m3nano6

nano6  时间:2021-01-17  阅读:()
SupportingInformationFacile,environmentallybenignandscalableapproachtoproducepristinefewlayersgraphenesuitableforpreparingbiocompatiblepolymernanocompositesGejoGeorge1,SujaBhargavanSisupal1,TeenuTomy1,AlaganandamKumaran1,PrabhaVadivelu2,VemparthanSuvekbala1,SwaminathanSivaram3andLakshminarayananRagupathy1*1CorporateR&DCenter,HLLLifecareLimited,Akkulam,Sreekariam(P.
O),Trivandrum695017,India2CSIR-NationalInstituteforInterdisciplinaryScienceandTechnology,IndustrialEstate(P.
O),Pappanamcode,Trivandrum695019,India3PolymersandAdvancedMaterialsLaboratory,NationalChemicalLaboratory,Dr.
HomiBhabhaRoad,Pune411008,India*Correspondingauthor:laks@lifecarehll.
com,laks77@gmail.
comContentsS1Planetaryballmilling(drygrinding)ofgraphitewithcurcumin/tetrahydrocurcumin/quercetinasexfoliatingagentsS1.
1PlanetaryballmillingtechniqueS2Characterizationofexfoliatedgraphite(usingcurcumin/tetrahydrocurcumin/quercetinasexfoliatingagent)producedusingplanetaryballmilling(solidphaseexfoliation)S2.
1XRDS2.
2RamanspectroscopyS2.
3TEManalysisS3Characterizationofexfoliatedgraphite(curcuminasexfoliatingagent)producedusingplanetaryballmilling(solution-phaseexfoliation)S3.
1XRDS3.
2RamanSpectroscopyS3.
3TEManalysisS4Characterizationofexfoliatedgraphite(curcuminasexfoliatingagent)producedusingsandgrinder(solution-phaseexfoliation)S4.
1XRDS4.
2RamanSpectroscopyS4.
3TEManalysisS5Toxicityofgrapheneexfoliatingagents/chemicals/salts/etc.
S6ComputationalstudiesoninteractionofgraphenewithcurcuminS7Preparationoffewlayergraphene-NRthinfilmnanocompositeS8Characterizationoffewlayergraphene-NRthinfilmnanocompositeS8.
1TEManalysisS8.
2StabilityofcurcuminundertheprocessingconditionS9Biocompatibilityofgraphene-NRlatexthinfilmnanocompositeS1Planetaryballmillingofgraphitewithcurcumin/tetrahydrocurcumin/quercetinTheplanetaryballmillusedwasaRestchPM400with4grindingbowlfasteners.
Inatypicalprocedure20gofgraphitewasmilledwith60gcurcumin/tetrahydrocurcumin/quercetin(1:3ratio)and2.
5gDarvanI(stabilizer)for1hat100rpm(15min.
grindingfollowedby15min.
pausetoavoidexcessiveheatproduction).
Zirconiacontainersandzirconiaballswereusedfortheballmillingprocedure.
Aftergrinding,thesamplesaredispersedinwaterandsonicatedfor2min.
at25%amplitudeusinga750Wsonicator.
S2Characterizationofexfoliatedgraphite(curcumin/tetrahydrocurcumin/quercetinasexfoliatingagent)producedusingplanetaryballmilling(solidphaseexfoliation)S2.
1XRDofquercetinexfoliatedgraphiteTheXRDofGraphite:Quercetin:Darvan(1:3:0.
125beforeandaftergrinding)sampleandgraphiteisshownasFigureS1.
FigureS1:NormalizedXRDofgraphiteandgrapheneproducedusingquercetinastheexfoliatingagent(ratioscorrespondtoGraphite:Quercetin:Darvan).
S2.
2Ramanspectraofcurcumin/tetrahydrocurcumin/quercetinexfoliatedgraphiteTheRamanspectraofGraphite:Quercetin:DarvansampleandgraphiteisshownasFigureS2.
Theshapeof2Dband1:3:0.
125Graphite:Quercetin:Darvanshowsthattheproducedgraphenesareabout10layers1-3thick.
FigureS2:Ramanspectraofgraphenesamplesproducedusingquercetinastheexfoliatingagent.
The2DbandofallGraphite:Curcumin:DarvansamplesisshownasFigureS3.
Hereagain,aclearshiftofthe2Dbandtothelowerwavelengthisvisible.
Theshapeof2Dbandin1:3:0.
125Graphite:Curcumin:Darvanshowsthattheproducedgraphenesarefewlayers1-5.
ThezoomedinfiguresofDand2Dbandsof1:3:0.
125Graphite:Curcumin:DarvanareshowninFigureS4.
FigureS3:2Dbandofgraphiteandgraphite/curcuminsamplemilledatdifferentratios.
TheDarvanratiois0.
125inallthecases.
FigureS4:Dand2Dbandsofgraphiteandmilledgraphite/curcumin/Darvan(1:3:0.
125)samples.
The2DbandofallGraphite:TetrahydroCurcumin:DarvansamplesisshownasFigureS5.
Hereagain,aclearshiftofthe2Dbandtothelowerwavelengthisvisible.
Theshapeof2Dband1:3:0.
125Graphite:TetrahydroCurcumin:Darvanshowsthattheproducedgraphenesarefewlayer1-3.
FigureS5:2Dbandofgraphiteandgraphite/tetrahydrocurcumin/darvansamplemilledatdifferentratios.
