary batteries, solid electrolyte thin film used in fuel cells, and fluorine-containing organic polymer film; at the same time, we are using plasma methods and thermal Chemical Vapor Deposition (CVD) to modify the surface of inorganic materials such as magnetic materials, metal materials, and organic polymers using nitrogen trifluoride, and examining their properties. In short, we are not only using fluoride gases to produce novel functional materials like inorganic and organic polymer films, but also using surface treatment to give new functions to common materials and modify it into functional materials. Through this research we are aiming to elucidate the mechanisms by which materials express their function.
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Fundamental elucidation of lithium-ion battery and fuel cell electrode reactions, and development of new materials
Electrochemical energy conversion systems such as lithium secondary batteries and fuel cells are highly efficient and clean. They are key technology for solving various environmental issues facing society in the 21st century, including the efficient use of fossil fuels and the reduction of greenhouse gases, by way of power supply for electric vehicles, distributed power storage for electric power leveling and stationary cogeneration. We are working on a fundamental elucidation of the electrode reactions employed in these electrochemical energy conversion systems and on the development of new materials, with the aim of making the systems more highly efficient and rapidly putting them to practical use. 1) Lithium-ion Batteries: Putting large lithium-ion batteries used in electric vehicle power supply and distributed power storage to practical use will require a significant improvement in battery energy density, output density, and safety. To achieve this increase in performance, we are working on a fundamental elucidation of the electrode reactions using novel "in situ" analysis methods such as Raman spectroscopy and atomic force microscopy (AFM). To this end, we are also focusing on the development of new electrode materials that aim at higher performance, and working on the development of high-capacity silicon negative-electrodes and high-potential high-safety titania negative-electrodes. 2) Fuel Cells: The practical application of polymer electrolyte fuel cells (PEFC) for use in fuel cell vehicles, stationary cogeneration and the like, will necessitate improvements in durability and cost reductions. This laboratory is participating in an industry-government-academia-run national project concerned with the development of platinum core-shell catalysts which aims at high-activation thus reducing platinum usage. We are also
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working on the development of anion exchange membrane fuel cells (AEMFC) and ammonia-based solid oxide fuel cells (SOFC) in the hope of creating a hydrogen energy-based society for the future.
Keywords
Electrochemistry Molten salt electrolysis Nitrogen trifluoride Silicon carbide Plasma etching
Energy conversion Lithium-ion batteries Fuel cells Platinum catalysts
Annex3-3 Doshisha University
Prof. Yoshifumi KIMURA, Yoshiro YASAKA
Laboratory of Physical Chemistry http://istc.doshisha.ac.jp/en/course/chemistry/laboratories/labo_physical_chemistry.html Research Contents
Science of Designer Fluid Most chemical syntheses are performed in solution phase. Solute Molecules dissolved in solution are continuously affected by the solvent molecules surrounding the solutes. The changes of the solvent species, temperature, and pressure cause the changes of the solute-solvent interaction, which results in the changes of the electronic structure and dynamics of the solute molecules in various time scales. These variations induce the selectivity of the chemical reactions. In reverse, we can control the chemical reaction by the regulation of solvent. From this point of view, fluids such as supercritical fluids and ionic liquids are attracting materials which open new science of chemical reaction. These fluids are called designer fluids in the sense that their properties can be tuned for the purpose of the application, and they are widely studied in various fields like material science, environmental chemistry, electric chemistry, and so on. In our laboratory, by applying the laser spectroscopy, NMR, and electric conductivity under various thermodynamic conditions such as high pressure and high temperature, the properties of designer fluids, their applications to chemical reactions, and synthesis of new materials using designer fluids are under investigation. What is ionic liquid? Ordinal salt (such as NaCl) which is composed of cation (Na+) and anion (Cl-) is in a solid state under ambient condition due to the strong Coulomb interaction between ions. In order to liquidize the salt we have to heat the salt to the very high temperature (ca. 1081 K for NaCl). On the other hand, very recently, liquid salts at ambient temperature have been produced by the combination of organic cations and inorganic anions. These liquid salts are called ionic liquids (ILs), and they are in liquids state although they are composed of ions. They are quite new materials which did not exist before, and provide us a new field of science. Typical properties of ILs are (1)electric conductivity, (2)very low vapor pressure., (3) inflammable, which are not common to conventional organic solvents. ILs can dissolve various organic and inorganic materials and by utilizing the properties (2) and (3) ILs are paid attention to as green solvent. Further the property (1) makes ILs the basic materials in battery and condenser, and the property (2) makes ILs the material available under vacuum. Recently ILs which dissolve proteins keeping their activity are developed, and they are expecting new materials for biochemical science. What is supercritical fluid? When gaseous carbon dioxide is compressed at 25℃, phase transition from gas to liquid can be observed under certain pressure (6.4MPa). In such a case we can see both phases (gas and liquid) and further compression of the mixture the amount of gas decreases and finally all component becomes a single phase (liquid). However, if gaseous carbon dioxide is compressed at 35℃, no phase transition is observed in contrast to the case at 25℃. Above a certain temperature all gases can be compressed continuously without causing any phase transition from the gaseous phase (dilute fluid) to the liquid phase (dense fluid). The temperature of the border is called critical temperature, and the end point of the separation line between gas
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and liquid the critical point. Generally the fluid above the critical temperature and near its critical point is called supercritical fluid. In supercritical fluid, slight compression of the fluid induces a dramatic change of the fluid properties such as density, transport properties, and solubility, which is utilized for the extraction and nano-particle synthesis. Water is also available under the supercritical condition at high temperature and high pressure. Supercritical water can dissolve organic materials in contrast to water under ambient condition, and various kinds of reactions which cannot be done under ambient condition can be performed in supercritical water. Decomposition of pet is a typical example. Approach to the objects In our laboratory, the various physico-chemical properties of designer fluids are investigated by using various spectroscopic methods, and researches are performed on the application of designer fluids to the development of materials and new design of chemical reactions. For example,
1. Studies on the elementary chemical reaction process and molecular dynamics by using various kinds of laser spectroscopy.
