Research ArticleNew Ni-Anthracene Complex for Selective and SensitiveDetection of 246-Trinitrophenol
Kumbam Lingeshwar Reddy Anabathula Manoj KumarAbhimanew Dhir and Venkata Krishnan
School of Basic Sciences and Advanced Materials Research Center Indian Institute of Technology MandiMandi Himachal Pradesh 175005 India
Correspondence should be addressed to AbhimanewDhir abhimanewiitmandiacin and Venkata Krishnan vkniitmandiacin
Received 26 August 2017 Accepted 4 January 2018 Published 6 February 2018
Academic Editor Guillermo Moyna
Copyright copy 2018 Kumbam Lingeshwar Reddy et al This is an open access article distributed under the Creative CommonsAttribution License which permits unrestricted use distribution and reproduction in any medium provided the original work isproperly cited
Selective and sensitive detection of explosive materials through a simple approach is an attractive area of research havingimplications on public safety and homeland security Considering this implication in mind a new Ni-anthracene complexwas designed and synthesized and has been demonstrated as an efficient fluorescence chemosensor for the selective andsensitive detection of 246-trinitrophenol Firstly a fluorescent anthracene ligand (A) was synthesized by treating anthracene-9-carboxaldehyde with 13-diaminopropane in presence of a weak acid To achieve superior selectivity and great quenchingefficiency for 246-trinitrophenol (TNP) a Ni complex namely [Ni(120583
2-L)(NO
3)] (B) was synthesized via the reaction of A with
Ni(NO3)2sdot6H2O Complex B showed strong emission peak (120582max) at 412 nm and exhibited high selectivity towards TNP among
other nitroaromatics and anions 100 equivalents of TNP made 95 fluorescence quenching of B and its detection limit for TNPwas calculated as 28120583M
1 Introduction
Nitroaromatic compounds are generally used in many indus-tries for the preparation of dyes pharmaceuticals rubberproducts explosives chemical fibres and pesticides andso forth [1] These nitroaromatic compounds were releasedinto the environment as industrial wastage and are one ofthe main reasons for the pollution Moreover due to theirpoisonousness carcinogenicity to living beings and the riskto homeland safety they cause serious intimidations to ourlives [2] 246-TNT 24-DNT 24-DNB 26-DNT and 246-TNP are the key constituents of environmental pollutantsand explosive products [3] Out of these compounds TNP inparticular creates health hazards and chronic skin and eyediseases and is used as a powerful explosive similar to TNT[4] Furthermore TNP is a more potent explosive than themore commonly used explosive TNT [5]
Various detection techniques such as electrochemicalsensing cyclic voltammetry Raman spectroscopy Liquid
chromatography-mass spectrometry (LC-MS) photolumi-nescence spectroscopy (PL) and several other techniqueshave been used to detect different types of explosives includ-ing TNP Nevertheless most of them are pretty sophisti-cated time taking andor difficult to operate [6 7] Amongthese reported procedures PL based method offers shorterresponse time and improved sensitivity and is economicallyworthwhile [7 8] Hence with the above stated problemsfrom TNP and the benefits of PL TNP sensing throughoptical detection is highly needed
Till now many fluorescent sensors have been devel-oped for the detection of nitroaromatic explosives [7ndash10]Nitroaromatics are electron deficient in nature due to thisreason some electron-rich fluorescent probes can always pro-duce nonfluorescent Meisenheimer or 120587-stacking complexeswith nitroaromatics [11 12] Selective detection of TNP is verydifficult as it has strong electron affinity [13]Through donor-acceptor electron transfer mechanism TNP can quench thefluorescence emission of various molecules such as metal
HindawiInternational Journal of SpectroscopyVolume 2018 Article ID 1321427 5 pageshttpsdoiorg10115520181321427
Among various fluorophores used for designing ofchemosensors anthracene based compounds have been usedfor the detection of several analytes due to their high chemi-cal stability richness of 120587-electrons and strong fluorescence[18 19] Mainly anthracene based compounds are widelyused for the sensing of anions and cations Neverthelessthere are very limited compounds reported for the detectionof explosivesnitroaromatics [20ndash22] In consequence byconsidering the significance of the new photoluminescentmaterial for TNP sensing in this work we synthesized a newanthracene based nickel complex with fluorescent activity forthe detection of TNP Solution phase spectral studies confirmthe sensitivity of complex with TNP
2 Materials and Methods
21 Materials Anthracene-9-carboxaldehyde 13-diamino-propane nickel nitrate tetra butyl ammonium salts of anionsNitroaromatic compounds and other chemicals are pur-chased from Sigma-Aldrich India and used without furtherpurification
22 Synthesis of A Anthracene-9-carboxaldehyde (02 g097mM) was dissolved in 10mL of methanol 13-Diamino-propane (0036 g 0485mM) and acetic acid (278 120583L0485mM) are added to the above solutionwhile stirringTheyellow colored solution mixture was refluxed for 12 h Uponcooling the yellow precipitate (7E19E)-N-((anthracen-10-yl)methylene)-1198731015840-((anthracen-9-yl)methylene)propane-13-diamine A was separated by filtration under reducedpressure and then washed with excess methanolThe productwas recrystallized from methanol Yield 8532 1H NMR(500MHz CDCl
23 Synthesis of B To the solution of A (100mg 022mM inTHF) nickel nitrate [Ni(NO
3)2sdot6H2O 056 g 193mM] was
added and stirred for two hours at room temperature Theyellowish green precipitate was separated out under reducedpressure Yield 8396 HR-MS [M + 1]+ found 108234
24 Characterizations The 1H and 13C NMR spectra ofthe A have been recorded on a Bruker 400MHz NMR
instrument Mass spectra of the B have been recorded onKratos PC Axima HR-Mass spectrometer in linear modeThe fluorescence quenching measurements were performedusing Cary Eclipse Fluorescence spectrophotometer Theexcitation and emission slit widths (each 10 nm) and scan rate(500 nmminminus1) were kept constant for all the measurementsThe optical absorption spectral measurements were recordedusing a Shimadzu UV-2450 spectrophotometer with a quartzcuvette (path length 1 cm) Energy dispersive X-ray spectra(EDAX) were obtained using scanning electron microscope(SEM) FEI Nova Nano SEM-450
3 Results and Discussion
Condensation of 13-diaminoprone 2 with anthracene-9-carboxaldehyde 1 produced a fluorescent ligand A whichgave a nickel complexBwith the addition of Ni(NO
3)2sdot6H2O
at RT (Scheme 1)The as-synthesized complex was character-ized by mass spectrometry where the parent ion (119898119911) peakappeared at 1082 corresponding to the species [2AsdotNi(NO
3)2]
(see supplementary Figure S3) The presence of all theelements in complex B is confirmed through elementalanalysis (see supplementary Figure S4) As we are developinga chemosensor for TNP the main motivation behind thesynthesis of compound A is that it was expected to becomea nonfluorescent moiety as photoinduced electron transfer(PET) process can take place due to presence of iminonitrogen atom [23] The binding of nickel ions to the iminonitrogen of compound A will prevent the PET process andit eventually results in the perseverance of fluorescenceConsequently TNP can perhaps quench the fluorescenceemission of B with electron transfer or energy transfermechanism and could be sensed [24]