TheratioscorrespondtoGraphite:tetrahydrocurcumin:darvan.
Thedeconvolutionofthe2Dbandin1:3:0.
125Graphite:Curcumin:Darvansampleleadstofourlorenztianpeaksat2666.
31,2688.
46,2708.
88and2725.
91cm-1andthedeconvolutionof2Dbandofthe1:3:0.
125Graphite:TetrahydroCurcumin:Darvanyieldsfourlorenztianpeaksappearingat2664.
87,2684.
26,2701.
85and2721.
23cm-1.
ID/ID',ID/IGandin-planecrystallitesizes,LaofgraphenesamplespreparedaregiveninTableS1.
TableS1.
ID/ID',ID/IGandin-planecrystallitesizes,Laofgraphenesamplespreparedusingdifferentexfoliatingagents.
S.
No:SampledetailsID/IDID/IGLa(nm)1.
Graphite:Curcumin:Darvan(1:3:0.
125)0.
85,1.
23,1.
090.
54,0.
45,0.
4028,37,412.
Graphite:Tetrahydrocurcumin/Darvan(1:3:0.
125)0.
97,0.
74,0.
810.
28,0.
21,0.
3559,79,473.
Graphite:Quercetin:Darvan(1:3:0.
125)No.
ofgraphenelayersis10,therefore,D'peakisnotobservedhere.
0.
17,0.
10,0.
2198,167,79S2.
3TEManalysisTheTEMimagesof1:3:0.
125Graphite:Quercetin:DarvansampleisshownasFigureS6.
Theimagesclearlyshowthattheproducedgrapheneismultilayered(≥5)evidencedbythereducedtransparencyofthegraphenesheets.
FigureS6:TEMimagesof1:3:0.
125Graphite:Quercetin:Darvansample.
S3Characterizationofexfoliatedgraphiteproducedusingplanetaryballmilling(solutionphaseexfoliation)S3.
1XRDFigureS7:XRDofgraphite,curcuminandGraphite:Curcumin:Darvan(mixture)sampleswithvaryingsolventratios.
ThenormalizedXRDspectrumofgraphite,curcumin&Graphite:Curcumin:Darvansampleswithvaryingsolventratios(acetone:water)isshownasFigureS7.
S3.
2RamanSpectraTheRamanspectraofGraphite:Curcumin:Darvansamplespreparedusingdifferentsolventratios(acetone:water)areshownasFigureS8.
ThisdemonstratesthatinthecaseofGraphite:Curcumin:Darvanwith50:50(acetone:water)mixturethegrapheneproducedisabi-layerwhereasinothersolventratiositisfoundtobeapproximately5layers(2Dbanddeconvolutesinto2Lorentzianpeaks)1-3.
ID/ID',ID/IGandin-planecrystallitesizes,Laofgraphenesamplespreparedusing50:50(acetone:water)solventmixtureGraphite:Curcumin:DarvanisshownasTableS2.
FigureS8:RamanspectraofGraphite:Curcumin:Darvan(mixture)sampleswithvaryingsolventratios(acetone:water).
TableS2.
ID/ID',ID/IGandin-planecrystallitesizes,Laofgraphenesamplespreparedusingwetgrindingmethodin50:50wt%acetone:waterusingcurcumin.
S.
No.
SampledetailsID/IDID/IGLa(nm)1.
Graphite:Curcumin:Darvan(1:3:0.
125)0.
88,0.
92,1.
120.
16,0.
20,0.
23104,83,73ID/ID'valuesclearlyindicatesthatnonewdefectsareintroducedintothegraphenesamplesduringthegrindingprocess.
S3.
3TEManalysisTEMimagesofGraphite:Curcumin:Darvan(50:50acetone:water)systemwith1:3:0.
125ratioisshownasFigureS9.
(a)(b)FigureS9:TEMimagesof(a)&(b)Graphite:Curcumin:Darvan(50:50actone:water)sampleandc)SAEDpatternS4CharacterizationofexfoliatedgraphiteproducedusingsandgrinderS4.
1XRDThenormalizedXRDofgraphiteandGraphite:Curcumin:Darvan(1:3:0.
125)sampleproducedusingsandgrindingtechniqueisshownasFigureS10.
FigureS10:NormalizedXRDofgraphiteandGraphite:Curcumin:Darvan(1:3:0.
125wt.
ratio)sampleproducedusingsandgrindingtechnique.
S4.
2RamanSpectraTheRamanspectraofgraphiteandgraphene(Graphite:Curcumin:Darvan,1:3:0.
125)producedusingsandgrindingprocess,alongwiththedeconvolutionof2DbandisshownasFigureS11andthecorrespondingID/IGratiosintableS3.
FigureS11:RamanspectraofgraphiteandGraphite:Curcumin:Darvan(1:3:0.
125)sampleproducedusingsandgrinderandthedeconvoluted2Dband.
TableS3.
ID/ID',ID/IGandin-planecrystallitesizes,Laofgraphenesamplespreparedusingsandgrinder.
S.
No.
SampledetailsID/IDID/IGLa(nm)1.
Graphite:Curcumin:Darvan(1:3:0.
125)0.
78,0.
55,0.
480.
11,0.
10,0.
05152,167,335S.
4.
3TEManalysisTheTEMimagesofGraphite:Curcumin:Darvansample(1:3:0.
125)producedbysandgrindingtechniqueisshownasFigureS12.
(a)(b)FigureS12:(a)&(b)TEMimagesofGraphite:Curcumin:Darvan(1:3:0.