2. Studies on the structure and molecular dynamics by NMR. 3. Studies on the molecular dynamics by electric conductivity. 4. Studies on the structure by Raman and IR spectroscopies. 5. Syntheses of new ionic liquids as a reaction media and elucidation of the reaction mechanism. 6. Syntheses of metal-nano materials by using ionic liquids and supercritical fluids 7. Studies on structure and dynamics by computer simulations.
Laser experimental system of fs-time resolution
Keywords
Supercritical fluid
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Ionic liquid Laser spectroscopy
Conductivity Nuclear spin resonance spectroscopy Molecular and reaction dynamics
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Prof. Nobuyuki HIGASHI, Tomoyuki KOGA
Polymer Chemistry Laboratory http://istc.doshisha.ac.jp/en/course/chemistry/laboratories/labo_41.html Research Topics
Research and development of functional peptide nano-materials
Development of high-function block polymers through hybridization of artificial peptides and synthetic polymers
Elucidation of biopolymer self-assembly
Design of a functional biointerface
Research and development of supra-molecular artificial membranes and functional design based on their higher-order structure
Research Contents
Research at the Polymer Chemistry Laboratory is aimed at producing innovative high-function polymer assemblies with structural control at the nano-scale. To meet this objective, the highly sophisticated molecular systems found in organisms are a fitting reference point. For example, proteins express their essential function by way of highly-organized conformations based on amino-acid sequences. We model these biological functions at a molecular level, elucidate the fundamental and academically important mechanisms for the expression of biofunctions, and consider the formation of energy-efficient, functional polymer elements for use in engineering. And, to accomplish these goals, we work comprehensively on the design of molecular organization systems, the molecular synthesis required for it, and its functional assessment.
Keywords
Biopolymer Functional peptide Polymer with specific structures Nano-structure Molecular assembly
Self-assembly
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Polymer synthesis Biomaterial Artificial membrane
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Prof. Ken HIROTA, Masaki KATO
Laboratory of Inorganic Synthetic Chemistry http://istc.doshisha.ac.jp/en/course/chemistry/laboratories/labo_42.html Research Topics
Production of metal/ceramic composites used for Induction Heating (IH) Development of oxide thermoelectric materials Production of carbon nano fiber dispersed engineering ceramics Production of ceramic micro particles for use in dye-sensitized solar cells Production of antibacterial ceramics Effect of elemental substitution on magnetic interactions in layered copper oxide Effect of elemental substitution on magnetism in indium (In), copper (Cu) oxide with its particularly
low-dimensional structure Elemental substitution effect and microscopic electronic properties of pyrochlore oxide Synthesis and physical properties of iron-based superconductive compounds and properties Synthesis and physical properties of titanium oxide as a new transparent electrode
Research Contents
Research Contents (Prof. Ken HIROTA)
<1> Production and characterization of ultrafine particle (nanometer-sized) powder. We use new methods of powder production to prepare oxide powders of spinel compounds such as MgFe2O4 and (Mn,Zn)Fe2O4, as well as the semi-conducting perovskite compound CaMnO3 and its related compounds, and examine the powder properties (including particle size, crystalline phase, phase transition, and specific surface area). High density ceramics are produced using various sintering methods, and then the microstructure and electrical, magnetic and thermoelectric properties are evaluated.
<2> Production and evaluation of high-density ceramics/ceramics composite materials using high-temperature/high-pressure processes.
Ultra-high pressure sintering (1,500°C, 500 - 1,000 MPa (5,000 - 10,000 kg/cm2)) Hot isostatic pressing (HIP: 2,000°C, 200 MPa (2,000 kg/cm2)) Pulsed Electric-Current Pressure Sintering (PECPS, or Spark Plasma Sintering: SPS: 1,800°C,
30 - 50 MPa (300 - 500 kg/cm2)) If a material shows poor sinterability and it is difficult to evaluate its properties or put it to practical use, the material is densified by using the above-mentioned process, and then the properties of the highly dense sintered ceramics and composite material are evaluated.
<3> Production of inorganic compound powders with high melting points such as nitrides, silicides, borides, and carbides using self-propagating high-temperature synthesis (SHS) and their powder characterization, and production and evaluation of high-density ceramics obtained using process 2 above. We synthesize the inorganic compound powders with high melting points using SHS, and aim to
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produce the dense bulk materials with the same composition during the SHS process. Then we characterize these powders and evaluate the mechanical, electrical, and magnetic properties of the bulk materials in relation to their microstructures.
<4> Nano composites
Fabrication and evaluation of nano-composites, in which carbon nano fibers (CNT; one of the novel carbon allotropes that leads the way in a nano technology) or the similar carbon nano fibers (CNF) are dispersed homogeneously into the ceramic matrix.
Production and properties-evaluation of magnetic nano-composites consisting of magnetic metals particles and magnetic ferrite materials, that reveal superior electrical and magnetic properties at high frequencies.
Production and properties-evaluation of new thermoelectric materials featuring high electrical and low-thermal conductivities of CNF homogeneously dispersed perovskite oxides.
<5> Production of new/functional materials
Production of novel titanium oxide TiO2(B) powders (used as an electrode in lithium batteries and solar cells), zinc oxide ZnO powder (with its sustainable antibacterial properties under dark) using a hydrothermal reaction.
Research Contents (Associate Prof. Masaki KATO) Superconductivity is a phenomenon whereby perfect diamagnetism (property which internally cancel the external magnetic field) called Meissner effect occurs with zero electric resistivity. The applications are too numerous to mention (e.g. development of ultra-strong magnetic fields, lossless power transmission, linear-motor trains and other modes of transport that use magnetic levitation, power storage, nuclear fusion), but the development of materials that become superconductive at high temperatures remains a major issue. To this end, a fundamental elucidation of the mechanisms regarding emergence of superconductivity is necessary.