Complex B (1 120583M) showed reasonably good emissionintensity of anthracene monomeric species at 412 nm inTHF HEPES (95 05) when excited at 120582ex = 365 nm [25]On addition of TNP (150 120583M) to the solution of B (1 120583M) inTHF HEPES (95 05) the emission band shows quenchingof emission band (Figure 1) To observe the selectivity of BtowardsTNPwe carried out the fluorescence titration exper-iments with similar amount of 150120583Mother nitroderivativesnamely nitrotoluene (NT) 24-dinitrotoluene (24 DNT)and 14-dinitrobenzene (14 DNB) and anions (Fminus Clminus BrminusIminus OHminus HSO3
minus CNminus NO3minus CH
3COOminus ClO4
minus and PO4minus)
with tetrabutyl ammonium as counter ion and observed nosignificant change in the emission spectrum of B depictingthe selectivity of B (Figure 2) Detection limit (DL) wascalculated using the equation DL = 3120572119870 where 120572 is the
International Journal of Spectroscopy 3
0
100
200
300
400
500
600
700
Inte
nsity
(au
)
400 425 450 475 500 525 550375Wavelength (nm)
BBBB
BBBB
+ 20 － TNP－ TNP－ TNP
－ TNP－ TNP－ TNP－ TNP
+ 40
+ 60
+ 80
+ 100
+ 120
+ 150
Figure 1 Change in emission spectrum of B (1120583M) on addition ofTNP (150 120583M) in THF HEPES (95 05) (]])
Analytes
0102030405060708090
100
Perc
enta
ge o
f que
nchi
ng
TNP
Ｌminus
minus
minus）minus
minus
Ｆminus
（
minus
4-N
T2
4-D
NT
14
-DN
B
Ｆ
4minus
（３
3minus
０
42minus
3minus
Figure 2 Fluorescence response of B (1 120583M) in THF HEPES(95 05) (]]) among various nitroaromatics and anions All ana-lytes are tested in the same molar ratio to B
standard deviation calculated by measuring the fluorescenceintensity of complex B for more than 15 times and 119870presents the slope of fitting curve between variation of thefluorescence intensity (119868
0minus 119868) and the added amount of TNP
at low concentration According to the linear fitting curve(Figure S5 shown in supporting information) the detectionlimit of complex B for sensing of TNP was found to be2857 120583M [26] The complex B DL in sensing of TNP isas comparable with the existing materials (see Table S1 insupporting information)
We also examined the meddling of other anions andnitroaromatics towards the sensing of TNP (Figure 3) andit was confirmed that the B was detecting TNP even in thepresence of other potential analytes The emission plot of B
Analytes
TNP
Ｌminus
minus
minus）minus
minus
Ｆminus
（
minus
4-N
T2
4-D
NT
14
-DN
B
0
20
40
60
80
100
Perc
enta
ge o
f que
nchi
ng
Ｆ
4minus
（３
3minus
０
42minus
3minus
Figure 3 Fluorescence quenching in B with the addition of TNPalone and TNP in the presence of other analytes The molar ratio toB used in each case is 100 equivalents
00
05
10
15
20
25
30
35
40Ab
sorb
ance
(au
)
120 equivalents
250 300 350 400 450 500200Wavelength (nm)
Figure 4 Change in absorption spectra of 4 (1 120583M) with theaddition of TNP in a mixed aqueous medium of THF HEPES(95 05) (]])
in the presence of TNP was studied using Stern-Volmer rela-tionship Stern-Volmer plot seemed like a hyperbolic curve(see supplementary Figure S6) which may be accredited tothe combination of static and dynamic (collision) quenching[27]
We have also detected these variations with the assistanceof UV-vis analysis Nickel complex B (1 120583M) in THF HEPES(95 05) showed an absorbance band at 260 nm (Figure 4)On addition of TNP (120 120583M) along with the formation ofband at 340 nm corresponding to TNP (Figure 4) there wassubsequent increase in the band at 260 nm presenting thatthere is some photochemical process happening between Band TNP To have a deep insight into the mechanism wemade plot between the absorbance spectrum of TNP andemission spectrum of B (Figure 5) The overlap betweenthe two plots suggests an energy transfer mechanism fromphotoexcited 120587-electron-rich derivative B to ground state
4 International Journal of Spectroscopy
Emission of BAbsorbance of TNP
00
02
04
06
08
10
12
Nor
mal
ized
inte
nsity
(au
)
00
02
04
06
08
10
12
Nor
mal
ized
abso
rban
ce (a
u)
325 350 375 400 425 450 475 500300Wavelength (nm)
Figure 5 Spectral overlap of the absorption of TNP (red line) withthe emission spectrum of B (blue line)
electron-deficient TNP Thus the changes occurring in theoptical properties of B on addition of TNP are attributed tothe energy transfer process
4 Conclusions
In conclusion we have designed and synthesized a new pho-toluminescent Ni-anthracene complex The luminescencebehaviour of the complex was assessed towards differentnitroaromatics and other analytes The synthesized Ni-anthracene complex shows selective and sensitive detectionof TNP and could be a helpful tool for the people working inforensic sciences
Conflicts of Interest
The authors declare that they have no conflicts of interestregarding the publication of this article
Acknowledgments
Advanced Materials Research Center (AMRC) IIT Mandiis gratefully acknowledged for the laboratory and charac-terization facilities Abhimanew Dhir and Venkata Krishnanacknowledge Department of Science and Technology Indiafor INSPIRE faculty award Kumbam Lingeshwar Reddyis grateful to Ministry of Human Resource Development(MHRD) India for research fellowship
Supplementary Materials
Figure S1 1HNMRspectrumof A Figure S2 13CNMR spec-trum of A Figure S3 mass spectrum of complex B FigureS4 energy dispersive X-ray spectrum (EDAX) of complex BFigure S5 change in fluorescence intensity of complex B atlow concentrations of TNP Figure S6 Stern-Volmer plot forthe quenching of the fluorescence of B upon the addition of120 120583Mof TNP Table S1 comparison of detection limit withdifferent reported materials (Supplementary Materials)
References
[1] P Kovacic and R Somanathan ldquoNitroaromatic compoundsenvironmental toxicity carcinogenicity mutagenicity therapyand mechanismrdquo Journal of Applied Toxicology vol 34 no 8pp 810ndash824 2014
[2] G He H Peng T Liu M Yang Y Zhang and Y Fang ldquoA novelpicric acid film sensor via combination of the surface enrich-ment effect of chitosan films and the aggregation-inducedemission effect of silolesrdquo Journal of Materials Chemistry vol19 no 39 pp 7347ndash7353 2009
[3] S K Samanta B BhushanAChauhan andRK Jain ldquoChemo-taxis of a Ralstonia sp SJ98 toward different nitroaromaticcompounds and their degradationrdquoBiochemical andBiophysicalResearch Communications vol 269 no 1 pp 117ndash123 2000
[4] J Shen J Zhang Y Zuo et al ldquoBiodegradation of 246-trinitrophenol by Rhodococcus sp isolated from a picric acid-contaminated soilrdquo Journal of Hazardous Materials vol 163 no2-3 pp 1199ndash1206 2009
[5] M E Germain and M J Knapp ldquoOptical explosives detectionfrom color changes to fluorescence turn-onrdquo Chemical SocietyReviews vol 38 no 9 pp 2543ndash2555 2009
[6] S Chen Q Zhang J Zhang J Gu and L Zhang ldquoSynthesisof two conjugated polymers as TNT chemosensor materialsrdquoSensors and Actuators B Chemical vol 149 no 1 pp 155ndash1602010
[7] M S Meaney and V L McGuffin ldquoLuminescence-based meth-ods for sensing and detection of explosivesrdquo Analytical andBioanalytical Chemistry vol 391 no 7 pp 2557ndash2576 2008