125)samplesproducedbysandgrindingand(c)SAEDpatternofthegraphenesheet.
S5.
TableS4.
Toxicityofgrapheneexfoliatingagents/chemicals/saltsetc.
S.
No.
ExfoliationMethod/agentReportedno.
oflayersGrapheneproductionrate(yield)ing/hrD/GRatioToxicityOraltoxicitySkintoxicityChronictoxicity1Solid-phase:(a)BallmillingwithCurcumin(Currentwork,solid-phaseexfoliation,solution-phaseexfoliation).
(b)sandGrindingwithCurcumin2-10(a)45.
7(solid-phase),20(solution-phase).
(b)10(sandgrinding).
(a)0.
40-0.
54(solid-phase),0.
16-0.
23(solution-phase).
(b)0.
05-0.
11(sandgrinding).
LD50Oral-Mouse->2,000mg/kg.
LD50Oral-Rat->2,000mg/kg.
54Slightlyhazardousincaseofskincontact(irritant).
55Curcumin,administeredbeforeorafterradiation,markedlyreducedacuteandchronicskintoxicityinmice(p20,000mg/kg.
60N-methylpyrrolidoneLD50Dermal-Rabbit-8,000mg/kg.
59--5Solid-phase:BallmillingwithMelamine1,6.
Fewlayers0.
0151and22.
960.
41-0.
49LD50Oral-Rat-male-3,161mg/kg.
61LD50.
Dermal-Rabbit->1,000mg/kg.
11Noskinirritation.
61Acutedermaltoxicityinrabbitspresentswhentheexposureis1g/kgbodywt.
62Long-termexposuretomelaminereducesfertilityandresultsinfetaltoxicityinanimalstudies.
Themostcommonlyreportedchronicrenaltoxicityisstoneformation.
626Solution-phase:Wetstirredmediamillingwithsodiumdodecylsulfate7.
SingletoMultilayers1.
5-2.
5~0.
6-0.
7(532nm)LD50Oral-Rat-maleandfemale-1,200mg/kg.
63Skinirritation(Rabbit24hOECDTestGuideline404).
63InanimalstudiesSDSappearstocauseskinandeyeirritation.
64SDSmayworsenskinproblemsinindividualswithchronicskinhypersensitivity.
647Solution-phase:CVDwithsodiumethoxide8.
Few(4)layers1~1(532nm)LD50Oral-Rat-maleandfemale-598mg/kg(OECDTestGuideline401).
65Causessevereburnsonskin(Rabbit-3minOECDTestGuideline404).
15Createredness,painblistersandskinburns.
668Solution-phase:KIntercalationwithacid(HNO3andH2SO4)-intercalated/exfoliatedgraphite9.
30-400.
9gNoRamanLD50Intraperitoneal-Mouse-700mg/kg.
67Exposuretoradiationcandamagethebasalcelllayerofskin,resultingininflammation,erythema,anddryormoistdesquamation.
689Solution-phase:Interlayer1-30.
4gNoRamanFeCl2LD50Oral-Rat-FeCl2NoskinH2O2MaterialiscatalyticexfoliationwithFeClandHO10.
>500mg/kg.
69H2O2Oral-Rat-910mg/kg.
70irritation(Rabbit-OECDTestGuideline404).
69H2O2LD50Dermal-Rat-4060mg/kgVeryhazardousincaseofskincontact(irritant).
70destructivetotissueofthemucousmembranesandupperrespiratorytract.
Exposurecancauselungirritation,chestpainandoedemawhichmaybefatal.
7010Solution-phase:NainliquidNHReduction11.
10.
33g~1.
4(514nm)AmmoniaLC50Inhalation-Rat-4h-2000ppm.
71LC50Rabbitinhalation7,050mg/cum/1hr.
72LD50Ratoral350mg/kg.
73LD50Mouseinhalation4,837ppm/1hr.
74AmmoniaThevaporeveninlowconcentrationisextremelyirritatingtoskin,eyesandrespiratorypassages.
75AmmoniaExposuresof500ppmfor30minhavecausedupperrespiratoryirritation,tearing,increasedpulserate,andbloodpressure.
7611Solution-phase:ExfoliationwithchlorosulfonicacidandHO12.
Fewlayers(3)~0.
25g0(514nm)chlorosulfonicacidLC50mouseinhalation52.
5mg/cum/2hr.
LC50ratinhalation38.
5mg/cum/4hr.
77chlorosulfonicacidHighlyirritating&corrosivetoeyes,skin,mucousmembranes.
7812Solution-phase:Sonicationofexpandedgraphitewith1-pyrenesulfonicacidsodiumsalt(Mosteffectiveone)13.
Fewlayer0.
020.
33---13Solution-phase:SonicationwithIsopropanol.
141-5~0.
0150.
2-0.
4(633nm)LD50Oral-Rat-5,045mg/kgRemarks:Behavioral:Alteredsleeptime(includingchangeinrightingreflex).
Somnolene(generaldepressedactivity).
LC50Inhalation-Rat-8h-16000ppm.
79Mildskinirritant.
LD50Dermal-Rabbit-12,800mg/kg.
79Repeatedexposuresproducedtoxiceffectsonlyatthehighestconcentration(5000ppm)andakidneychangeinmaleratsofunknownbiologicalsignificance.
8014Solution-phase:Hornultrasonicationofnaturallyoccurringgraphiteflakeswithbilesaltsodiumcholate15.
Fewlayers0.