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Notably, it is becoming clear that the dimensionality of the crystalline structure are closely linked to superconductivity and magnetism since the recent discovery of high temperature oxide superconductors and their related compounds. This strong association between structure and electron properties (conductivity and magnetism) is particularly noteworthy in inorganic compounds including transition-metals, and this stems from a much stronger correlation (strong electron correlation) in solids than in ordinary materials. This is a major topic in properties research of interest from both an experimental and theoretical viewpoint. For example, it can be said that all unique electric and magnetic phenomena in transition-metal compounds (such as materials that transition from metal to insulator at a certain temperature, itinerant electron magnets in which the electrons responsible for electrical conductivity also display magnetism, and heavy electron systems of compounds including rare metals in which the effective mass of electrons increases up to 100-1,000 times than normal) are based on strong electron correlation. However, research on strong electron correlation in solids is still in the early stages, and theoretical discussion is extremely difficult; thus a fundamental understanding will require consolidation of more experimental knowledge. Thus, this laboratory synthesizes such electrically and magnetically unique materials. Specifically, we produce layered inorganic ceramic compounds controlled materially and structurally on a nanoscale by introducing various atoms and molecules between layers in layered transition-metal compounds. We then analyze their structure using X-ray diffraction, electron microscope observation, and the like, and evaluate their physical properties using such measurements as magnetic susceptibility/electrical resistivity measurement, nuclear magnetic resonance (NMR) measurement, and neutron diffraction, in order to come to an understanding on a nanoscale of the various phenomena (or quantum criticality) based on superconductivity or electron correlation or the like. The knowledge gleaned is fed back into the synthesis, with the ultimate aim of producing new functional inorganic compounds.
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<1> Production and characterization of ultrafine particle (nanometer-sized) powder. We use new methods of powder production to prepare oxide powders of spinel compounds such as MgFe2O4 and (Mn,Zn)Fe2O4, as well as the semi-conducting perovskite compound CaMnO3 and its related compounds, and examine the powder properties (including particle size, crystalline phase, phase transition, and specific surface area). High density ceramics are produced using various sintering methods, and then the microstructure and electrical, magnetic and thermoelectric properties are evaluated.
<2> Production and evaluation of high-density ceramics/ceramics composite materials using high-temperature/high-pressure processes.
Ultra-high pressure sintering (1,500°C, 500 - 1,000 MPa (5,000 - 10,000 kg/cm2)) Hot isostatic pressing (HIP: 2,000°C, 200 MPa (2,000 kg/cm2)) Pulsed Electric-Current Pressure Sintering (PECPS, or Spark Plasma Sintering: SPS: 1,800°C,
30 - 50 MPa (300 - 500 kg/cm2)) If a material shows poor sinterability and it is difficult to evaluate its properties or put it to practical use, the material is densified by using the above-mentioned process, and then the properties of the highly dense sintered ceramics and composite material are evaluated.
<3> Production of inorganic compound powders with high melting points such as nitrides, silicides, borides, and carbides using self-propagating high-temperature synthesis (SHS) and their powder characterization, and production and evaluation of high-density ceramics obtained using process 2 above. We synthesize the inorganic compound powders with high melting points using SHS, and aim to produce the dense bulk materials with the same composition during the SHS process. Then we characterize these powders and evaluate the mechanical, electrical, and magnetic properties of the bulk materials in relation to their microstructures.
<4> Nano composites
Fabrication and evaluation of nano-composites, in which carbon nano fibers (CNT; one of the novel carbon allotropes that leads the way in a nano technology) or the similar carbon nano fibers (CNF) are dispersed homogeneously into the ceramic matrix.
Production and properties-evaluation of magnetic nano-composites consisting of magnetic metals particles and magnetic ferrite materials, that reveal superior electrical and magnetic properties at high frequencies.
Production and properties-evaluation of new thermoelectric materials featuring high electrical and low-thermal conductivities of CNF homogeneously dispersed perovskite oxides.
<5> Production of new/functional materials
Production of novel titanium oxide TiO2(B) powders (used as an electrode in lithium batteries and solar cells), zinc oxide ZnO powder (with its sustainable antibacterial properties under dark) using a hydrothermal reaction.
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Research Contents (Prof. Masaki KATO)
Superconductivity is a phenomenon whereby perfect diamagnetism (property which internally cancel the external magnetic field) called Meissner effect occurs with zero electric resistivity. The applications are too numerous to mention (e.g. development of ultra-strong magnetic fields, lossless power transmission, linear-motor trains and other modes of transport that use magnetic levitation, power storage, nuclear fusion), but the development of materials that become superconductive at high temperatures remains a major issue. To this end, a fundamental elucidation of the mechanisms regarding emergence of superconductivity is necessary. Notably, it is becoming clear that the dimensionality of the crystalline structure are closely linked to superconductivity and magnetism since the recent discovery of high temperature oxide superconductors and their related compounds. This strong association between structure and electron properties (conductivity and magnetism) is particularly noteworthy in inorganic compounds including transition-metals, and this stems from a much stronger correlation (strong electron correlation) in solids than in ordinary materials. This is a major topic in properties research of interest from both an experimental and theoretical viewpoint. For example, it can be said that all unique electric and magnetic phenomena in transition-metal compounds (such as materials that transition from metal to insulator at a certain temperature, itinerant electron magnets in which the electrons responsible for electrical conductivity also display magnetism, and heavy electron systems of compounds including rare metals in which the effective mass of electrons increases up to 100-1,000 times than normal) are based on strong electron correlation. However, research on strong electron correlation in solids is still in the early stages, and theoretical discussion is extremely difficult; thus a fundamental understanding will require consolidation of more experimental knowledge.
