PolymerCompositeswithFunctionalizedNanoparticles

Shorttitle:Chapter14PolymerCompositesContainingFunctionalizedNanoparticles

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PolymerCompositesContainingFunctionalizedNanoparticlesandtheEnvironment

JamalSeyyed (Name:Jamal;Surname:SeyyedMonfaredZanjani)MonfaredZanjani1,2

OguzhanOguz1,2

BurcuSanerOk (Name:Burcu;Surname:SanerOkan)an1,2

MehmetYildiz1,2

YusufZiyaMenceloglu1,2

1FacultyofEngineeringandNaturalSciences,MaterialsScienceandNanoEngineering,SabanciUniversity,Orhanli,Tuzla,Istanbul,Turkey

2SabanciUniversityIntegratedManufacturingTechnologiesResearchandApplicationCenter&CompositeTechnologiesCenterofExcellence,TeknoparkIstanbul,Pendik,Istanbul,Turkey

14.1IntroductionNanoparticles in general and functional nanoparticles in particular are of considerable interest for various industrial and technological applications due to their small dimensions, enhanced functional

propertiesandfeaturestheyofferthatarenotavailableinparticleswithlargerdimensionsorbulkofsamematerials[1–3].TheEuropeanCommission(EC)definesananomaterialas[4]:“Anatural, incidentalor

manufacturedmaterialcontainingparticles,inanunboundstateorasanaggregateorasanagglomerateandwhere,for50%ormoreoftheparticlesinthenumbersizedistribution,oneormoreexternaldimensions

isinthesizerange1–100nm.”Nanoparticlescanbemanufacturedfromvariousmaterialsincludingmetals,ceramics/glass,polymers,andsemiconductors[5–11].Theseparticlescanbeproducedinvariousshapes

suchassphere[12],cube[13],rod[14],nanoplate[15],andothers[16].Thepropertiesofnanoparticlesarecloselylinkedtotheirsize,shape,andsurfacefunctionalities.Thesevariationsandtailorablepropertieshave

ledtoawiderangeofapplicationsofthisclassofmaterials inthedevelopmentofstate-of-the-artmaterialstobeusedinstructuralapplications,electronics,biomedicine,cosmetics,energy,catalysts, filters,and

sensors[17].Asaresultoftheiruniquepropertiesandawiderangeofapplications,theproductionofvariousnanoparticleshasdramaticallyincreasedinrecentyears,whichbringsaboutthedilemmaoftheirpositive

andnegativeeffectontheenvironmentandhumanhealth.Thesematerialscanbeusedinbiologicalapplications,watertreatment,biosensors,filters,andenergytechnologiestosavetheenvironmentandprovide

higherlifequalityforhumankind.However,evennanoparticlessynthesizedfrombiologicallyinertmaterialscanbeharmfulto

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thecellbydamagingcellmembrane,disruptingcellfunction,oralteringthegeneticsofthecellbyattachingtoitsDNA[18].

Nanoparticletoxicologyisascienceofstudyingtheabilityofnanoparticlestodamageorchangethefunctionofcells,genes,andlivingorgansanddeterminethemechanismofthatdamage[19].However,

nanotechnologyboundariesarealwaysbeingpushedtocreateextremelysmallsizeparticleswithdimensionssmallerthanthatofcellularstructures[20,21].Theextremelysmallsizeofparticlesinducesasignificant

impactonnanoparticles’propertiesandbehavior inthebiologicalenvironmentduetotheirultrahighsurfaceareaandshapefactorssuchasextremesharpedges,whichhave ledtothe intrinsic toxicityofsuch

materials[22–24].Thenanoscaledimensionrendersthechemical/physicalpropertiesoftheparticlesinawaythattoxicologicalbehaviorofnanoparticlescannotbeextrapolatedfrominformationandavailabledataof

largerparticlesofthesamecomposition[24,25].