018----15Solution-phase:SonicationwithN-Methyl-2-pyrrolidone(NMP)andthermaltreatment16.
1-45100ppm.
81LD50Dermal-Rabbit-8,000mg/kg.
81Theno-observed-effectlevelforNMPwas5000ppmformaleandfemalerats,600ppmformalemice,and1200ppmforfemalemice.
8216Solution-phase:Intercalationofalkalimetal(ternaryKCl-NaCl-ZnCl2eutecticsystem)betweengraphiteInterlayers17.
Fewlayers(18%ofaresingle/doublelayer)0.
0120.
15(514nm)---17Solution-phase:SonicationwithGumArabic(biopolymer)18.
5-20~610-3~0.
25(633nm),LD50Oral-Rat->16,000mg/kg.
83--18Solution-phase:Grindingwithionicliquids(1-Butyl-3-methylimidazoliumhexafluorophosphate)19.
2-50.
010.
23(514nm)---19Solution-phase:Dissolutioninsuperacids(chlorosulphonicacid)20a&20b.
Single(70%)~4.
210-30.
1-0.
5(514nm)LC50mouseinhalation52.
5mg/cum/2hr.
84Highlyirritating&corrosivetoeyes,skin,mucousmembranes.
85-20Solution-phase:SonicationinCyclohexanone21.
Few3x10-3NoRamanLD50Oral-Rat-12,705mg/kgLC50Inhalation-Rat-4h-34,000mg/l(OECDTestGuideline403)LD50Dermal-Rabbit->2,000mg/kg.
86Noskinirritation.
86Chronicorrepeatedexposurecanresultinskinirritationduetodefattingoftheskin.
8721Solution-phase:SonicationwithSodiumdodecylbenzenesulfonate.
22Fewlayers(>40%andMonolayer(3%)2.
5x10-30onthickfilms(largeFLG),~0.
4onthinfilms(smallflakes),532nmLD50Oral-Rat-438mg/kg.
88Skinirritatant.
88-22Solution-phase:Sonicationwithvinylcaprolactam.
23Fewlayers(5-7)2.
1x10-3~0.
l4(532nm),0.
1inpowderLD50Oral-Rat-male/female1,860mg/kg.
89LD50Dermal-Rabbit-maleandfemale-1,700mg/kg(OECDTestGuideline402).
90Repeatedexposuretosmallquantitiesmayaffectcertainorgans.
Damagestheliver.
8923Solution-phase:GrindingwithIonicliquid(1-hexyl-3-methylimidazoliumhexafluorophosphate)followedbysonication24.
Fewlayers2.
2x10-3~0.
l4(532nm),0.
1inpowder-Causesskinirritation.
91-24Solution-phase:Sonicationwithsodiumchloatesurfactant25.
BiandMultilayers2x10-30(488nm)LD50Rat-1200mg/kg.
92Hazardousincaseofskincontact(irritant).
92-25Solution-phase:High-shearmixingwithorthodichlorobenzeneand(DCB)sonication26.
Fewlayers(3,000mg/kg.
11238Solution-phase:Sonicationofnanoribbonsinhypophosphorousacid39.
Multilayers3.
310-3Nodataavailable---39Solution-phase:Sonicationwithorganosilanes(Phenyltriethoxysilaneand3-glycidoxypropyltrimethoxysilane)40.
Fewlayers3.
310-30.
65(532nm)PhenyltriethoxysilaneLD50Oral-Rat-2,734mg/kg.
1133-glycidoxypropyltrimethoxysilaneLD50Oral-Rat-8,030mg/kg.
114PhenyltriethoxysilaneLD50Dermal-Rabbit-3,167mg/kg.
1133-glycidoxypropyltrimethoxysilaneLD50Dermal-Rabbit-4,248mg/kg.
114-40Solution-phase:MicrowaveassistedexfoliationofFeCl3andCH3NO2co-intercalatedgraphite.
41Multilayers1.
610-30butlayergraphenes(5)FeCl3LD50Oral-Mouse-1,300mg/kg.
115CH3NO2LD50Oral-Rat-maleandfemale-1,478mg/kg.
115FeCl3LD50Dermal-Rabbit->2,000mg/kg.
115-41Solution-phase:SonicationwithN-Methylpyrrolidone42.
Single,biandfewlayers/fewlayers/fewlayers(50-10layersofgraphene,respectively.
-0(633nm)---50Solution-phase:ElectrochemicalexfoliationwithLiCl/propylenecarbonate51.
5,000mg/kg.
119-PropylenecarbonateLD50Dermal-Rabbit->2,000mg/kg.
119--51Solution-phase:K(THF)xC24(THF=tetrahydrofuran,x=1-3)x52.
Multilayers->1---52Solution-phase:MethodsproducedthroughGO(e.
g.
ConcentratedSulfuricacid(H2SO4)(a)incombinationwithfumingNitricacid(HNO3)andPotassiumchlorate(KClO3)(Staudenmaiermethod)or(b)incombinationwithconcentratedHNO3andKClO3(Hofmannmethod)or(c)intheabsenceofHNO3butinthepresenceofSodiumnitrate(NaNO3)andPotassiumpermanganate(KMnO4)(Hummersmethod)53.
-≤0.
450.
9-≥1H2SO4LD50Oral-Rat-2,140mg/kg.
120HNO3-KClO3LD50Oral-Rat-1,870mg/kg.
121NaNO3LD50Oral-Rat-3,430mg/kg.