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Thus, this laboratory synthesizes such electrically and magnetically unique materials. Specifically, we produce layered inorganic ceramic compounds controlled materially and structurally on a nanoscale by introducing various atoms and molecules between layers in layered transition-metal compounds. We then analyze their structure using X-ray diffraction, electron microscope observation, and the like, and evaluate their physical properties using such measurements as magnetic susceptibility/electrical resistivity measurement, nuclear magnetic resonance (NMR) measurement, and neutron diffraction, in order to come to an understanding on a nanoscale of the various phenomena (or quantum criticality) based on superconductivity or electron correlation or the like. The knowledge gleaned is fed back into the synthesis, with the ultimate aim of producing new functional inorganic compounds.
Keywords
Carbon nano fibers (CNF) Nano powder, Nano-composites Electronic ceramics Engineering ceramics Quantum critical phenomena
Superconductivity Low-dimensional magnetism Strongly-correlated electron system Metal-insulator transition
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Prof. Koji KANO, Hiroaki KITAGISHI Functional Organic Chemistry Laboratory
http://istc.doshisha.ac.jp/en/course/chemistry/laboratories/labo_44.html
Research Contents
Research on supramolecular chemistry Supramolecule is the term for a noncovalent molecular assembly of multiple molecules that displays functions different to those of the original comprising molecules. At the Functional Organic Chemistry Laboratory, we conduct research on supramolecular chemistry from various perspectives.
Chemistry of protein supramolecules Within living organisms, many proteins function to sustain life. Some of these proteins function independently, but most form complexes (supramolecular complexes) of homologous or heterologous proteins by way of noncovalent binding interactions and display their vital function only through such binding. In short, weak interactions of noncovalent binding (as opposed to covalent binding) are used sophisticatedly in the natural world in order to reversibly control the binding of proteins according to the circumstances. Since the concept of supramolecular chemistry was propounded by Jean-Marie Lehn (who won the Nobel Prize in Chemistry 1987) and others, it has been developed using synthetic small molecules such as crown ether and cyclodextrin. Many researchers are still fascinated with supramolecules, and research is continuing. At the Functional Organic Chemistry Laboratory, we focus on massive biomolecules such as proteins as one unit of the supramolecule and our challenge is to control chemically the various molecular aggregation processes that occur within organisms. Function is controlled in vivo by protein interactions, and if we can replicate this synthetically, various innovative medical applications can be expected. In addition, we use supramolecular chemistry in the production of highly biocompatible nano materials using proteins, nucleic acid, cells, and various other materials.
Our protein research is expanding greatly as part of collaborative research with the Doshisha Women's College of Liberal Arts, Faculty of Pharmaceutical Sciences, and this research theme is expected to be of great interest in the future.
Chemistry of porphyrin-cyclodextrin supramolecules Cyclodextrins (CD) contain six to eight glucopyranose units in a ring, creating a cylinder shape, and are called α-CD, β-CD, and γ-CD respectively. Various molecules can be inserted (included) into the ring cavity by way of noncovalent binding, and thus CDs are renowned for being pioneering within the supramolecular chemistry field. The interior of CD dissolved in water is a highly hydrophobic space, despite being in water, and the inclusion of molecules in water leads to various phenomena that do not occur in uniform aqueous solutions. This CD-regulated environment has brought to light a number of very interesting supramolecules.
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Porphyrin is the generic term for large π conjugated compounds that form pigment components that are found abundantly in nature. It is possible to insert various metal ions in the cavity; and numerous different functions are expressed depending on the type of metal. Porphyrin is well known as the coenzyme for hemoglobin in human blood. We have identified various interesting supramolecules, including 1:2 inclusion complexes formed from O-methylated β-CD (TMe-β-CD) and anionic meso-tetrakis(4-sulfonatophenyl)porphyrin (TPPS). These inclusion complexes are extremely stable, and so large that the coupling constant was almost impossible to be determined. Through experiments using our micro-calorimeter, we discovered that major negative enthalpy change is seen when these inclusion complexes are formed and therefore proved that great stability can be obtained mainly driven by van der waals interaction.
However, not only are these inclusion complexes stable: importantly, they also isolate TPPS completely from water. This "separation of porphyrin from water" is an extremely common phenomenon in the natural world, whereby globin proteins of hemoglobins or myoglobins extract porphyrin-iron complexes (hemes) from the external water phase. Thus, we predicted that TMe-β-CD could be an alternative to the globin proteins. Based on this hypothesis, we started looking at cyclodextrin protein model synthesis bearing in mind the structures of hemoglobin and myoglobin. More specifically, we have designed and synthesized Py3CD molecules by linking two TMe-β-CD units with a pyridine ring, and coordinting nitrogen atoms to the TPPS central metal. By mixing this Py3CD with Fe (III) TPPS in water, and reducing to Fe (II) using a reducing agent, the oxygen molecules in water bind reversibly to the central Fe (II). This function is very similar to that of hemoglobin or myoglobin. In water, the catalysis of the water normally induces an oxidation reaction of oxygen molecules from Fe (II) to Fe (III) and oxygen binding capacity is lost, but the inclusion of Py3CD markedly interferes with the proximity of water to Fe (II), and the adsorption and desorption of oxygen molecules in water is remarkable. Complexes that can bind oxygen in water like this have never before been discovered. We have called such supramolecular complexes "hemoCD." Capturing oxygen from water is essential in the functioning of synthetic blood. And, at the Functional Organic Chemistry Laboratory, we are researching these hemoCD with a view to implement real-life applications such as synthetic blood and oxygen storage materials.