One may say that in polymeric nanocomposites, nanoparticles are fundamentally bound up in the structure of polymeric nanocomposites, but there is the potential for exposure to nanoparticles and

nanomaterials throughout theproduct chainduringmanufacture, application, andwastemanagement [22].One issuemakingparticle toxicologymore complex thanother toxicologybranches is the variation in

behaviorofnanoparticlesofinterestbyseveralstructuralandenvironmentalfactorsthatenabletheunfavorableeffectofnanoparticlesindiversescenarios[22].

Thischapterinitiallydiscussestherecentprogressintheunderstandingofthetoxicbehaviorofvariousnanoparticlesthatareusedcommerciallyandintensivelyinnanocompositeproduction.Thissection

reviewsthesenanoparticles’effectonlivingorgansbyelaborationonmechanismsandparameterscontributingtosuchbehavior.Inthesecondpartofthischapter,differentapplicationsofnanocompositestopromote

humanqualityoflifeandcontributingtothewellbeingoftheenvironmentarediscussedinselectedareastoemphasizetheimportanceofnanocompositesintechnologicaladvancements.

14.2ToxicologicalandExposureThenanoparticleswithdimensionsintherangebelow100nmarepronetohavearangeofunexpectedeffectsonbiologicalsystems.Theseparticlesaresosmallthattheycanpassthroughthephagocytic

defensesystemwithoutbeingdetected,givingthemaccesstobloodflowandthenervoussystem,andtheycanalsoaccumulateinthevitalorgans.Furthermore,thesenanoparticleshavetheabilitytointeractwith

proteinsandinactivatetheirfunctionorcreateanautoimmuneeffectinlivingorgans.Humansareexposedtonanoparticlesbylungexposurethroughenvironmentalairpollution,skinexposurethroughcosmetic

products,andinhalationandconsequentredistributiontootherorgans[21,26].Therearemanyknowledgegapsinourunderstandingonthetoxicityofnanoparticlesandtheirrelationswithparticlesize,roughness,

shape,charge,composition,surfacecoating,andphysiologicalmechanisms[24].Therefore,acomprehensiveunderstandingofthepotentiallyharmfuleffectsofnanoparticlesisnecessarytoprovideasafefacilitation

ofthesematerialstoour

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lives and ensure future wellbeing. In this section, a summary of nanotoxicological studies of some important nanoparticles with high volume use such as carbon nanotubes (CNTs), graphene, nanoclays, and

variousmetallicnanoparticlesisdiscussedandtheirtoxicitymechanismsaswellastheeffectofnanoparticles’physicalandchemicalstructureintheenvironmentaredeliberatedwhenavailable.

14.2.1CarbonNanotubesCNTsarethethinnesttubeshumanshaveevermade.Theyarechemicallyandthermallyverystablewithdiversepropertiesandbroadapplicationrange[27–29].SomeofCNTs’distinguishedpropertiesarehighstrength,high

toughness,extremelyhighsurfacearea,andexcellentthermalandelectricconductivity.CNTs’diameterrangesfrom~0.4to3nmforsinglewallandfrom~1.4to100nmformultiwallnanotubes[30–32].CNTsarelongthinstructures

thatcanhavelengthuptomanyseveraltensofmicrometers.Fig.14–1exhibitsthemolecularrepresentationsofsingle-walledCNTsandmultiwalledCNTs(MWCNTs)andtheirtypicaltransmissionelectronmicrographs.

Figure14–1TEMimagesandschematicillustrationsofCNTtypesshowingtypicaldiametersandseparationbetweenthegraphenelayersinMWCNT:(A)single-walledcarbonnanotube(SWCNT)and(B)MWCNT.