[8] S J Toal andW C Trogler ldquoPolymer sensors for nitroaromaticexplosives detectionrdquo Journal ofMaterials Chemistry vol 16 no28 pp 2871ndash2883 2006
[9] NVenkatramaiahDMG C Rocha P Srikanth F A AlmeidaPaz and J P C Tome ldquoSynthesis and photophysical char-acterization of dimethylamine-derived Zn(II)phthalocyaninesexploring their potential as selective chemosensors for trinitro-phenolrdquo Journal ofMaterials Chemistry C vol 3 no 5 pp 1056ndash1067 2015
[10] J-F Xiong J-X Li G-Z Mo et al ldquoBenzimidazole derivativesSelective fluorescent chemosensors for the picogram detectionof picric acidrdquoThe Journal of Organic Chemistry vol 79 no 23pp 11619ndash11630 2014
[11] B Xu X Wu H Li H Tong and L Wang ldquoSelective detectionof TNT and picric acid by conjugated polymer film sensors withdonor-acceptor architecturerdquo Macromolecules vol 44 no 13pp 5089ndash5092 2011
[12] S Xu H Lu J Li et al ldquoDummy molecularly imprintedpolymers-capped CdTe quantum dots for the fluorescent sens-ing of 246-trinitrotoluenerdquoACSAppliedMaterialsamp Interfacesvol 5 no 16 pp 8146ndash8154 2013
[13] S S Nagarkar B Joarder A K Chaudhari S Mukherjee andS K Ghosh ldquoHighly selective detection of nitro explosives bya luminescent metal-organic frameworkrdquo Angewandte ChemieInternational Edition vol 52 no 10 pp 2881ndash2885 2013
[14] V Bhalla S Kaur V Vij and M Kumar ldquoMercury-modulatedsupramolecular assembly of a hexaphenylbenzene derivative forselective detection of picric acidrdquo Inorganic Chemistry vol 52no 9 pp 4860ndash4865 2013
[15] W Wu S Ye L Huang et al ldquoA conjugated hyperbranchedpolymer constructed from carbazole and tetraphenylethylenemoieties convenient synthesis through one-pot ldquoA2 + B4rdquo
International Journal of Spectroscopy 5
suzuki polymerization aggregation-induced enhanced emis-sion and application as explosive chemosensors and PLEDsrdquoJournal of Materials Chemistry vol 22 no 13 pp 6374ndash63822012
[16] X-G Hou Y Wu H-T Cao et al ldquoA cationic iridium(iii)complex with aggregation-induced emission (AIE) propertiesfor highly selective detection of explosivesrdquo Chemical Commu-nications vol 50 no 45 pp 6031ndash6034 2014
[17] DK Singha S Bhattacharya PMajee S KMondalMKumarand P Mahata ldquoOptical detection of submicromolar levels ofnitro explosives by a submicron sized metal-organic phosphormaterialrdquo Journal of Materials Chemistry A vol 2 no 48 pp20908ndash20915 2014
[18] R Pandey L Reddy S Ishihara A Dhir and V KrishnanldquoConformation induced discrimination between picric acidand nitro derivativesanions with a Cu-pyrene array the firstdecision making photonic devicerdquo RSC Advances vol 3 no 44pp 21365ndash21368 2013
[19] K L Reddy A M Kumar A Dhir and V Krishnan ldquoSelectiveand sensitive fluorescent detection of picric acid by new pyreneand anthracene based copper complexesrdquo Journal of Fluores-cence vol 26 no 6 pp 2041ndash2046 2016
[20] B Gole S Shanmugaraju A K Bar and P S MukherjeeldquoSupramolecular polymer for explosives sensing role of H-bonding in enhancement of sensitivity in the solid staterdquoChemical Communications vol 47 no 36 pp 10046ndash100482011
[21] S Shanmugaraju S A Joshi and P SMukherjee ldquoFluorescenceand visual sensing of nitroaromatic explosives using electronrich discrete fluorophoresrdquo Journal of Materials Chemistry vol21 no 25 pp 9130ndash9138 2011
[22] S Shaligram P P Wadgaonkar and U K Kharul ldquoFluorescentpolymeric ionic liquids for the detection of nitroaromaticexplosivesrdquo Journal of Materials Chemistry A vol 2 no 34 pp13983ndash13989 2014
[23] B Valeur and I Leray ldquoDesign principles of fluorescent molec-ular sensors for cation recognitionrdquo Coordination ChemistryReviews vol 205 no 1 pp 3ndash40 2000
[24] S R Wallenborg and C G Bailey ldquoSeparation and detectionof explosives on a microchip using micellar electrokineticchromatography and indirect laser-induced fluorescencerdquoAna-lytical Chemistry vol 72 no 8 pp 1872ndash1878 2000
[25] J N Demas and G A Crosby ldquoThe measurement of photolu-mineseence quantum yields a reviewrdquo The Journal of PhysicalChemistry C vol 75 no 8 pp 991ndash1024 1971
[26] G L Long and J D Winefordner ldquoLimit of detection a closerlook at the IUPAC definitionrdquo Analytical Chemistry vol 55 no7 pp 712ndash724 1983
[27] D Zhao and T M Swager ldquoSensory responses insolution vs solid state a fluorescence quenching study ofpoly(iptycenebutadiynylene)srdquoMacromolecules vol 38 no 22pp 9377ndash9384 2005
TribologyAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal ofInternational Journal ofPhotoenergy
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
Hindawiwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2018
Bioinorganic Chemistry and ApplicationsHindawiwwwhindawicom Volume 2018
Among various fluorophores used for designing ofchemosensors anthracene based compounds have been usedfor the detection of several analytes due to their high chemi-cal stability richness of 120587-electrons and strong fluorescence[18 19] Mainly anthracene based compounds are widelyused for the sensing of anions and cations Neverthelessthere are very limited compounds reported for the detectionof explosivesnitroaromatics [20ndash22] In consequence byconsidering the significance of the new photoluminescentmaterial for TNP sensing in this work we synthesized a newanthracene based nickel complex with fluorescent activity forthe detection of TNP Solution phase spectral studies confirmthe sensitivity of complex with TNP
2 Materials and Methods
21 Materials Anthracene-9-carboxaldehyde 13-diamino-propane nickel nitrate tetra butyl ammonium salts of anionsNitroaromatic compounds and other chemicals are pur-chased from Sigma-Aldrich India and used without furtherpurification
22 Synthesis of A Anthracene-9-carboxaldehyde (02 g097mM) was dissolved in 10mL of methanol 13-Diamino-propane (0036 g 0485mM) and acetic acid (278 120583L0485mM) are added to the above solutionwhile stirringTheyellow colored solution mixture was refluxed for 12 h Uponcooling the yellow precipitate (7E19E)-N-((anthracen-10-yl)methylene)-1198731015840-((anthracen-9-yl)methylene)propane-13-diamine A was separated by filtration under reducedpressure and then washed with excess methanolThe productwas recrystallized from methanol Yield 8532 1H NMR(500MHz CDCl
23 Synthesis of B To the solution of A (100mg 022mM inTHF) nickel nitrate [Ni(NO
3)2sdot6H2O 056 g 193mM] was
added and stirred for two hours at room temperature Theyellowish green precipitate was separated out under reducedpressure Yield 8396 HR-MS [M + 1]+ found 108234
24 Characterizations The 1H and 13C NMR spectra ofthe A have been recorded on a Bruker 400MHz NMR
instrument Mass spectra of the B have been recorded onKratos PC Axima HR-Mass spectrometer in linear modeThe fluorescence quenching measurements were performedusing Cary Eclipse Fluorescence spectrophotometer Theexcitation and emission slit widths (each 10 nm) and scan rate(500 nmminminus1) were kept constant for all the measurementsThe optical absorption spectral measurements were recordedusing a Shimadzu UV-2450 spectrophotometer with a quartzcuvette (path length 1 cm) Energy dispersive X-ray spectra(EDAX) were obtained using scanning electron microscope(SEM) FEI Nova Nano SEM-450
3 Results and Discussion