122KMnO4LD50Oral-Rat-1,090mg/kg.
123H2SO4Extremelycorrosiveanddestructivetotissue.
120HNO3-KClO3LD50Dermal-Rat-maleandfemale->2,000mg/kg.
121NaNO3LD50Dermal-Rat->5,000mg/kg.
122KMnO4Corrosive.
123S.
6ComputationalstudiesoninteractionofgraphenewithcurcuminFigureS13:Theoptimizedstructuresofcurcuminconformerswiththeirenergies(a.
u)atB97-D/6-31G**leveloftheory.
53SolutionandSolid-phaseDryballmillinggraphiteinthepresenceofhydrogen,carbondioxide,sulfurtrioxide,orcarbondioxide/sulfurtrioxidemixture128.
Fewlayers(Edgefunctionalized)0.
10.
79-1.
44SO3LC50Inhalation-Rat-4h-375mg/m3Extremelycorrosiveanddestructivetotissue.
129SO3Severeskinirritant.
12954SolutionPhaseGraphitesonicatedwiththebiobasedsolventcyrenefor15minutesandthencentrifugedtoobtaingrapheneoxide130.
Monotofewlayergraphene(lessthan10)0.
060.
20LD50Oral-Rat-female->2,000mg/kg131.
Noskinirritation-Curcuminconformersandcurcumin-demethoxyderivativesCurcumin(keto-enolicform-1)Curcumin(keto-enolicform-2)Standardorientation:Curcumin(keto-enolicform-3)Curcumin(di-ketoform)DemethoxyCurcuminBis-demethoxyCurcuminGraphenemodelsC160H32C168H36C156H36C160H32/curcuminC160H32/demethoxycurcuminC160H32/bis-demethoxycurcuminC168H36/curcuminC156H36/curcuminS7.
Productionoffewlayergraphene-NRthinfilmnano-composite(a)Preparationofgraphenedispersion:MilledGraphite:Curcumin:Darvan(1:3:0.
125)samplewasmadeintoa30wt.
%aqueousdispersionbyusingprobesonicationindistilledwater(2min.
at25%amplitude).
(b)Preparationofgraphene-NRlatexmixture:Theabovegraphenedispersion(at0.
3,0.
7,1.
5,3and5phr)wasthenaddedtothecompoundedNRlatexusingprobesonicationtechnique(3min.
at20%amplitude).
(c)Regulationofcompound:Thegraphene-NRLatexwasstabilizedbyadditionof1%ammoniaandhadasolidscontentof48±3%.
Themixturewasstirredslowlytoensurehomogeneityandtheoptimumcurewascheckedusingthefollowingchloroformtest.
Ina50mLbeaker5mLoftheabovemadeNRlatexwastransferred.
Then,5mLofchloroformwasaddedtothesameandstirredthemixturegentlyandcontinuouslytoobtainacoagulum.
Thismixturewasthenkeptbetweentwofilterpapersandpressed.
Thissolidmaterialwasbrokenoffgentlyandjudgedthenatureofcure.
AllthenanocompositesweremadefromnormalcureNRlatex.
Grapheneincorporatednaturalrubbernanocompositethinfilmswereproducedusingthefollowingsteps;(1)Pre-treatmentofglassmolds(2)Latexdipping(3)Vulcanizationfollowedbystrippingthethinfilmfrommouldusingsilicapowder.
Priortoeachdippingprocedurecleaningofglassmoldsweredonebybrushingwithdetergentwaterfollowedbywashingwithhotwater.
Later,themoldsweredriedinhotairovenat70°C.
Forlabscaleproduction,wehaveusedasemi-automatictypedippingmachinesuppliedbyPLASTOMEKPrivateLtd.
India.
Thethicknessoftheproducednanocompositethinfilmsamplescanbecontrolledbyvaryingthedippingspeed.
Subsequenttoeachdipping,theskimandcreamontheNRlatexsurfacewereremovedusingaclothorsponge.
Thepresenceofanybubbleswasalsoremovedinordertoavoidanyweakspotsonthethinfilms.
ThemoldfittedonmachineisthendippedslowlyintotheNRlatexatarateofspeedofdippingfrom1-1.
5cm/sec.
Afterimmersingmolduptoarequiredlength,themoldwaswithdrawnslowlyandrotatedthemoldtoensureauniformflowoftheNRLatex.
Then,themoldwaskeptinhotairovenfordryingat70°Cfor2-3min.
Afterdryingandcooling,aseconddippingwasdoneandkeptfordryingagainat70°Cfor2-3min.
Forvulcanization,thethinfilmsonthemoldaretransferredtoahotairovenandheatedtheproductforabout45min.
atatemperatureof80±5°C.
S8Characterizationoffewlayergraphene-NRthinfilmnano-compositeS8.
1TEManalysisMorphologyofthefewlayergrapheneNRthinfilmnano-compositeswasanalyzedusingaJEOLJEM-2010TEMat200kV.
Sampleswerepreparedbycryo-microtomingat-70C.
S8.
1.
1TEManalysisofGraphite:Curcumin:Darvan-NRthinfilmnanocompositeTheTEMimagesof1.
5phrGraphite:Curcumin:DarvancontainingNRthinfilmnano-compositeareshownasFigureS14.
Thesamplesshowanetworklikestructure.
FigureS14TEMimagesof1.
5phrgraphene(Graphite:Curcumin:Darvan)reinforcedNRlatexthinfilms.
S8.
2Stabilityofcurcuminundertheprocessingcondition1.