CNTsareusuallysynthesizedbyoneofthefollowingtechniques:Carbon-arcdischarge,laserablationofcarbon,orchemicalvapordeposition(CVD)[34].Thefirsttwomethodsemploysolid-statecarbonprecursorsascarbon

sourcesbyvaporizationathightemperature.Ontheotherhand,CVDmethodutilizeshydrocarbongasesascarbonsourcesandmetalparticlesas“seeds”fornanotubegrowth[35].TheseCNTproductionmethodsrequireahigh

amountofenergyandgeneratelargeamountsofbyproducts,whichlimitstheirproductioninlargescaleandraisesseveralenvironmentalconcerns.CNTsareoneoftheleastbiodegradablemanmadematerials.Theinsolubilityin

solventsandlipophilicbehaviorofCNTsmaketheirremovalfromenvironmentandorgansalmostimpossible[36,37].TheseCNTscanentertheenvironmentatallstagesofsynthesis,processing,application,anddisposal,

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and exhibit their toxic properties. The toxicity and polluting effect of CNTs differ depending on their structural properties such as length, surface chemistry, and oxidative potential as well as the types of cells they are

interactingwith[38].

ThehealthriskandenvironmentaleffectofCNTsstronglydependontheirphysicalproperties,shape,andsurfacefunctionalgroups.ThetoxicityofCNTsisaresultofboththeirphysicalandchemicalproperties.Theintensive

interactionsbetweenCNTsandcellmembranesmaycausephysicaldamageandconsequentcelldeath.Moreover,CNTsareabletochemicallyinteractwithcellsandpromotecellularoxidativestress,whichcanleadtocellmalfunction

orevencelldeath[39].SizeisoneofthemostimportantparametersdeterminingthetoxicityofCNTs,forexample,CNTslongerthan20μmcausethesametypesofpathologythatlongbiopersistentfiberscausesuchasfibrosis,

cancer,pleuralchanges,andmesothelioma.Ontheotherhand,CNTswithshorterlengthof15–20μmactlikenanoparticlesinwhichadverseeffectandtoxicbehavioraredrivenbythesmallsizeandlargesurfaceareaoftheCNTs

[26].ThesurfacefunctionalitiesofCNTsplayacriticalroleintheirbehavior,toxicity,andstateofaggregationintheenvironment.ThesurfacefunctionalizationofCNTsthroughacidtreatmentsoranyothermethodscanchangetheir

dispersionbehaviorsignificantly[40].ThesurfacefunctionalizedCNTsdisplayedhighmobility inwater,whichassessesthepotentialmigrationinnaturalporousmedia[41]. Inaddition,thehighsurfaceareaandconsequenthigh

surfaceenergyofCNTsleadtoattachmentofotherpotentialpollutantsandtheirtransportthroughouttheenvironment[42].Furthermore,thesurfacefunctionalgroupsdetermineCNTs’interactionwithcellsandconsequenttoxic

effects. The surface charge of CNTs is another parameter influenced by surface functionalization,which plays a critical role in the toxicity of CNTs. Shen et al. [43] showed that in vitro cytotoxicity and the biocompatibility of

functionalizedCNTsislargelydependentontheirsurfacepotential.Theyappliedpolyethyleneiminefunctionalizationontheacid-treatedCNT,whichresultedinwater-solubleandstableCNTs.Thementionedstudyshowedthatneutral

andnegativelychargedCNTsarenontoxictotargetedcellsataconcentrationupto100μg/mL,whereaspositivelychargedMWCNTsshowedtoxicityat10μg/mL[43].Nevertheless,Pulskampetal.[44]didnotobserveacutetoxicity

forthreecommercialgradesofnonfunctionalizedsingle-walledCNTs,whereasJosetal.[45]confirmedthecytotoxicityofcarboxylicfunctionalizedsingle-walledCNTsondifferentiatedandnondifferentiatedCaco-2cellsderivedfroma

human intestinaladenocarcinomaatconcentrationshigher than100μg/mL. Inanotherwork,Saxenaetal. [46]observed thatacid functionalizedsingle-walledCNTexertedstronger toxiceffects invitro (cytotoxicity,cell cycling