Condensation of 13-diaminoprone 2 with anthracene-9-carboxaldehyde 1 produced a fluorescent ligand A whichgave a nickel complexBwith the addition of Ni(NO
3)2sdot6H2O
at RT (Scheme 1)The as-synthesized complex was character-ized by mass spectrometry where the parent ion (119898119911) peakappeared at 1082 corresponding to the species [2AsdotNi(NO
3)2]
(see supplementary Figure S3) The presence of all theelements in complex B is confirmed through elementalanalysis (see supplementary Figure S4) As we are developinga chemosensor for TNP the main motivation behind thesynthesis of compound A is that it was expected to becomea nonfluorescent moiety as photoinduced electron transfer(PET) process can take place due to presence of iminonitrogen atom [23] The binding of nickel ions to the iminonitrogen of compound A will prevent the PET process andit eventually results in the perseverance of fluorescenceConsequently TNP can perhaps quench the fluorescenceemission of B with electron transfer or energy transfermechanism and could be sensed [24]
Complex B (1 120583M) showed reasonably good emissionintensity of anthracene monomeric species at 412 nm inTHF HEPES (95 05) when excited at 120582ex = 365 nm [25]On addition of TNP (150 120583M) to the solution of B (1 120583M) inTHF HEPES (95 05) the emission band shows quenchingof emission band (Figure 1) To observe the selectivity of BtowardsTNPwe carried out the fluorescence titration exper-iments with similar amount of 150120583Mother nitroderivativesnamely nitrotoluene (NT) 24-dinitrotoluene (24 DNT)and 14-dinitrobenzene (14 DNB) and anions (Fminus Clminus BrminusIminus OHminus HSO3
minus CNminus NO3minus CH
3COOminus ClO4
minus and PO4minus)
with tetrabutyl ammonium as counter ion and observed nosignificant change in the emission spectrum of B depictingthe selectivity of B (Figure 2) Detection limit (DL) wascalculated using the equation DL = 3120572119870 where 120572 is the
International Journal of Spectroscopy 3
0
100
200
300
400
500
600
700
Inte
nsity
(au
)
400 425 450 475 500 525 550375Wavelength (nm)
BBBB
BBBB
+ 20 － TNP－ TNP－ TNP
－ TNP－ TNP－ TNP－ TNP
+ 40
+ 60
+ 80
+ 100
+ 120
+ 150
Figure 1 Change in emission spectrum of B (1120583M) on addition ofTNP (150 120583M) in THF HEPES (95 05) (]])
Analytes
0102030405060708090
100
Perc
enta
ge o
f que
nchi
ng
TNP
Ｌminus
minus
minus）minus
minus
Ｆminus
（
minus
4-N
T2
4-D
NT
14
-DN
B
Ｆ
4minus
（３
3minus
０
42minus
3minus
Figure 2 Fluorescence response of B (1 120583M) in THF HEPES(95 05) (]]) among various nitroaromatics and anions All ana-lytes are tested in the same molar ratio to B
standard deviation calculated by measuring the fluorescenceintensity of complex B for more than 15 times and 119870presents the slope of fitting curve between variation of thefluorescence intensity (119868
0minus 119868) and the added amount of TNP
at low concentration According to the linear fitting curve(Figure S5 shown in supporting information) the detectionlimit of complex B for sensing of TNP was found to be2857 120583M [26] The complex B DL in sensing of TNP isas comparable with the existing materials (see Table S1 insupporting information)
We also examined the meddling of other anions andnitroaromatics towards the sensing of TNP (Figure 3) andit was confirmed that the B was detecting TNP even in thepresence of other potential analytes The emission plot of B
Analytes
TNP
Ｌminus
minus
minus）minus
minus
Ｆminus
（
minus
4-N
T2
4-D
NT
14
-DN
B
0
20
40
60
80
100
Perc
enta
ge o
f que
nchi
ng
Ｆ
4minus
（３
3minus
０
42minus
3minus
Figure 3 Fluorescence quenching in B with the addition of TNPalone and TNP in the presence of other analytes The molar ratio toB used in each case is 100 equivalents
00
05
10
15
20
25
30
35
40Ab
sorb
ance
(au
)
120 equivalents
250 300 350 400 450 500200Wavelength (nm)
Figure 4 Change in absorption spectra of 4 (1 120583M) with theaddition of TNP in a mixed aqueous medium of THF HEPES(95 05) (]])
in the presence of TNP was studied using Stern-Volmer rela-tionship Stern-Volmer plot seemed like a hyperbolic curve(see supplementary Figure S6) which may be accredited tothe combination of static and dynamic (collision) quenching[27]
We have also detected these variations with the assistanceof UV-vis analysis Nickel complex B (1 120583M) in THF HEPES(95 05) showed an absorbance band at 260 nm (Figure 4)On addition of TNP (120 120583M) along with the formation ofband at 340 nm corresponding to TNP (Figure 4) there wassubsequent increase in the band at 260 nm presenting thatthere is some photochemical process happening between Band TNP To have a deep insight into the mechanism wemade plot between the absorbance spectrum of TNP andemission spectrum of B (Figure 5) The overlap betweenthe two plots suggests an energy transfer mechanism fromphotoexcited 120587-electron-rich derivative B to ground state
4 International Journal of Spectroscopy
Emission of BAbsorbance of TNP
00
02
04
06
08
10
12
Nor
mal
ized
inte
nsity
(au
)
00
02
04
06
08
10
12
Nor
mal
ized
abso
rban
ce (a
u)
325 350 375 400 425 450 475 500300Wavelength (nm)
Figure 5 Spectral overlap of the absorption of TNP (red line) withthe emission spectrum of B (blue line)
electron-deficient TNP Thus the changes occurring in theoptical properties of B on addition of TNP are attributed tothe energy transfer process
4 Conclusions
In conclusion we have designed and synthesized a new pho-toluminescent Ni-anthracene complex The luminescencebehaviour of the complex was assessed towards differentnitroaromatics and other analytes The synthesized Ni-anthracene complex shows selective and sensitive detectionof TNP and could be a helpful tool for the people working inforensic sciences
Conflicts of Interest
The authors declare that they have no conflicts of interestregarding the publication of this article
Acknowledgments
Advanced Materials Research Center (AMRC) IIT Mandiis gratefully acknowledged for the laboratory and charac-terization facilities Abhimanew Dhir and Venkata Krishnanacknowledge Department of Science and Technology Indiafor INSPIRE faculty award Kumbam Lingeshwar Reddyis grateful to Ministry of Human Resource Development(MHRD) India for research fellowship
Supplementary Materials
Figure S1 1HNMRspectrumof A Figure S2 13CNMR spec-trum of A Figure S3 mass spectrum of complex B FigureS4 energy dispersive X-ray spectrum (EDAX) of complex BFigure S5 change in fluorescence intensity of complex B atlow concentrations of TNP Figure S6 Stern-Volmer plot forthe quenching of the fluorescence of B upon the addition of120 120583Mof TNP Table S1 comparison of detection limit withdifferent reported materials (Supplementary Materials)
References
[1] P Kovacic and R Somanathan ldquoNitroaromatic compoundsenvironmental toxicity carcinogenicity mutagenicity therapyand mechanismrdquo Journal of Applied Toxicology vol 34 no 8pp 810ndash824 2014
[2] G He H Peng T Liu M Yang Y Zhang and Y Fang ldquoA novelpicric acid film sensor via combination of the surface enrich-ment effect of chitosan films and the aggregation-inducedemission effect of silolesrdquo Journal of Materials Chemistry vol19 no 39 pp 7347ndash7353 2009
[3] S K Samanta B BhushanAChauhan andRK Jain ldquoChemo-taxis of a Ralstonia sp SJ98 toward different nitroaromaticcompounds and their degradationrdquoBiochemical andBiophysicalResearch Communications vol 269 no 1 pp 117ndash123 2000