5phrfewlayergraphene-NRthinfilmnano-compositeweighingabout1.
11gwasSoxhletextractedusing200mLofdichloromethanefor2h.
Aftercompletionofextraction,agreenishorangecolorextractwasobtainedwhichwasthencooled,concentratedusingrotavaportogetagreenishorangeprecipitate.
Characterizationofcurcumin(obtainedafterSoxhletextraction)bythinlayerchromatography:TheextractobtainedafterextractionwassubjectedtoTLCusingpre-coatedsilicagel(Merck60F254,20cm*20cm)plates.
Thecurcuminwasseparatedusingchloroform:methanol:(9.
5:0.
5.
(FigureS15).
FigureS15:TheTLCresultsofdichloromethaneextractobtainedafterSoxhletextraction.
*WhereA=Soxhletextractfromnaturalrubberlatex(controlsample)B=CommercialsampleofcurcuminC=Soxhletextractfromcontrolcurcumin(thinfilmhaving0.
7phrcurcuminandnographene)D=Soxhletextractfrom1.
5phrgraphene(Graphene/Curcumin/Darwan)/-NRthinfilmnanocompositeAcommercialsampleofcurcumin(B)exhibitsthreespots(Rfvalues0.
78,0.
54,0.
50).
Similarspotsareobtainedfromcontrolcurcumin(C)and1.
5phrgraphene(drymilledGraphene/Curcumin/Darwan)/-NRthinfilmnano-composite(D).
Theresultsconfirmthattheleachedoutextractfrombothcontrolcurcumin(C)and1.
5phrgraphene(D)iscurcumin.
Thustheprocessdoesnotresultinanydegradationofcurcumin.
Characterizationofcurcumin(obtainedafterSoxhletextraction)byHighPerformanceLiquidChromatography(HPLC):TheHPLCsystemconsistingofAgilent1260seriesPDAdetectorwasusedforthisstudy.
ChromatographicseparationwasachievedusingAgilentRP-C18column(4.
6mm*150mm,5m).
ThemobilephasecomprisedofsolventA:water(1%aceticacid)whichwasadjustedtopHof3.
0using50%triethanolamineandsolventB:Acetonitrileintheratioof50:50v/v.
Theisocraticelutionwascarriedoutwiththeflowrateof1.
5ml/minatambienttemperature.
Priortouse,allthesampleswerefilteredthrougha0.
45mmembranefilter.
Thechromatogramwasobtainedatwavelengthof254nm.
PreparationofstandardanddifferentsamplesolutionsforHPLC:Stocksolutionsofstandardcurcumin,dichloromethaneextractsobtainedafterSoxhletextractionofnaturalrubberthinfilm,curcuminincorporatednaturalrubberthinfilmand1.
5phrfewlayergraphenenaturalrubbernanocompositethinfilmsampleswerepreparedbydissolving10mgofsampleinmethanol.
Theobservedpeaks(FigureS16)areinagreementwiththeHPLCchromatogramsofstandardcurcuminasreportedbypreviousresearchers131.
FigureS16:HPLCchromatogramofSoxhletextractobtainedfrom1.
5phrGraphite:Curcumin:Darvanthinfilmsample.
S9Biocompatibilityofgraphene-NRlatexthinfilmnanocompositeTableS5.
Qualitativegradingschemeforscoringcytotoxicitybasedonmorphologyofcells(Balb/c3T3).
GradeReactivityConditionsofallculture0NoneDiscreteintracytoplasmaticgranules,nocelllysis,noreductionofcellgrowth1SlightNotmorethan20%ofthecellsareround,looselyattachedandwithoutintracytoplasmicgranules,orshowchangesinmorphology;occasionallysedcellsarepresent;onlyslightgrowthinhibitionobservable2MildNotmorethan50%ofthecellsareround,devoidofintracytoplasmicgranules,noextensivecelllysis;notmorethan50%growthinhibitionobservable3ModerateNotmorethan70%ofthecelllayerscontainroundedcellsorarelysed;celllayersnotcompletelydestroyed,butmorethan50%growthinhibitionobservable4SevereNearlycompleteorcompletedestructionofthecelllayersTableS6:PrimaryindexusedtopredicttheskintoxicityonNewZealandwhiteRabbits.
MeanScoreResponsecategory0to0.
4Negligible0.
5to1.
9Slight2to4.
9Moderate5to8SevereTableS7:Experimentalprocedureusedforperformingskinsensitizationonguineapigs.
GroupNo.
AnimalNo.
SexTreatmentGroupIntradermalInductionPhase(0.
1mL)Topicalinductionphase(0.
5mLusingapatch)*Challengephase#(0.