inhibition,andapoptosis)andinvivoincomparisonwithunmodifiedsingle-walledCNT,andtheyshowedthatthosetoxiceffectscouldbereversedbyneutralizingthenegativesurfacecharges.Magrezetal. [29]showedthatthe

toxicityofCNTsincreasesignificantlywhencarbonyl(C–O),carboxyl(COOH),and/orhydroxyl(OH)groupsarepresentontheirsurfacewithoutanyclarificationontheexactmechanisms.Incontrast,Sayesetal.[47]observedthatan

increaseinthedegreeofsidewallfunctionalizationofsingle-walledCNTsdecreasestheircytotoxicproperty.

Ingeneral,size,shape,andsurfacechargeofnanoparticlesarebelievedtobethethreemostimportantfactorsaffectingthenanoparticles’toxicity.However,thetoxicbehaviorof

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CNTs isalsorelated toenvironmentalparameterssuchaspH, temperature,and light. In fact, the toxicityofnanoparticles ingeneralandCNTs, inparticular, isacomplicatedprocessrelated to thewholeeffectof theirphysical

propertiesinteractedwithspecificbiomoleculesorthereleasingcontentsofdissolvedtoxicionsinbiologicalmedia.Therefore,duetothecontributionofnumerouseffectiveparametersinCNTpollutingandtoxicity,theinvestigation,

control,andpredictionofitsbehaviorandeffectsonorgansandenvironmentsisachallengingtask.However,ahighleveloffundamentalunderstandingofbiocompatibilityandeffectsofCNTsonhumanhealthandenvironmentshould

beachievedtoensurethesafeintegrationofCNT-basedproductsinourlives.Consideringthisinformation,extraprecautionsinmanipulationandfunctionalizationofCNTsareneededtobetakeninmanufacturingandapplicationsof

ReprintedfromKaseemM,HamadK,KoYG.Fabricationandmaterialspropertiesofpolystyrene/carbonnanotube(PS/CNT)composites:areview.EurPolymJ2016;79:36–62[33],bypermissionofElsevier.

functionalizedCNTswhereCNTsareindirectcontactwithlivingorganisms.

14.2.2GrapheneGraphenewith its unique 2D structure and exceptional physical and chemical properties has attracted the attention of scientists and engineers in various advanced applications such as development of novel polymeric

compositeswithuniqueproperties[15,48–50].Grapheneisoneofthestrongestmaterials,havingatheoreticalYoung’smodulusof1060GPaandanultimatestrengthof130GPa,andalsohighspecificsurfacearea,whichmakesita

suitablecandidatefornanocompositeproductionwithextendedphysicalandchemicalproperties[48].Thesenovelnanocompositematerialshavegreatpotential forvariousapplications,rangingfromhigh-performancestructures,

energystoragedevices,electricallyconductivepolymericmaterials,aswellasantibacterialmaterials[51].

Severalgraphenegradescanbefoundinthegraphenefamilymaterialssuchasfew-layergraphene,graphenenanosheets,grapheneoxide(GO),andreducedgrapheneoxide(rGO)andgraphiteasshowninFig.14–2[52].Each

memberof thegraphene familyhasuniquebehaviorandsometimesdiversepropertiescomparedwithothers.Graphene familyproductsaregrowingata rapidrateand theyarecommercialized invariousapplications [53].This

increases the graphene production rate and consequently their release to the environment. The graphene/polymer nanocomposites may release graphene during manufacturing, degradation of the polymeric matrix, or direct

environmentalapplicationssuchaswaterorsoil treatment[54–56].Thereleasedgraphene intotheenvironmenthasthehighpotential tohavesignificantadverse impactsatdifferent levels frombacteriaandmammaliancells to

animals.