[4] J Shen J Zhang Y Zuo et al ldquoBiodegradation of 246-trinitrophenol by Rhodococcus sp isolated from a picric acid-contaminated soilrdquo Journal of Hazardous Materials vol 163 no2-3 pp 1199ndash1206 2009
[5] M E Germain and M J Knapp ldquoOptical explosives detectionfrom color changes to fluorescence turn-onrdquo Chemical SocietyReviews vol 38 no 9 pp 2543ndash2555 2009
[6] S Chen Q Zhang J Zhang J Gu and L Zhang ldquoSynthesisof two conjugated polymers as TNT chemosensor materialsrdquoSensors and Actuators B Chemical vol 149 no 1 pp 155ndash1602010
[7] M S Meaney and V L McGuffin ldquoLuminescence-based meth-ods for sensing and detection of explosivesrdquo Analytical andBioanalytical Chemistry vol 391 no 7 pp 2557ndash2576 2008
[8] S J Toal andW C Trogler ldquoPolymer sensors for nitroaromaticexplosives detectionrdquo Journal ofMaterials Chemistry vol 16 no28 pp 2871ndash2883 2006
[9] NVenkatramaiahDMG C Rocha P Srikanth F A AlmeidaPaz and J P C Tome ldquoSynthesis and photophysical char-acterization of dimethylamine-derived Zn(II)phthalocyaninesexploring their potential as selective chemosensors for trinitro-phenolrdquo Journal ofMaterials Chemistry C vol 3 no 5 pp 1056ndash1067 2015
[10] J-F Xiong J-X Li G-Z Mo et al ldquoBenzimidazole derivativesSelective fluorescent chemosensors for the picogram detectionof picric acidrdquoThe Journal of Organic Chemistry vol 79 no 23pp 11619ndash11630 2014
[11] B Xu X Wu H Li H Tong and L Wang ldquoSelective detectionof TNT and picric acid by conjugated polymer film sensors withdonor-acceptor architecturerdquo Macromolecules vol 44 no 13pp 5089ndash5092 2011
[12] S Xu H Lu J Li et al ldquoDummy molecularly imprintedpolymers-capped CdTe quantum dots for the fluorescent sens-ing of 246-trinitrotoluenerdquoACSAppliedMaterialsamp Interfacesvol 5 no 16 pp 8146ndash8154 2013
[13] S S Nagarkar B Joarder A K Chaudhari S Mukherjee andS K Ghosh ldquoHighly selective detection of nitro explosives bya luminescent metal-organic frameworkrdquo Angewandte ChemieInternational Edition vol 52 no 10 pp 2881ndash2885 2013
[14] V Bhalla S Kaur V Vij and M Kumar ldquoMercury-modulatedsupramolecular assembly of a hexaphenylbenzene derivative forselective detection of picric acidrdquo Inorganic Chemistry vol 52no 9 pp 4860ndash4865 2013
[15] W Wu S Ye L Huang et al ldquoA conjugated hyperbranchedpolymer constructed from carbazole and tetraphenylethylenemoieties convenient synthesis through one-pot ldquoA2 + B4rdquo
International Journal of Spectroscopy 5
suzuki polymerization aggregation-induced enhanced emis-sion and application as explosive chemosensors and PLEDsrdquoJournal of Materials Chemistry vol 22 no 13 pp 6374ndash63822012
[16] X-G Hou Y Wu H-T Cao et al ldquoA cationic iridium(iii)complex with aggregation-induced emission (AIE) propertiesfor highly selective detection of explosivesrdquo Chemical Commu-nications vol 50 no 45 pp 6031ndash6034 2014
[17] DK Singha S Bhattacharya PMajee S KMondalMKumarand P Mahata ldquoOptical detection of submicromolar levels ofnitro explosives by a submicron sized metal-organic phosphormaterialrdquo Journal of Materials Chemistry A vol 2 no 48 pp20908ndash20915 2014
[18] R Pandey L Reddy S Ishihara A Dhir and V KrishnanldquoConformation induced discrimination between picric acidand nitro derivativesanions with a Cu-pyrene array the firstdecision making photonic devicerdquo RSC Advances vol 3 no 44pp 21365ndash21368 2013
[19] K L Reddy A M Kumar A Dhir and V Krishnan ldquoSelectiveand sensitive fluorescent detection of picric acid by new pyreneand anthracene based copper complexesrdquo Journal of Fluores-cence vol 26 no 6 pp 2041ndash2046 2016
[20] B Gole S Shanmugaraju A K Bar and P S MukherjeeldquoSupramolecular polymer for explosives sensing role of H-bonding in enhancement of sensitivity in the solid staterdquoChemical Communications vol 47 no 36 pp 10046ndash100482011
[21] S Shanmugaraju S A Joshi and P SMukherjee ldquoFluorescenceand visual sensing of nitroaromatic explosives using electronrich discrete fluorophoresrdquo Journal of Materials Chemistry vol21 no 25 pp 9130ndash9138 2011
[22] S Shaligram P P Wadgaonkar and U K Kharul ldquoFluorescentpolymeric ionic liquids for the detection of nitroaromaticexplosivesrdquo Journal of Materials Chemistry A vol 2 no 34 pp13983ndash13989 2014
[23] B Valeur and I Leray ldquoDesign principles of fluorescent molec-ular sensors for cation recognitionrdquo Coordination ChemistryReviews vol 205 no 1 pp 3ndash40 2000
[24] S R Wallenborg and C G Bailey ldquoSeparation and detectionof explosives on a microchip using micellar electrokineticchromatography and indirect laser-induced fluorescencerdquoAna-lytical Chemistry vol 72 no 8 pp 1872ndash1878 2000
[25] J N Demas and G A Crosby ldquoThe measurement of photolu-mineseence quantum yields a reviewrdquo The Journal of PhysicalChemistry C vol 75 no 8 pp 991ndash1024 1971
[26] G L Long and J D Winefordner ldquoLimit of detection a closerlook at the IUPAC definitionrdquo Analytical Chemistry vol 55 no7 pp 712ndash724 1983
[27] D Zhao and T M Swager ldquoSensory responses insolution vs solid state a fluorescence quenching study ofpoly(iptycenebutadiynylene)srdquoMacromolecules vol 38 no 22pp 9377ndash9384 2005
TribologyAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal ofInternational Journal ofPhotoenergy
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
Hindawiwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2018
Bioinorganic Chemistry and ApplicationsHindawiwwwhindawicom Volume 2018
SpectroscopyAnalytical ChemistryInternational Journal of
Hindawiwwwhindawicom Volume 2018
MaterialsJournal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
BioMed Research International Electrochemistry
International Journal of
Hindawiwwwhindawicom Volume 2018
Na
nom
ate
ria
ls
Hindawiwwwhindawicom Volume 2018
Journal ofNanomaterials
Submit your manuscripts atwwwhindawicom
International Journal of Spectroscopy 3
0
100
200
300
400
500
600
700
Inte
nsity
(au
)
400 425 450 475 500 525 550375Wavelength (nm)
BBBB
BBBB
+ 20 － TNP－ TNP－ TNP
－ TNP－ TNP－ TNP－ TNP
+ 40
+ 60
+ 80
+ 100
+ 120
+ 150
Figure 1 Change in emission spectrum of B (1120583M) on addition ofTNP (150 120583M) in THF HEPES (95 05) (]])
Analytes
0102030405060708090
100
Perc
enta
ge o
f que
nchi
ng
TNP
Ｌminus
minus
minus）minus
minus
Ｆminus
（
minus
4-N
T2
4-D
NT
14
-DN
B
Ｆ
4minus
（３
3minus
０
42minus
3minus
Figure 2 Fluorescence response of B (1 120583M) in THF HEPES(95 05) (]]) among various nitroaromatics and anions All ana-lytes are tested in the same molar ratio to B
standard deviation calculated by measuring the fluorescenceintensity of complex B for more than 15 times and 119870presents the slope of fitting curve between variation of thefluorescence intensity (119868
0minus 119868) and the added amount of TNP
at low concentration According to the linear fitting curve(Figure S5 shown in supporting information) the detectionlimit of complex B for sensing of TNP was found to be2857 120583M [26] The complex B DL in sensing of TNP isas comparable with the existing materials (see Table S1 insupporting information)