5mLusingapatch)*InjectionIInjectionIIInjectionIII10%SLSTreatmentG11-5FPolarsolventcontrol1:1mixture(v/v)FCA+(saline)Polarsolventalone50%w/vformulationofthevehicleina1:lmixture(v/v)FCA+(saline)YesPolarsolventPolarsolvent&PolarextractofTestitemG26-15FTestiteminpolarsolvent1:1mixture(v/v)FCA+(saline)TestiteminpolarsolventPolarextractofTestitemina1:1mixture(v/v)FCA+(saline)YesPolarextractofTestitemPolarsolvent&PolarextractofTestitemG316-20FNonpolarsolventcontrol1:1mixture(v/v)FCA+(sunfloweroil)Nonpolarsolventalone50%w/vformulationofthevehicleina1:lmixture(v/v)FCA+(sunfloweroil)YesNonpolarsolventNonpolarsolvent&NonpolarextractofTestitemG421-30FTestiteminnonpolarsolvent1:1mixture(v/v)FCA+(sunfloweroil)TestiteminnonpolarsolventNonpolarextractofTestitemina1:1mixture(v/v)FCA+(sunfloweroil)YesNonpolarextractofTestitemNonpolarsolvent&NonpolarextractofTestitemF-Female;FCA-Freund'sCompleteAdjuvant;SLS-SodiumLaurylSulphate;*Patcharea=8cm2approximately;#GauzesoakedintherespectivepreparationIntradermalInjectionwasgivenonDay0atsitesA,BandCTopicalapplicationwasappliedonDay7ChallengedosewasappliedonDay21SitesA,BandCareshownbelow:FigureS17:1–Cranialend;2–0.
1mlintradermalinjectionsites;3–clippedintrascapularregion;4–CaudalendTableS8.
Positivecontrolexperimentsperformedwithα-Hexylcinnamaldehydeforskinsensitizationonguineapigs.
Concentrationofα-HexylcinnamaldehydeVehicleusedResultInductionIInduction2ChallengeNoofanimals+veMaximumreactiongrading0.
5%v/v50%v/v10%v/v4:1v/vacetone:sunfloweroil+vein7/10animalsGrade2-ModerateandconfluenterythemaTableS9.
Primaryindexusedtopredictforskinsensitizationonguineapigs.
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Isopropanol;MSDSProductNo.
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docountry=IN&language=en&productNumber=W292907&brand=ALDRICH&PageToGoToURL=http%3A%2F%2Fwww.
sigmaaldrich.
com%2Fcatalog%2Fsearch%3Fterm%3DIsopropanol%26interface%3DAll%26N%3D0%26mode%3Dmatch%2520partialmax%26lang%3Den%26region%3DIN%26focus%3Dproduct(Accessedon27.
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Availablefrom,asofSeptember22,2011:http://www.
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N-Methyl-2-pyrrolidone;MSDSProductNo.
W292907;AvailablefromSigma-Aldrich.
http://www.
sigmaaldrich.
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docountry=IN&language=en&productNumber=328634&brand=SIAL&PageToGoToURL=http%3A%2F%2Fwww.
sigmaaldrich.
com%2Fcatalog%2Fsearch%3Fterm%3DN-Methyl-2-pyrrolidone%26interface%3DAll%26N%3D0%26mode%3Dmatch%2520partialmax%26lang%3Den%26region%3DIN%26focus%3Dproduct(Accessedon27.
04.
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82.
MalleyLAetal;DrugChemToxicol24(4):315-38(2001).
83.
Gumarabic;MSDSProductNo.
G9752;AvailablefromSigma-Aldrich.
http://www.
sigmaaldrich.
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docountry=IN&language=en&productNumber=G9752&brand=SIGMA&PageToGoToURL=http%3A%2F%2Fwww.
sigmaaldrich.
com%2Fcatalog%2Fsearch%3Fterm%3DGum%2Barabic%2Bfrom%2Bacacia%2Btree%26interface%3DProduct%2520Name%26N%3D0%2B%26mode%3Dmode%2520matchpartialmax%26lang%3Den%26region%3DIN%26focus%3DproductN%3D0%2520220003048%2520219853286%2520219853147(Accessedon27.
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Cyclohexane;MSDSProductNo.
P6001;AvailablefromSigma-Aldrich.
http://www.
sigmaaldrich.
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docountry=IN&language=en&productNumber=227048&brand=SIAL&PageToGoToURL=http%3A%2F%2Fwww.
sigmaaldrich.
com%2Fcatalog%2Fsearch%3Fterm%3DCyclohexane%26interface%3DAll%26N%3D0%26mode%3Dmatch%2520partialmax%26lang%3Den%26region%3DIN%26focus%3Dproduct(Accessedon27.
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Sodiumdodecylbenzenesulfonate;MSDSProductNo.
289957;AvailablefromSigma-Aldrich.
http://www.
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docountry=IN&language=en&productNumber=289957&brand=ALDRICH&PageToGoToURL=http%3A%2F%2Fwww.
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com%2Fcatalog%2Fsearch%3Fterm%3DSodium%2Bdodecylbenzenesulfonate%26interface%3DProduct%2520Name%26N%3D0%2B%26mode%3Dmode%2520matchpartialmax%26lang%3Den%26region%3DIN%26focus%3DproductN%3D0%2520220003048%2520219853286%2520219853147(Accessedon27.
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89.
n‐Vinylcaprolactam;PMSDSProductNo.
M‐218;ScientificpolymerProducts,Inc.
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90.
n-Vinylcaprolactam;MSDSProductNo.
415464;AvailablefromSigma-Aldrich.
http://www.
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docountry=IN&language=en&productNumber=415464&brand=ALDRICH&PageToGoToURL=http%3A%2F%2Fwww.
sigmaaldrich.
com%2Fcatalog%2Fsearch%3Fterm%3Dvinylcaprolactam%26interface%3DAll%26N%3D0%26mode%3Dmatch%2520partialmax%26lang%3Den%26region%3DIN%26focus%3Dproduct(Accessedon27.
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Sodiumchlorate;MSDSProductNo.
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93.
OrganizationforEconomicCooperationandDevelopment;ScreeningInformationDataSetfor1,2-Dichlorobenzene,95-50-1p.