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Keywords
Supramolecular chemistry Proteins Porphyrin
Cyclodextrin Enzyme model Thermodynamics
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Prof. Masahito KODERA, Yutaka HITOMI Bioinorganic and Chemical Biology Laboratory
http://istc.doshisha.ac.jp/en/course/chemistry/laboratories/labo_46.html Research Topics
Development and reaction analysis of enzyme functional model complexes using dinucleating ligands
Development of spontaneous construction methods for multinuclear metal complexes displaying enzyme function
Development of enzyme functional model complexes that function in water Development of oxidative-stress-sensing probes Development of bio-compatible multifunctional nanoparticles
Research Contents
We aim to deepen a chemical understanding of life processes through the synthesis of artificial molecules that can
mimic the masterfully designed reactions that take place within living organisms, and based on this knowledge, we
work on the development of functional molecules (catalysts, sensors, etc.) of use to humankind. This approach
may be called biomimetics or bio-inspired, and it is expected to become a more and more important approach.
At this laboratory, we are dedicated to developing a group of useful substances by focusing specifically on
biological reactions involving metal ions, synthesising artificial molecules that can mimic these in vivo reactions in
order to understand life processes at the molecular level. We are also trying to introduce artificial molecules
(designed based on an understanding of in vivo reactions) into living cells to examine the chemical reactions within
living organisms.
Keywords
Dioxygen complex Oxidation reaction Enzyme functional model complex Bio-inspired metal complex Reactive oxygen species Oxidative stress
Homeostasis Fluorescent probes Bio-imaging Chemical biology Bioinorganic chemistry
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Prof. Tadashi MIZUTANI Laboratory of Biofunctional Chemistry
http://istc.doshisha.ac.jp/en/course/chemistry/laboratories/labo_47.html Research Topics
Synthesis of artificial receptor molecules Development of molecular electronic materials Functional chemistry of linear tetrapyrrole Development of tools of “in situ” observation of in vivo responses using NMR and fluorescent dyes Study of artificial evolution of nucleic acid from a selection/amplification viewpoint, and procurement
of functional nucleic acid materials
Research Contents
When it comes to various biological functions, organic molecules, inorganic molecules, organic polymers and
inorganic crystals are adeptly brought together to each play their own role in the creation of superior catalytic
activity, information processing, mechanical properties, and the like. At our laboratory, we look at these systems at
a molecular level, with the aim of developing superior materials.
<1> Elucidation of the mechanisms of precise biomolecular recognition in water by synthesizing artificial receptor
molecules. In particular, elucidation of the fundamentals of hydrophobic interaction thermodynamics.
<2>
Synthesis of molecules that undergo external stimuli-induced structural changes, and understanding of the
fundamental molecular mechanisms of information transmission and information processing.
<3>
Development of linear tetrapyrrole synthetic reactions by oxidative cleavage of porphyrin-iron complex.
<4>
Synthesis of liquid crystals using aggregation of bilindione and other helically asymmetric molecules.
<5>
Chemical understanding of the formation and decomposition of bioceramics consisting of inorganic crystals and
organic polymers.
1. Direct intracellular monitoring of biological responses using multiple-resonance NMR Development of new imaging technologies for identifying diseases (cancer, vascular diseases, etc.) at an early stage using specific probes
2. Analysis of intracellular dynamic behavior of nucleic acid (particularly RNA) using fluorescent RNA module as a tag Analysis of intracellular dynamic behavior of nucleic acid in relevance to protein expression using fluorescent ribonucleic acid (RNA) rather than fluorescent proteins (Nobel Prize); understanding biological information transfer as well as aiming at drug discovery
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Keywords
Molecular recognition
Porphyrin
Molecular elements
Nano-aggregates
"In situ" observation of in vivo responses
Functional nucleic acid materials
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Prof. Jusuke HIDAKA, Yoshiyuki SHIRAKAWA
Powder Technology Laboratory http://istc.doshisha.ac.jp/en/course/chemistry/laboratories/labo_48.html
Research Topics
Optimum design and control methods for powder processes
Establishment of powder materials engineering such as functional ceramics
Development of novel particle method simulations
Design of aggregated nanoparticle dispersion operation
Design of electrophotographic systems
Elucidation of mechanism of morphological control in crystals using molecular simulations
Establishment of liquid-liquid interfacial crystallization methods
Production of coated composite particles using non-uniform nucleation
Production of composite materials using mechano-chemical methods
Development of patterning technology using electrophoresis
Research Contents
We use computer engineering, specifically powder simulations, to conduct research on the production of
high-function materials involving powder particles and on the design of powder particle systems. In particular, we
introduce the concept of systems engineering to create optimum designs for high-function powder materials
formed by the aggregation of numerous particles with varying chemical compositions, the production processes for
these materials, and the devices that use these materials.
Keywords
Powder properties Granular processes Chemical simulations (MC method, MD method) Particle simulations (DEM, MPS) Slurry dispersion/drying Powder forming/sintering
Mechano-chemical reactions Solid electrolytes
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Composite electron materials Crystallization Electrophotography
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Prof. Yasushige MORI, Katsumi TSUCHIYA Transport Phenomena Laboratory http://istc.doshisha.ac.jp/en/course/chemistry/laboratories/labo_49.html
Research Contents
A. Colloid and Surface Engineering
<1>
Preparation and reaction mechanism of fine particles
We conduct basic studies on the precipitation process of fine particles where molecules aggregate in solution by
transport phenomena (diffusion, flow, etc.), and finally become particles through clusters or nuclei (phase
transition). We consider to not only the solute concentration or the solution temperature but also the reaction field
itself and external force field as parameters of the reaction mechanism. The micelles or reverse micelles which are
the spontaneous association of surfactant in an aqueous solution or organic solvent, and the gel formed from
polymers or clay particles are investigated as the reaction field during the preparation process of metal, ceramic, or
polymer particles. We also examine the particle formation using the electric or ultrasonic fields as the external force
field.