We also examined the meddling of other anions andnitroaromatics towards the sensing of TNP (Figure 3) andit was confirmed that the B was detecting TNP even in thepresence of other potential analytes The emission plot of B
Analytes
TNP
Ｌminus
minus
minus）minus
minus
Ｆminus
（
minus
4-N
T2
4-D
NT
14
-DN
B
0
20
40
60
80
100
Perc
enta
ge o
f que
nchi
ng
Ｆ
4minus
（３
3minus
０
42minus
3minus
Figure 3 Fluorescence quenching in B with the addition of TNPalone and TNP in the presence of other analytes The molar ratio toB used in each case is 100 equivalents
00
05
10
15
20
25
30
35
40Ab
sorb
ance
(au
)
120 equivalents
250 300 350 400 450 500200Wavelength (nm)
Figure 4 Change in absorption spectra of 4 (1 120583M) with theaddition of TNP in a mixed aqueous medium of THF HEPES(95 05) (]])
in the presence of TNP was studied using Stern-Volmer rela-tionship Stern-Volmer plot seemed like a hyperbolic curve(see supplementary Figure S6) which may be accredited tothe combination of static and dynamic (collision) quenching[27]
We have also detected these variations with the assistanceof UV-vis analysis Nickel complex B (1 120583M) in THF HEPES(95 05) showed an absorbance band at 260 nm (Figure 4)On addition of TNP (120 120583M) along with the formation ofband at 340 nm corresponding to TNP (Figure 4) there wassubsequent increase in the band at 260 nm presenting thatthere is some photochemical process happening between Band TNP To have a deep insight into the mechanism wemade plot between the absorbance spectrum of TNP andemission spectrum of B (Figure 5) The overlap betweenthe two plots suggests an energy transfer mechanism fromphotoexcited 120587-electron-rich derivative B to ground state
4 International Journal of Spectroscopy
Emission of BAbsorbance of TNP
00
02
04
06
08
10
12
Nor
mal
ized
inte
nsity
(au
)
00
02
04
06
08
10
12
Nor
mal
ized
abso
rban
ce (a
u)
325 350 375 400 425 450 475 500300Wavelength (nm)
Figure 5 Spectral overlap of the absorption of TNP (red line) withthe emission spectrum of B (blue line)
electron-deficient TNP Thus the changes occurring in theoptical properties of B on addition of TNP are attributed tothe energy transfer process
4 Conclusions
In conclusion we have designed and synthesized a new pho-toluminescent Ni-anthracene complex The luminescencebehaviour of the complex was assessed towards differentnitroaromatics and other analytes The synthesized Ni-anthracene complex shows selective and sensitive detectionof TNP and could be a helpful tool for the people working inforensic sciences
Conflicts of Interest
The authors declare that they have no conflicts of interestregarding the publication of this article
Acknowledgments
Advanced Materials Research Center (AMRC) IIT Mandiis gratefully acknowledged for the laboratory and charac-terization facilities Abhimanew Dhir and Venkata Krishnanacknowledge Department of Science and Technology Indiafor INSPIRE faculty award Kumbam Lingeshwar Reddyis grateful to Ministry of Human Resource Development(MHRD) India for research fellowship
Supplementary Materials
Figure S1 1HNMRspectrumof A Figure S2 13CNMR spec-trum of A Figure S3 mass spectrum of complex B FigureS4 energy dispersive X-ray spectrum (EDAX) of complex BFigure S5 change in fluorescence intensity of complex B atlow concentrations of TNP Figure S6 Stern-Volmer plot forthe quenching of the fluorescence of B upon the addition of120 120583Mof TNP Table S1 comparison of detection limit withdifferent reported materials (Supplementary Materials)
References
[1] P Kovacic and R Somanathan ldquoNitroaromatic compoundsenvironmental toxicity carcinogenicity mutagenicity therapyand mechanismrdquo Journal of Applied Toxicology vol 34 no 8pp 810ndash824 2014
[2] G He H Peng T Liu M Yang Y Zhang and Y Fang ldquoA novelpicric acid film sensor via combination of the surface enrich-ment effect of chitosan films and the aggregation-inducedemission effect of silolesrdquo Journal of Materials Chemistry vol19 no 39 pp 7347ndash7353 2009
[3] S K Samanta B BhushanAChauhan andRK Jain ldquoChemo-taxis of a Ralstonia sp SJ98 toward different nitroaromaticcompounds and their degradationrdquoBiochemical andBiophysicalResearch Communications vol 269 no 1 pp 117ndash123 2000
[4] J Shen J Zhang Y Zuo et al ldquoBiodegradation of 246-trinitrophenol by Rhodococcus sp isolated from a picric acid-contaminated soilrdquo Journal of Hazardous Materials vol 163 no2-3 pp 1199ndash1206 2009
[5] M E Germain and M J Knapp ldquoOptical explosives detectionfrom color changes to fluorescence turn-onrdquo Chemical SocietyReviews vol 38 no 9 pp 2543ndash2555 2009
[6] S Chen Q Zhang J Zhang J Gu and L Zhang ldquoSynthesisof two conjugated polymers as TNT chemosensor materialsrdquoSensors and Actuators B Chemical vol 149 no 1 pp 155ndash1602010
[7] M S Meaney and V L McGuffin ldquoLuminescence-based meth-ods for sensing and detection of explosivesrdquo Analytical andBioanalytical Chemistry vol 391 no 7 pp 2557ndash2576 2008
[8] S J Toal andW C Trogler ldquoPolymer sensors for nitroaromaticexplosives detectionrdquo Journal ofMaterials Chemistry vol 16 no28 pp 2871ndash2883 2006
[9] NVenkatramaiahDMG C Rocha P Srikanth F A AlmeidaPaz and J P C Tome ldquoSynthesis and photophysical char-acterization of dimethylamine-derived Zn(II)phthalocyaninesexploring their potential as selective chemosensors for trinitro-phenolrdquo Journal ofMaterials Chemistry C vol 3 no 5 pp 1056ndash1067 2015
[10] J-F Xiong J-X Li G-Z Mo et al ldquoBenzimidazole derivativesSelective fluorescent chemosensors for the picogram detectionof picric acidrdquoThe Journal of Organic Chemistry vol 79 no 23pp 11619ndash11630 2014
[11] B Xu X Wu H Li H Tong and L Wang ldquoSelective detectionof TNT and picric acid by conjugated polymer film sensors withdonor-acceptor architecturerdquo Macromolecules vol 44 no 13pp 5089ndash5092 2011
[12] S Xu H Lu J Li et al ldquoDummy molecularly imprintedpolymers-capped CdTe quantum dots for the fluorescent sens-ing of 246-trinitrotoluenerdquoACSAppliedMaterialsamp Interfacesvol 5 no 16 pp 8146ndash8154 2013
[13] S S Nagarkar B Joarder A K Chaudhari S Mukherjee andS K Ghosh ldquoHighly selective detection of nitro explosives bya luminescent metal-organic frameworkrdquo Angewandte ChemieInternational Edition vol 52 no 10 pp 2881ndash2885 2013
[14] V Bhalla S Kaur V Vij and M Kumar ldquoMercury-modulatedsupramolecular assembly of a hexaphenylbenzene derivative forselective detection of picric acidrdquo Inorganic Chemistry vol 52no 9 pp 4860ndash4865 2013
[15] W Wu S Ye L Huang et al ldquoA conjugated hyperbranchedpolymer constructed from carbazole and tetraphenylethylenemoieties convenient synthesis through one-pot ldquoA2 + B4rdquo
International Journal of Spectroscopy 5
suzuki polymerization aggregation-induced enhanced emis-sion and application as explosive chemosensors and PLEDsrdquoJournal of Materials Chemistry vol 22 no 13 pp 6374ndash63822012
[16] X-G Hou Y Wu H-T Cao et al ldquoA cationic iridium(iii)complex with aggregation-induced emission (AIE) propertiesfor highly selective detection of explosivesrdquo Chemical Commu-nications vol 50 no 45 pp 6031ndash6034 2014
[17] DK Singha S Bhattacharya PMajee S KMondalMKumarand P Mahata ldquoOptical detection of submicromolar levels ofnitro explosives by a submicron sized metal-organic phosphormaterialrdquo Journal of Materials Chemistry A vol 2 no 48 pp20908ndash20915 2014