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docountry=IN&language=en&productNumber=227056&brand=SIAL&PageToGoToURL=http%3A%2F%2Fwww.
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104.
Sodiumdodecylsulfate;MSDSProductNo.
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105.
Dodecylbenzenesulfonicacid;MSDSProductNo.
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106.
Hexadecyltrimethylammoniumbromide;MSDSProductNo.
H5882;AvailablefromSigmaAldrich.
http://www.
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docountry=IN&language=en&productNumber=H5882&brand=SIGMA&PageToGoToURL=%252Fcatalog%252Fproduct%252Fsigma%252Fh5882%253Flang%253Den(Accessedon26.
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107.
Myristyltrimethylammoniumbromide;MSDSProductNo.
T4762;AvailablefromSigmaAldrich.
http://www.
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docountry=IN&language=en&productNumber=T4762&brand=SIGMA&PageToGoToURL=%252Fcatalog%252Fproduct%252Fsigma%252Ft4762%253Flang%253Den(Accessedon26.
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108.
Sodiumdeoxycholate;MSDSProductNo.
D6750;AvailablefromSigmaAldrich.
http://www.
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109.
IGEPALCO-890;MSDSProductNo.
238678;AvailablefromSigmaAldrich.
http://www.
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110.
Tween20;MSDSProductNo.
P1379;AvailablefromSigmaAldrich.
http://www.
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111.
Tween80;MSDSProductNo.
P1754;AvailablefromSigmaAldrich.
http://www.
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docountry=IN&language=en&productNumber=P1754&brand=SIAL&PageToGoToURL=%252Fcatalog%252Fsearch%253Fterm%253Dtween%2B80%2526interface%253DAll%2526N%253D0%2526mode%253Dpartialmax%2526lang%253Den%2526region%253DIN%2526focus%253Dproduct(Accessedon30.
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112.
Tetra(ethyleneglycol)diacrylate;MSDSProductNo.
398802;AvailablefromSigmaAldrich.
http://www.
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113.
Triethoxyphenylsilane;MSDSProductNo.
175609;AvailablefromSigmaAldrich.
http://www.
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docountry=IN&language=en&productNumber=175609&brand=ALDRICH&PageToGoToURL=%252Fcatalog%252Fproduct%252Faldrich%252F175609%253Flang%253Den(Accessedon26.
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114.
3-Glycidyloxypropyl)trimethoxysilane;MSDSProductNo.
440167;AvailablefromSigmaAldrich.
http://www.
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docountry=IN&language=en&productNumber=440167&brand=ALDRICH&PageToGoToURL=%252Fcatalog%252Fproduct%252Faldrich%252F440167%253Flang%253Den253Den(Accessedon26.
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115.
Iron(III)chloride;MSDSProductNo.
F7134;AvailablefromSigmaAldrich.
http://www.
sigmaaldrich.
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docountry=IN&language=en&productNumber=F7134&brand=SIAL&PageToGoToURL=%252Fcatalog%252Fproduct%252Fsial%252Ff7134%253Flang%253Den(Accessedon26.
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116.
Nitromethane;MSDSProductNo.
108170;AvailablefromSigmaAldrich.
http://www.
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117.
1-butyl-3-methyl-imidazoliumbis(trifluoromethanesulfonyl)imide;MSDSProductNo.
77896;AvailablefromSigmaAldrich.
http://www.
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docountry=IN&language=en&productNumber=77896&brand=ALDRICH&PageToGoToURL=%252Fcatalog%252Fproduct%252Faldrich%252F77896%253Flang%253Den(Accessedon30.
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118.
1,2-dichloroethane;MSDSProductNo.
284505;AvailablefromSigmaAldrich.
http://www.
sigmaaldrich.
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119.
Propylenecarbonate;MSDSProductNo.
310328;AvailablefromSigmaAldrich.
http://www.
sigmaaldrich.
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docountry=IN&language=en&productNumber=310328&brand=SIAL&PageToGoToURL=%252Fcatalog%252Fproduct%252Fsial%252F310328%253Flang%253Den(Accessedon31.
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120.
Sulfuricacid;MSDSProductNo.
435589;AvailablefromSigmaAldrich.
http://www.
sigmaaldrich.
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docountry=IN&language=en&productNumber=435589&brand=SIAL&PageToGoToURL=%252Fcatalog%252Fproduct%252Fsial%252F435589%253Flang%253Den(Accessedon31.
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121.
Potassiumchlorate;MSDSProductNo.
255572;AvailablefromSigmaAldrich.
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sigmaaldrich.
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docountry=IN&language=en&productNumber=255572&brand=SIGALD&PageToGoToURL=%252Fcatalog%252Fsearch%253Fterm%253DKClO3%2526interface%253DAll%2526N%253D0%2526mode%253Dpartialmax%2526lang%253Den%2526region%253DIN%2526focus%253Dproduct(Accessedon31.
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122.
Sodiumnitrate;MSDSProductNo.
S5506;AvailablefromSigmaAldrich.
http://www.
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123.
Potassiumpermanganate;MSDSProductNo.
60458;AvailablefromSigmaAldrich.
http://www.
sigmaaldrich.
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docountry=IN&language=en&productNumber=60458&brand=SIGALD&PageToGoToURL=%252Fcatalog%252Fsearch%253Fterm%253DKMnO4%2526interface%253DAll%2526N%253D0%2526mode%253Dpartialmax%2526lang%253Den%2526region%253DIN%2526focus%253Dproduct(Accessedon31.
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