<2>
Particle assembly for functional materials
Particle assemblies for functional materials are investigated using advective flow and external field such as
electrostatic or vibrational fields. Monolayer ordered particle assembly of polystyrene latex (PSL) particles was
formed on the glass plate using the continuous coating operation controlled by interaction forces among particles
and between particles and a glass plate, as well as the operation conditions such as the advective flow rate,
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drawing speed of the plate, and feed rate of particle suspension. As the application of this assembly, we
demonstrated to make the dots array prepared by gold nanoparticles, which we expect to apply the substrate for
surface-enhanced Raman scattering. We also try to make the electrode of titania nanoparticles for dye-sensitized
solar cell by using electrophoresis.
<3>
Fabrication of nanocomposites
There are three types of composite materials; that is metal, ceramic and polymer system. And there are two types
of polymer composite systems; where fibrous materials or fine particles are added as additives. The well dispersed
state of the additives is very important for the performance of nanocomposite of polymer system, especially when
the size of the additives decreases to submicrometer or nanometer order. We are examining methods how to
disperse nanoparticles in polymers, and working on the development of methods for evaluating the particle
dispersion state.
<4>
Measurement of fine particle size and interaction forces between solid surfaces
In the research on nanoparticles and fine particles, the particle size is one of the most important characteristics to
know the actual physical quantity. Another important characteristic in colloid research field is the evaluation or the
calculation of the interaction forces acting among particles or between particles and other solid surfaces, because
these interaction forces could control particle dispersion and aggregation behavior. We study these research topics
in detail using various analytical equipments, where they are very fundamental topics, but the outcoming results
will be extremely important.
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<5>
Formation of particles by continuous synthesis operation
Electrostatic atomization and tubular flow reactor methods are used to produce particles with uniform size, but the
mechanisms of particle formation are not clear yet. We are examining the effect of various operating conditions,
specifically when producing silica particles from sodium silicate aqueous solution and when preparing alginate gel
from alginate aqueous solution. We are also examining operations to control the distribution of residence time in
flow reactors with the aim of producing silica monodispersed particles.
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B. Global environment and energy issues: research on the gas-liquid-solid dispersed flow process
<1>
Global warming strategy: removal and sequestration of atmospheric carbon dioxide
Global warming and the resulting climate change are major issues facing the global environment. High-efficiency
ocean carbon dioxide fixation (Gas Lift Advanced Dissolution system, GLAD system) has been developed to
combat this issue; it adeptly uses the properties of gas-liquid dispersed flow. We use "rapid visualization" to
analyze the dissolution process of the air bubbles and the dynamic behavior of the air bubbles within the circulatory
flow, with the aim of elucidating the gas dissolution process within the gas-liquid multiphase flow inside the GLAD
system dissolution pipe.
<2>
Analysis and control of local interfacial transport properties in complex multiphase flow processes
We use "Visualization" and "Computational Fluid Dynamics (CFD) simulations" to analyze the complex dynamics
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engendered by interphase interaction. Specifically, we are creating methods to measure mass dispersion based on
Laser-Induced Fluorescence (LIF) and ascertaining the state of mass dispersion around the interface using
rapid/high-sensitivity fluorescent imaging with the aim of controlling the reaction based on quantification of the
spatio-temporal distribution of concentration of the dissolved component as well as the local flow structure and
concentration/dispersion pattern within the multiphase flow.
<3>
Simulation of jet-induced gas mixing and combustion in reactors
We use "CFD simulations" to conduct numerical analysis of the flow, mixing and reaction of the mixing dispersion
when multiple gases of different reactivity (e.g. high temperature/low temperature) are injected into the reactor, and
we compute a design for the mixing process including the mixed-gas injection nozzle by different methods of
introducing gasses and under different operating conditions. We also conduct cold model analysis using "flow
visualization" to research the optimum design for the mixing process.
<4>
Development of energy-saving separation process for volatile organic compounds using ultrasonic atomization
As opposed to universal separation processes such as those that use distillation columns, we are working on the
development of an advanced separation process for organic solvents including alcohols and other amphiphatic
compounds suitable for use in high-mix low-volume manufacturing (when there is limited facilities space, or short
production lead time). More specifically, we are working on the production of "temperature-seal type single-pass
ultrasonic atomizing separator" and conducting performance evaluation of this separator. In addition, we are
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looking at the separation and removal of various organic compounds using this atomization technology, with the
aim of establishing this as one of environmental technologies.
<5>
Evaluation of transport and fractionation of fine particles through microchannels
To control the basic properties (particle size, dispersion, etc) of fine particle transport required for aggregation of
fine particles, we need to establish evaluation techniques including the distribution of the liquid phase flow rate, the
fine particle pathways, and the interaction between fine particles to elucidate the properties of fine particle
transport and fractionation that accompany pathway changes and curves. To this end, we use "CFD simulation" to
analyze fluid and particle motion through microchannels, leading to guidelines for the design of microchannels.
Based on this, we will produce a prototype, and use "longitudinal micro-PIV measurement techniques" to conduct
"high-resolution, rapid visualization" analysis of fine particle transport and fractionation phenomena in the channel
flow field.