Herein,wewilltrytobrieflyreviewtheavailableliteraturetoprovideanunderstandingontheeffectofgraphene-basedmaterialsonvariousorganisms,themechanismsinvolvedintheirtoxicity,andalsocomparetheirtoxicity

withothersimilarmaterials.ItiswellknownthatGOandrGOastworenownedmembersofthegraphenefamilyshowhigherantibacterialactivityovergraphiteoxideandgraphite.Thisstemsfromtheirfinersizeandthinnerlayers,

whichgivethemthesharpedgestodamagetheplasmamembranesonbacterialcellsandkillthecell[39,57].ThesharpedgesofGOandrGOarenotavailableinothercarbon

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nanomaterials such as carbon black, which restricts their antimicrobial activities through thementionedmechanism. In addition, GO shows higher cytotoxicity comparedwith rGO; this is because of its higher dispersibility in

aqueousmedia,andpresenceofactivesurfacefunctionalgroups,whichpromotethepossibilityofdirectcontactwithcellsandinducinghigherintracellularoxidativestress[49].Contrarily,somestudiesshowedhighertoxicityofrGO

iscorrelatedwithitsthinnerstructureintheabsenceofoxygenfunctionalgroups(0.34nm)comparedwiththatofGO(1nm),whichcreatessharperedgestodamagethecellmembraneeasily[58,59].Furthermore,itisobservedthat

higherelectricalconnectivityofrGOincreasestheoxidativestressonintracellularglutathioneby enhancingtheelectrontransferbetweentheedgestomembraneswhichpromotes toxiceffectoncells[60–62].Onthe

otherhand,thehydrophobicityofrGOupholdsitsinteractionwiththecells’outerwall,whichcanhinderthenutrientabsorptionandgasexchangeacrossthecellmembrane[63,64].

Theenvironmentandcelltypehaveadisputableeffectonthetoxicityofgraphene.Asmallchangeintheenvironmentsmaychangethegraphene’sstructure,transport,aggregation,andtoxicity[65].GOcangothrougha

reductionprocessunderlightexposureorthroughexposuretochemicalcompounds[66–68].Furthermore,biodegradabilityisanotherissuethatshouldbeaddressedwhilediscussingtheconcernsaroundtheenvironmentaleffectsof

Figure14–2Graphenefamilynanomaterials.(a)Graphene,(b)few-layergraphene,(c)graphite,(d)reducedgrapheneoxide(rGO),and(e)grapheneoxide(GO)

ReprintedfromKiewSF,KiewLV,LeeHB,ImaeT,ChungLY.Assessingbiocompatibilityofgrapheneoxide-basednanocarriers:areview.JControlRelease2016;226:217–28,bypermissionofElsevier.

or enhancing its

grapheneanditsderivatives.GOhasshownbiodegradabilitypotentialinpresenceofenzymessuchasmyeloperoxidase[69].Surfacefunctionalizationisanotherparameterthatinfluencesthetoxicityofgraphenefamilymaterialsand

alterstheirbiodegradabilityanddispersibilityontheenvironment[70].GOhastheabilitytobedegradedbylowconcentrationsofenzymeswhilerGOshowsresistancetoenzymedegradation[71].Thepointisoxidationofgraphite

createsdefectsiteson thestructurepromoting thebiodegradationofgraphene.However,excessive functionalizationwith larger functionalgroupsmayprevent theirbiodegradation [72,73].Nevertheless, thenumberofeffective

enzymestobeusedin

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biodegradation of nanomaterial is very restricted and more biodegradation studies are needed to characterize better and more effective enzymes to provide biodegradability of graphene and minimize its effect on the

ecosystem[70].

14.2.3NanoclaysThefirstpolymernanocompositewasapolymer–clayhybridthatwasinventedatToyotaCentralR&DLabs,Inc.(Toyota)[74].Inthementionedhybridpolymercompositesystemasmallamountofsilicatelayerofclaymineral

israndomlyandhomogeneouslydispersedonamolecularlevelinapolymermatrix[75].Nanoclaysarelayeredmineralsilicates,whichareoneofthecommonadditivesforpolymernanocompositeproductionwithincreasedstrength,

modulus,andtoughnessandimprovedbarrierandflame-retardantproperties[76,77].Clay-basedpolymericnanocompositespossessalargeportionofthenanocompositemarketinvariousapplicationareas.