[18] R Pandey L Reddy S Ishihara A Dhir and V KrishnanldquoConformation induced discrimination between picric acidand nitro derivativesanions with a Cu-pyrene array the firstdecision making photonic devicerdquo RSC Advances vol 3 no 44pp 21365ndash21368 2013
[19] K L Reddy A M Kumar A Dhir and V Krishnan ldquoSelectiveand sensitive fluorescent detection of picric acid by new pyreneand anthracene based copper complexesrdquo Journal of Fluores-cence vol 26 no 6 pp 2041ndash2046 2016
[20] B Gole S Shanmugaraju A K Bar and P S MukherjeeldquoSupramolecular polymer for explosives sensing role of H-bonding in enhancement of sensitivity in the solid staterdquoChemical Communications vol 47 no 36 pp 10046ndash100482011
[21] S Shanmugaraju S A Joshi and P SMukherjee ldquoFluorescenceand visual sensing of nitroaromatic explosives using electronrich discrete fluorophoresrdquo Journal of Materials Chemistry vol21 no 25 pp 9130ndash9138 2011
[22] S Shaligram P P Wadgaonkar and U K Kharul ldquoFluorescentpolymeric ionic liquids for the detection of nitroaromaticexplosivesrdquo Journal of Materials Chemistry A vol 2 no 34 pp13983ndash13989 2014
[23] B Valeur and I Leray ldquoDesign principles of fluorescent molec-ular sensors for cation recognitionrdquo Coordination ChemistryReviews vol 205 no 1 pp 3ndash40 2000
[24] S R Wallenborg and C G Bailey ldquoSeparation and detectionof explosives on a microchip using micellar electrokineticchromatography and indirect laser-induced fluorescencerdquoAna-lytical Chemistry vol 72 no 8 pp 1872ndash1878 2000
[25] J N Demas and G A Crosby ldquoThe measurement of photolu-mineseence quantum yields a reviewrdquo The Journal of PhysicalChemistry C vol 75 no 8 pp 991ndash1024 1971
[26] G L Long and J D Winefordner ldquoLimit of detection a closerlook at the IUPAC definitionrdquo Analytical Chemistry vol 55 no7 pp 712ndash724 1983
[27] D Zhao and T M Swager ldquoSensory responses insolution vs solid state a fluorescence quenching study ofpoly(iptycenebutadiynylene)srdquoMacromolecules vol 38 no 22pp 9377ndash9384 2005
TribologyAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal ofInternational Journal ofPhotoenergy
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
Hindawiwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2018
Bioinorganic Chemistry and ApplicationsHindawiwwwhindawicom Volume 2018
SpectroscopyAnalytical ChemistryInternational Journal of
Hindawiwwwhindawicom Volume 2018
MaterialsJournal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
BioMed Research International Electrochemistry
International Journal of
Hindawiwwwhindawicom Volume 2018
Na
nom
ate
ria
ls
Hindawiwwwhindawicom Volume 2018
Journal ofNanomaterials
Submit your manuscripts atwwwhindawicom
4 International Journal of Spectroscopy
Emission of BAbsorbance of TNP
00
02
04
06
08
10
12
Nor
mal
ized
inte
nsity
(au
)
00
02
04
06
08
10
12
Nor
mal
ized
abso
rban
ce (a
u)
325 350 375 400 425 450 475 500300Wavelength (nm)
Figure 5 Spectral overlap of the absorption of TNP (red line) withthe emission spectrum of B (blue line)
electron-deficient TNP Thus the changes occurring in theoptical properties of B on addition of TNP are attributed tothe energy transfer process
4 Conclusions
In conclusion we have designed and synthesized a new pho-toluminescent Ni-anthracene complex The luminescencebehaviour of the complex was assessed towards differentnitroaromatics and other analytes The synthesized Ni-anthracene complex shows selective and sensitive detectionof TNP and could be a helpful tool for the people working inforensic sciences
Conflicts of Interest
The authors declare that they have no conflicts of interestregarding the publication of this article
Acknowledgments
Advanced Materials Research Center (AMRC) IIT Mandiis gratefully acknowledged for the laboratory and charac-terization facilities Abhimanew Dhir and Venkata Krishnanacknowledge Department of Science and Technology Indiafor INSPIRE faculty award Kumbam Lingeshwar Reddyis grateful to Ministry of Human Resource Development(MHRD) India for research fellowship
Supplementary Materials
Figure S1 1HNMRspectrumof A Figure S2 13CNMR spec-trum of A Figure S3 mass spectrum of complex B FigureS4 energy dispersive X-ray spectrum (EDAX) of complex BFigure S5 change in fluorescence intensity of complex B atlow concentrations of TNP Figure S6 Stern-Volmer plot forthe quenching of the fluorescence of B upon the addition of120 120583Mof TNP Table S1 comparison of detection limit withdifferent reported materials (Supplementary Materials)
References
[1] P Kovacic and R Somanathan ldquoNitroaromatic compoundsenvironmental toxicity carcinogenicity mutagenicity therapyand mechanismrdquo Journal of Applied Toxicology vol 34 no 8pp 810ndash824 2014
[2] G He H Peng T Liu M Yang Y Zhang and Y Fang ldquoA novelpicric acid film sensor via combination of the surface enrich-ment effect of chitosan films and the aggregation-inducedemission effect of silolesrdquo Journal of Materials Chemistry vol19 no 39 pp 7347ndash7353 2009
[3] S K Samanta B BhushanAChauhan andRK Jain ldquoChemo-taxis of a Ralstonia sp SJ98 toward different nitroaromaticcompounds and their degradationrdquoBiochemical andBiophysicalResearch Communications vol 269 no 1 pp 117ndash123 2000
[4] J Shen J Zhang Y Zuo et al ldquoBiodegradation of 246-trinitrophenol by Rhodococcus sp isolated from a picric acid-contaminated soilrdquo Journal of Hazardous Materials vol 163 no2-3 pp 1199ndash1206 2009
[5] M E Germain and M J Knapp ldquoOptical explosives detectionfrom color changes to fluorescence turn-onrdquo Chemical SocietyReviews vol 38 no 9 pp 2543ndash2555 2009
[6] S Chen Q Zhang J Zhang J Gu and L Zhang ldquoSynthesisof two conjugated polymers as TNT chemosensor materialsrdquoSensors and Actuators B Chemical vol 149 no 1 pp 155ndash1602010
[7] M S Meaney and V L McGuffin ldquoLuminescence-based meth-ods for sensing and detection of explosivesrdquo Analytical andBioanalytical Chemistry vol 391 no 7 pp 2557ndash2576 2008
[8] S J Toal andW C Trogler ldquoPolymer sensors for nitroaromaticexplosives detectionrdquo Journal ofMaterials Chemistry vol 16 no28 pp 2871ndash2883 2006
[9] NVenkatramaiahDMG C Rocha P Srikanth F A AlmeidaPaz and J P C Tome ldquoSynthesis and photophysical char-acterization of dimethylamine-derived Zn(II)phthalocyaninesexploring their potential as selective chemosensors for trinitro-phenolrdquo Journal ofMaterials Chemistry C vol 3 no 5 pp 1056ndash1067 2015
[10] J-F Xiong J-X Li G-Z Mo et al ldquoBenzimidazole derivativesSelective fluorescent chemosensors for the picogram detectionof picric acidrdquoThe Journal of Organic Chemistry vol 79 no 23pp 11619ndash11630 2014
[11] B Xu X Wu H Li H Tong and L Wang ldquoSelective detectionof TNT and picric acid by conjugated polymer film sensors withdonor-acceptor architecturerdquo Macromolecules vol 44 no 13pp 5089ndash5092 2011
[12] S Xu H Lu J Li et al ldquoDummy molecularly imprintedpolymers-capped CdTe quantum dots for the fluorescent sens-ing of 246-trinitrotoluenerdquoACSAppliedMaterialsamp Interfacesvol 5 no 16 pp 8146ndash8154 2013