Keywords
Transport phenomena Fine particle formation Nanoparticle Reverse micelles Gelation Sonochemistry
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Particle size distribution analysis Force between surfaces Particle ordering Monodispersed particles Optical properties of fine particles Gas-liquid-solid dispersed flow Controlling global warming
Carbon dioxide Bubble dissolution Multiphase flow Gas-liquid interface Mass dispersion Flow visualization CFD simulation Gas mixing and combustion Ultrasonic atomization Microchannels Fine particle transport and fractionation Micro PIV
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Prof. Masayuki ITOH Laboratory for Advanced Materials Science and Process Systems http://istc.doshisha.ac.jp/en/course/chemistry/laboratories/labo_51.html Research Topics
Engineering Researches on Advanced Energy Systems and Global Environmental Protection
Research Contents
A-1 Project for the development of therapeutic systems in medical engineering <1>
Development and standardization of synchronized inhalation therapy <2>
Development and evaluation of influenza vaccination by atomization techniques <3>
Construction of multivariate analysis for human immune-response models <4>
Risk analysis for human health factors in a safe and secure society
A-2 Corneal regeneration treatment project <1>
Evaluation of administration of epithelial and nerve growth factors on corneal wounds <2>
Suitable dose parameters estimated by corneal cell line culture <3>
Verification of growth factors for regenerated tissue observed by microscopic method <4>
Performance tests and safety verification for development of available therapeutic systems
B-1 R&D for the global environment protection and new energy resources <1>
Design and analysis of the Combined Heat & Power process with a high-temperature gas reactor to produce hydrogen gas by thermochemical direct water decomposition
<2> Synthesis of next-generation energy carriers by harnessing greenhouse gases and CHP processes-aiming new CCS and cost minimization of social infrastructure in the post Peak-Oil era
<3> Master design of the low GHG-emission Combined Power & Chemical Plant for the simultaneous production of electric power and chemical agricultural fertilizer for energy and food securities - demonstrative study with a laboratory system
<4> R&D of a novel fail-safe system to prevent coolant-leakage accidents in He based high-temperature gas nuclear reactor-aiming for the best possible security and cost minimization of HTGR
<5> Design of a smart grid simulator for the optimization of electrical power grid systems with a
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large-scale, multi-thread, many-core, high-speed GPU based small computer <6>
Forecast and assessment on the social system in the post Peak-Oil period by data mining methodology with GPU based grid computers
B-2 Nano-technology aiming the developing high potential energy-saving device <1>
Research of the high-efficient quantum-dot (QD) light collecting cell (solar concentrator) using QDs thin-film device
<2> Research on the synthesis and characterization of high-density, vertically aligned carbon nanotubes forest for the application to the high-efficient energy-saving quantum devices
Keywords
Energy systems Global environmental protection
Medical technology Therapeutic systems
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Prof. Kazuo KONDO, Michiaki MATSUMOTO Biochemical Engineering Laboratory http://istc.doshisha.ac.jp/en/course/chemistry/laboratories/labo_52.html
Research Contents
Development of advanced metallic ion separation technology There are various methods for recovering metallic ions from wastewater, including solvent extraction method
extracting these ions in an organic solvent, and adsorption method using an ion exchange resin.
At this laboratory, we are working on the development of new technology for the separation and recovery of such
materials, which uses extractant-impregnated microcapsules and allows a dramatic reduction in the volume of
toxic organic solvents used. We are also working on the development of mesoporous silica that displays high
levels of specific metal selectivity by imprinting metallic ions.
Efficient use and higher functionality of chitosan Chitosan is a biomass polymer found in abundance in the natural world that reacts with metals to form stable
compounds. Our research focuses on this property of chitosan, and aims to develop a method of separation and
recovery of valuable metals from industrial effluent, etc., using chitosan as the adsorbent. One feature of this
method is that metals can be efficiently recovered even from dilute metal aqueous solutions, and since the method
does not require organic solvents, it is suited to a recycling society.
Chitosan contains highly-reactive amino groups, and so various function groups can easily be chemically modified.
For example, the introduction of the functional groups shown in the diagrams below can yield a metal separation
and recovery process that displays more superior selectivity.
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Separation and purification of flora/fauna derived chitinase and functional development Chitin is the main component in the outer shells of Crustacea such as prawns and crabs. Chitin oligosaccharide
with a degree of polymerization of 5-7 is obtained through hydrolysis of chitin, and it displays various physiological
properties such as antitumor activity and immunostimulating activity, and thus could be of use in pharmaceuticals,
cosmetics and food manufacturing.
At present, chitin oligosaccharide is produced by means of acid hydrolysis, but more efficient production methods
are needed in order to achieve high-yield separation and purification of oligosaccharide with a random degree of
polymerization. Attention is now focused on one such method of chitin oligosaccharide preparation, which
combines the high enzymatic reaction specificity of chitin hydrolase (chitinase) and glycotransferase (chitin
synthase). At this laboratory, our research is aimed at developing a method of chitin oligosaccharide preparation,
using the separation and purification of plant seed derived chitinase and bacteria derived chitin synthase.
Development of environmental technology using microalgae Recently, global environmental issues caused by exhaust fumes such as carbon dioxide (CO2), sulphur oxide
(SOx) and nitrogen oxide (NOx) from the rapid combustion of fossil fuels are of major concern. One method of
mitigating these global environmental issues is the absorption and fixation of exhaust fumes using microalgae that
can grow in high concentrations of carbon dioxide. We are thus examining carbon dioxide and nitrogen oxide
fixation using green algae (chlamydomonas reinhardtti), and the effect of different culture conditions on the
production of useful dyes (β-carotene, phycobiliprotein) from blue algae (anabaena variabilis). In addition,
microorganisms are receiving much attention as a method of recovering metals from industrial effluent. We are
thus looking at growth inhibition when metals (Cu, Zn, Fe, etc.) are added to microalgae in culture, and at the
behavior of metal removal.
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Application of glucose separation membranes to active transport systems The establishment of glucose active transport systems is likely to be of use in a wide variety of fields; not only in
the glycoproteins and nucleoproteins used in medicine and physiology, but also in the recovery of useful
components from wastewater. They could also be of use in the issue of how to dispose of bio products
(microorganisms, water-soluble proteins, etc) that accompany the development of biotechnology.
Through the preparation of membranes which mainly consist of phenylboronic acid that displays high reactivity to
diols, we aim to develop conditions for selective separation of glucose.
In phenylboronic acid, the ester condensation reaction is accelerated under particularly high pH conditions.
And, by impregnating this material within the membrane, we are aiming to produce a polymer membrane with
glucose recognition capability. By inserting this membrane between the PMMA cells and changing various
conditions, we aim to identify the status of glucose membrane permeation.
At this point, we have achieved effective glucose membrane permeation by forming stable complex between a
quaternary ammonium salt cation and as an anionic phenylboronic acid-glucose.