Clays are abundant, highly stable, inexpensive, and believed to be an environmentally friendly nanoadditive [73].Montmorillonite is a natural clay and themost frequently used nanoclay in the preparation of polymer

nanocompositeswithplate-likeparticlescalledplatelets [78].Montmorilloniteplateletshaveanaverage thicknessofonly1nm,while theirdimensions in lengthandwidthcanbemeasuredup to1µm[78]. Fig. 14–3 shows the

structureofmontmorilloniteclay,whichconsistsoftwotetrahedralsheetscoveredwithoneoctahedralsheetinbetween[79].Despitetheseveralusefulbiologicalandenvironmentalapplicationsofnanoclays,theirnanoscalesize

enablesthemtopenetratetothecellmembranes,andinterferewithcellularprocesses[78,80].Severalmechanismscontributetotoxicityofnanoclaysincludingdecreaseinbothcellulargrowingrate,morphologicalchangesofcell,

cellularproliferation,mitochondrialdamage,reactiveoxygenspeciesgeneration,and

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DNAalteration[81–84].Itworthnotingthattheprudencyofeachdamagetypeiscloselyrelatedtostudiedcell,dosage,andsurfacefunctionalizationofclays.

Figure14–3Structuralunitofmontmorillonitenanoclay.

Reprintedfrom JayrajsinhS,ShankarG,AgrawalYK,BakreL.Montmorillonitenanoclayasa

multifaceteddrug-deliverycarrier:areview.JDrugDelivSciTechnol2017;39(Suppl.C):200–9,bypermissionofElsevier.

KaseemM,HamadK,KoYG.Fabricationandmaterialspropertiesofpolystyrene/carbonnanotube(PS/CNT)composites:areview.EurPolymJ2016;79:36–62;

In the clay structure, the interlayer space (known as the clay gallery) contains exchangeable cations such asNa+ orK+ [85].Organomodification of nanoclays is amethod to replace these cationswith organic cationic

surfactants.Thisorganomodificationincreasesgalleryspacing,improvesthecompatibility,makesclayhydrophobic,andenhancesitscompatibilitywithmostofthepolymericmatrices[86].Theorganomodificationorfunctionalization

ofclayswithorganicchainsplaysacriticalroleintheircytotoxicresponse.Somestudiesfindthatorganomodifiedclayshavegreatertoxicitycomparedwithunmodifiedones[78,87]whereasotherfindingsexpresslowertoxicityof

modifiedclayscomparedwiththeirunmodifiedcounterparts[88,89].Thesestudiesalsoexpresstheimportanceoffunctionalgrouptypeusedfororganomodificationonthetoxicityofnanoclays[90–92].

Theclay’sphysicalstructureandgeometry(plateletortubular)havesignificanteffectonitstoxicity[93].Vermaetal.[81]detectedanoticeabledifferenceinthenumberofdetachedanddeformedcellsexposedtoplatelet-type

nanoclayscomparedwithcellsincontactwithtubularclays,whichindicatesthatplateletstructurednanoclaysaremorecytotoxicthantubulartype.Theirstudyshowedthattubularclays,knownashalloysitenanotubes,donotshow

anytoxiceffectuntildosesof250μg/mL,whileplateletnanoclayscausetoxicityat25μg/mL[81].

Giventhecomplexanduncertaineffectsofnanoclaysonbiologicalenvironments,systemicmanagement,analysis,andprecautionsarerequiredtoassessandminimizetheexposuresduringtheirmanipulation,handling,and

disposal.Inaddition,moreresearcheffortsarenecessarytoevaluateandunderstandthemechanismsoftoxicityofnanoclaysincellsandfindapropersolutiontodesignsafeproductsofnanoclay-basedpolymericnanocompositesfor

futureapplications.