[13] S S Nagarkar B Joarder A K Chaudhari S Mukherjee andS K Ghosh ldquoHighly selective detection of nitro explosives bya luminescent metal-organic frameworkrdquo Angewandte ChemieInternational Edition vol 52 no 10 pp 2881ndash2885 2013
[14] V Bhalla S Kaur V Vij and M Kumar ldquoMercury-modulatedsupramolecular assembly of a hexaphenylbenzene derivative forselective detection of picric acidrdquo Inorganic Chemistry vol 52no 9 pp 4860ndash4865 2013
[15] W Wu S Ye L Huang et al ldquoA conjugated hyperbranchedpolymer constructed from carbazole and tetraphenylethylenemoieties convenient synthesis through one-pot ldquoA2 + B4rdquo
International Journal of Spectroscopy 5
suzuki polymerization aggregation-induced enhanced emis-sion and application as explosive chemosensors and PLEDsrdquoJournal of Materials Chemistry vol 22 no 13 pp 6374ndash63822012
[16] X-G Hou Y Wu H-T Cao et al ldquoA cationic iridium(iii)complex with aggregation-induced emission (AIE) propertiesfor highly selective detection of explosivesrdquo Chemical Commu-nications vol 50 no 45 pp 6031ndash6034 2014
[17] DK Singha S Bhattacharya PMajee S KMondalMKumarand P Mahata ldquoOptical detection of submicromolar levels ofnitro explosives by a submicron sized metal-organic phosphormaterialrdquo Journal of Materials Chemistry A vol 2 no 48 pp20908ndash20915 2014
[18] R Pandey L Reddy S Ishihara A Dhir and V KrishnanldquoConformation induced discrimination between picric acidand nitro derivativesanions with a Cu-pyrene array the firstdecision making photonic devicerdquo RSC Advances vol 3 no 44pp 21365ndash21368 2013
[19] K L Reddy A M Kumar A Dhir and V Krishnan ldquoSelectiveand sensitive fluorescent detection of picric acid by new pyreneand anthracene based copper complexesrdquo Journal of Fluores-cence vol 26 no 6 pp 2041ndash2046 2016
[20] B Gole S Shanmugaraju A K Bar and P S MukherjeeldquoSupramolecular polymer for explosives sensing role of H-bonding in enhancement of sensitivity in the solid staterdquoChemical Communications vol 47 no 36 pp 10046ndash100482011
[21] S Shanmugaraju S A Joshi and P SMukherjee ldquoFluorescenceand visual sensing of nitroaromatic explosives using electronrich discrete fluorophoresrdquo Journal of Materials Chemistry vol21 no 25 pp 9130ndash9138 2011
[22] S Shaligram P P Wadgaonkar and U K Kharul ldquoFluorescentpolymeric ionic liquids for the detection of nitroaromaticexplosivesrdquo Journal of Materials Chemistry A vol 2 no 34 pp13983ndash13989 2014
[23] B Valeur and I Leray ldquoDesign principles of fluorescent molec-ular sensors for cation recognitionrdquo Coordination ChemistryReviews vol 205 no 1 pp 3ndash40 2000
[24] S R Wallenborg and C G Bailey ldquoSeparation and detectionof explosives on a microchip using micellar electrokineticchromatography and indirect laser-induced fluorescencerdquoAna-lytical Chemistry vol 72 no 8 pp 1872ndash1878 2000
[25] J N Demas and G A Crosby ldquoThe measurement of photolu-mineseence quantum yields a reviewrdquo The Journal of PhysicalChemistry C vol 75 no 8 pp 991ndash1024 1971
[26] G L Long and J D Winefordner ldquoLimit of detection a closerlook at the IUPAC definitionrdquo Analytical Chemistry vol 55 no7 pp 712ndash724 1983
[27] D Zhao and T M Swager ldquoSensory responses insolution vs solid state a fluorescence quenching study ofpoly(iptycenebutadiynylene)srdquoMacromolecules vol 38 no 22pp 9377ndash9384 2005
TribologyAdvances in
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
International Journal ofInternational Journal ofPhotoenergy
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
Hindawiwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2018
Bioinorganic Chemistry and ApplicationsHindawiwwwhindawicom Volume 2018
SpectroscopyAnalytical ChemistryInternational Journal of
Hindawiwwwhindawicom Volume 2018
MaterialsJournal of
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom Volume 2018
BioMed Research International Electrochemistry
International Journal of
Hindawiwwwhindawicom Volume 2018
Na
nom
ate
ria
ls
Hindawiwwwhindawicom Volume 2018
Journal ofNanomaterials
Submit your manuscripts atwwwhindawicom
International Journal of Spectroscopy 5
suzuki polymerization aggregation-induced enhanced emis-sion and application as explosive chemosensors and PLEDsrdquoJournal of Materials Chemistry vol 22 no 13 pp 6374ndash63822012
[16] X-G Hou Y Wu H-T Cao et al ldquoA cationic iridium(iii)complex with aggregation-induced emission (AIE) propertiesfor highly selective detection of explosivesrdquo Chemical Commu-nications vol 50 no 45 pp 6031ndash6034 2014
[17] DK Singha S Bhattacharya PMajee S KMondalMKumarand P Mahata ldquoOptical detection of submicromolar levels ofnitro explosives by a submicron sized metal-organic phosphormaterialrdquo Journal of Materials Chemistry A vol 2 no 48 pp20908ndash20915 2014
[18] R Pandey L Reddy S Ishihara A Dhir and V KrishnanldquoConformation induced discrimination between picric acidand nitro derivativesanions with a Cu-pyrene array the firstdecision making photonic devicerdquo RSC Advances vol 3 no 44pp 21365ndash21368 2013
[19] K L Reddy A M Kumar A Dhir and V Krishnan ldquoSelectiveand sensitive fluorescent detection of picric acid by new pyreneand anthracene based copper complexesrdquo Journal of Fluores-cence vol 26 no 6 pp 2041ndash2046 2016
[20] B Gole S Shanmugaraju A K Bar and P S MukherjeeldquoSupramolecular polymer for explosives sensing role of H-bonding in enhancement of sensitivity in the solid staterdquoChemical Communications vol 47 no 36 pp 10046ndash100482011
[21] S Shanmugaraju S A Joshi and P SMukherjee ldquoFluorescenceand visual sensing of nitroaromatic explosives using electronrich discrete fluorophoresrdquo Journal of Materials Chemistry vol21 no 25 pp 9130ndash9138 2011
[22] S Shaligram P P Wadgaonkar and U K Kharul ldquoFluorescentpolymeric ionic liquids for the detection of nitroaromaticexplosivesrdquo Journal of Materials Chemistry A vol 2 no 34 pp13983ndash13989 2014
[23] B Valeur and I Leray ldquoDesign principles of fluorescent molec-ular sensors for cation recognitionrdquo Coordination ChemistryReviews vol 205 no 1 pp 3ndash40 2000
[24] S R Wallenborg and C G Bailey ldquoSeparation and detectionof explosives on a microchip using micellar electrokineticchromatography and indirect laser-induced fluorescencerdquoAna-lytical Chemistry vol 72 no 8 pp 1872ndash1878 2000
[25] J N Demas and G A Crosby ldquoThe measurement of photolu-mineseence quantum yields a reviewrdquo The Journal of PhysicalChemistry C vol 75 no 8 pp 991ndash1024 1971
[26] G L Long and J D Winefordner ldquoLimit of detection a closerlook at the IUPAC definitionrdquo Analytical Chemistry vol 55 no7 pp 712ndash724 1983
[27] D Zhao and T M Swager ldquoSensory responses insolution vs solid state a fluorescence quenching study ofpoly(iptycenebutadiynylene)srdquoMacromolecules vol 38 no 22pp 9377ndash9384 2005
TribologyAdvances in
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Hindawiwwwhindawicom Volume 2018
International Journal ofInternational Journal ofPhotoenergy
Hindawiwwwhindawicom Volume 2018
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Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
Hindawiwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2018
Bioinorganic Chemistry and ApplicationsHindawiwwwhindawicom Volume 2018
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