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Utilizing the reversible reactivity of phenylboronic acid to pH, we used the membrane conditions to combine a
series of reactions whereby glucose is captured on the high pH side and discharged on the low pH side. We are
applying such system to active transport systems, which was previously very difficult.
In the future, we aim to develop this fundamental research to establish membrane systems that can be put to
practical use.
New lactic acid fermentation process using organic solvent tolerant bacteria Conventional versatile plastics derived from oil have become quite ubiquitous, but the greenhouse gases emitted
on its disposal and the depletion of oil are now major issues. Thus, in recent years, biodegradable recycling
plastics made from corn or cassava starch have received much attention. These plastics have little load on the
environment since after disposal, they are broken down into water and carbon dioxide by microorganisms, which
are then reabsorbed by plants by way of photosynthesis.
There are two main types of polylactate, one of the biodegradable plastics; those produced by microorganisms and
those produced by chemical synthesis. Polylactic acid can only be created from optically active lactic acid, and L
type polylactic acid is superior to D type in terms of transparency and the like, and so optically active lactic acid
(L-lactic acid) is now produced by microorganism fermentation using plant materials, rather than the conventional
chemical production methods. Lactic acid producing bacteria are used in this microorganism fermentation, but
there are various issues with this; for instance, they are not resistant to extractants and other organic solvents, and
they are highly auxotrophic.
For this reason, we are focusing on Bacillus bacteria which have low auxotrophy and are tolerant to organic
solvents, and working on the design of a new lactic acid fermentation process using the toluene-tolerant
B.thuringiensis G11 bacteria acquired on screening.
Adsorption and separation of bio products with wood based waste materials Glucose is not only a structural component of organisms and a source of energy that supports life, but is also
extremely an important material within organisms, it involves with the immune responses and the signal
transmission between cells by linking with proteins, etc. The establishment of glucose separation systems would
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therefore be applied to various fields, including food and pharmaceuticals, and even recovery from wastewater and
wastewater treatment. Demand for bio products, including amino acids and proteins, has risen remarkably in
recent years along with the marked advances in biotechnology, and a new separation and recovery process for bio
products is needed.
An optimum separation process for glucose or bio products would be low-cost and with no negative impact on the
environment. To this end, we are researching the adsorption and separation of glucose and bio products using
wood powder from bamboo and larch that have previously been treated as scrap wood.
Optical resolution of epoxide using epoxy-decomposing microorganism producing enzymes Due to its high levels of reactivity, optically active epoxide is a notably useful chemical material in pharmaceutical
sciences and synthetic organic chemistry as an intermediate reaction product. The most common synthesis
method of optically active epoxide is direct epoxidation using heavy metal catalysts from alkene. However, this
production method requires high temperature and high pressure. In addition, the environmental impact of heavy
metals is a major concern. Thus, we are focusing our research on a new method of optically active epoxide
production; optical resolution of racemic epoxide using the enantio selectivity of epoxide hydrolase by way of a
microorganism producing enzyme.
Keywords
Biochemical engineering Enzymatic reaction Microcapsules Extractive fermentation
Solvent extraction Chitin Chitosan Metal separation
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Prof. Kazuhiko TSUKAGOSHI, Masahiko HASHIMOTO Separation and Detection Chemistry Laboratory (Analytical Chemistry Laboratory) http://istc.doshisha.ac.jp/en/course/chemistry/laboratories/labo_53.html Research Topics
Capillary electrophoresis-chemiluminescence detection
Micro-channel chemiluminescence analysis
Tube radial distribution chromatography
DNA analysis from a chemical systems engineering perspective
Bio-sensing in micro spaces
Research Contents
We are aiming to develop future-oriented novel methodologies (new separation and detection methods) which are
characterized by high-sensitivity, high-selectivity, and customization (micro-miniaturization, ultra-simplification) and
have major ramifications for other academic fields. We hope to advance new techniques and research in the
chemical engineering and separation engineering fields.
At present, capillary electrophoresis, microchip electrophoresis, flow injection analysis, microflow injection analysis,
and micro-channel analysis are used at our laboratory as methods of absorbance, fluorescence, and
chemiluminescence detection. Each of these is simple, rapid, and low-cost, and allows continuous analysis.
Absorbance, fluorescence, and chemiluminescence are closely linked to one another, and so we attempt to
adeptly employ experimental data on all three interactively in the establishment of new separation and detection
methods.
Some of our specific research objectives are "confronting micro analysis," "development of micro-miniature
analysis device 'μ-TAS' (micro-Total Analysis System)," "interpreting life and in vivo information," and "application
to food- and environmental-analysis."
From an educational perspective, we believe that such study of separation and detection methods from
perspectives of chemical engineering, separation engineering, and life sciences is of great benefit to students
going on to become engineers or researchers in the future.
Keywords
Microflow Electrophoresis Chemiluminescence
Biological constituents Genetic analysis
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Prof. Akihisa SHIOI, Daigo YAMAMOTO Molecular Chemical Engineering http://istc.doshisha.ac.jp/en/course/chemistry/laboratories/labo_54.html Research Topics
Chemical control of instability in oil/water interface containing surfactant
Design of a moving vesicle driven by chemical reaction
Spatiotemporal pattern formation in colloidal system
Regulated motion of a reactive droplet
Electrochemical control of interfacial instability
Research Contents
Our research at the Molecular Chemical Engineering Laboratory is aimed at designing chemical systems moving
like living matters and proposing potential ways that they could be of practical use. The meaning of "like living
matter" is that the systems change autonomously in response to variations in their surrounding environment, and
alter their temporal or spatial patterns to maintain their essential function. Such systems are only feasible in
nonequilibrium open systems, and are created using the nonlinearity of interfaces in highly-reacting and moving
materials.
Keywords
Surfactant Interface Nonlinear Dynamics Self-organization Self-assembly
Droplet Vesicle Colloidal system Autonomous motion Pattern formation