14.2.4MetalNanoparticlesTheincorporationofmetalnanoparticlesintopolymericmatricesisanemergingareatofurtherextendtheapplicationsofpolymericnanocomposites.Thequantumsizeeffectsonmetalnanoparticlesgivethemgreatpromise

inmany technical andalsomedical applications [94]. Theseuniqueproperties canbe tailoredby controlling thesemetal nanoparticles’ size, shape, andpreparationmethods.Metal nanoparticle-basedpolymeric nanocomposites

provideenhancedperformanceandmultifunctionalitiesaswellaspromisingpotentialapplicationsinelectronics,optics,environmental,andbiotechnologicalapplications,whichmaynotbepossiblewithlargermetalparticles.Metal

nanoparticlescanbecategorizedintometals,metaloxides,andothermetal-containingnanoparticles[95,96].Thewiderangeofapplicationofmetallicnanoparticlesandhighvolumeproductionconnectthisclassofmaterialswith

someenvironmentaleffectsuncertaintiesandserious risks.Thesematerialscanenter livingorganisms including thehumanbody throughactiveorpassivepathwaysandhave thehighpotential tocreateunrecoverabledamage

becauseoftheiractivatedtoxicityduetotheirintrinsicpropertiesandalsotheirnanoscalesize[97].Inthispart,the

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environmental effects of selected metal nanoparticles, which are used intensively in polymer nanocomposite productions such as titanium dioxide (TiO2), zinc oxide (ZnO), and silver (Ag) nanoparticles, are discussed in detail

includingtheeffectiveparametersandcorrespondingmechanismsintheirtoxicity.

TiO2 isanaturallyoccurringmineral thatcanbecategorized intoanatase, rutile,orbrookite typesbasedon itscrystal structure [98].TiO2nanoparticleshaveoneof thehighestproduction ratesworldwideamongother

nanoparticles[99].TiO2 isaneffectivereinforcingagentforseveralpolymericmatricesanditalsoprovidespolymericmaterialswithseveraluniqueproperties.TiO2nanoparticle isa largebandgapsemiconductor,whichgives it

exceptionalelectronic,optical,thermal,andphotocatalyticproperties.TheseuniquefunctionalitiesofTiO2nanoparticlesareofinterestforthedevelopmentofseveralfunctionalpolymericnanocomposites[100–102].TiO2nanoparticles

showbothbeneficialandtoxiceffectsonnaturedependingontheirintrinsicpropertiesandalsotheenvironmentalfactors[103].TiO2havebeenacceptedassafematerialsandtheircytotoxicityisoftenneglectedwhereasthereare

reports on their toxicity throughgeneration of reactive oxygen species, increased cell adhesion, andalterationon carbohydratemetabolism [104–106].Furthermore,TiO2 nanoparticles have genotoxicity properties and they can

interactwithDNAofcells[107].However,thereareseveralconflictingresultsontoxicitiesofTiO2nanoparticles,someclaimingnotoxicityeffectandsomehightoxiceffectoftheseparticlesinthelivingorgans.Theseconflictsstem

fromvariousmorphology,crystal structure, size,purity levels surfaceareas,andalsoconducted testconditions [108].Toresolve theseconflicts,aclearunderstandingof themolecularmechanismsbehind the toxicandnontoxic

responsesofTiO2nanoparticlesisneeded[104].

ThecrystalstructureofTiO2nanoparticlesplaysacriticalruleintheirtoxicbehavior[109].Innature,TiO2hasthreecommoncrystallinepolymorphs,namelybrookite,anatase,andrutileasshowninFig.14–4[110].However,

onlyrutileandanataseTiO2aregenerallymanufacturedintitaniumdioxidecommercialapplications.Therelativetoxicityofeach

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crystal structure of TiO2 nanoparticles with respect to biological systems is broadly debated; no solid conclusion is available. In general, it is accepted that anatase TiO2 nanoparticles aremore active under light exposure or

darkenvironmentandgeneratehigherreactiveoxygenspeciesandconsequentDNAdamagescomparedwithothercounterpartswithdifferentcrystalstructures[111,112].TheanataseTiO2nanoparticlesareabletospontaneously

generatereactiveoxygenspecieswhereasrutileTiO2nanoparticlesdonotexhibitsimilarbehavior[112].Itisworthnotingthatanatasenanoparticleshaveahighaffinitytoproteins,mainlyimpairingmitochondrialfunctionwhereas

therutileTiO2nanoparticleshavehigheraffinitytophospholipids,mainlytargetingtheplasmamembraneandthelysosomemembrane,andcausingreactiveoxygenspecies–independentcelldeath[109].Furthermore,therutileTiO2

nanoparticlesareabletoinducehydrogenperoxideandoxidativeDNAdamageintheabsenceoflightwhileanataseTiO2nanoparticlesdonothavethiseffect[113].Additionally,somestudiesshowedthehighertoxicityofamixtureof

anataseandrutileparticlesanditshigherabilitiestocreateDNAdamageintheabsenceoflightcomparedwithindividualanataseorrutileTiO2duetocontributionofmultipletoxicitymechanisms[113].

TiO2nanoparticlescanbedistributedtoallorgansortissuesfromtheoriginalsiteuponenteringthebloodanddepositedintheliver,lung,kidney,andotherorgans,whichcancauseseveredamagetoandmalfunctionofthat

organ[99,114,115].NanoparticlesingeneralandTiO2nanoparticles,inparticular,canenterthehuman/animalbodythroughvariousroutessuchasoral,dermal,orinjectionandcausevarioustoxicitiesindifferentorgans[99].Studies

show that oral exposure toTiO2 nanoparticles induces hepatic histopathologic damage,with alterations in serum lactate dehydrogenase and alpha-hydroxybutyrate dehydrogenase levels indicatingmyocardial damage aswell as

neurotoxicityandbraindamage[116,117].ThehighamountofapplicationforTiO2nanoparticlesincosmeticproductsmakesdermalexposureanimportantissue.However,thereareconflictingfindingsintheliteratureinwhichsome

groupsclaimedthatTiO2nanoparticlesareunable topenetratehumanskinwhereasotherspresentopposite findings [118–122].Despiteseveral recentstudieson the toxicityofTiO2, its toxicitymechanismsand itseffecton the

ecosystemarenotcompletelyunderstood.Therefore,furtherinvestigationsanddetailedresearchactivitiesarerequiredtounderstandthepotentialhealtheffectsandplanproperriskassessmentprocedurestopavethewayforthis

usefulmaterialimplementationinfutureapplications.

Zincoxide(ZnO)nanoparticleisanothermetallicnanoparticlewidelyusedinthepolymericnanocompositemanufacturing.ZnOisann-typesemiconductorwithwidebandgapenergyof3.3eVmakingitasuitablechoicefora

broad range of applications. The incorporation of ZnO nanoparticle into polymeric matrices provides them with various functionalities including enhanced mechanical performance, permeability, flame resistance, UV-shielding,

antimicrobialactivities,anduniquethermalandelectricalproperties[73,123–127].EventhoughZnOislistedasaGenerallyRecognizedasSafematerialbytheUSFoodandDrugAdministration(21CFR182.8991)anditiswidelyused

inproductsthathavedirectcontactwithhumanssuchfoodpackagingandcoatingsapplications,thereisamyriadofresearchreportingthetoxicbehaviorofZnOnanoparticles[128–131].TheZnOnanoparticleshavetheabilityto

inducemorphologicalmodifications,oxidativestress,lipid

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peroxidation, cytotoxicity, genotoxicity, and chromosomal breakage forms of toxicities [132–137]. The toxicity of ZnO nanoparticles can be influenced by ZnO nanoparticle surface composition, size, and shape [133,138,139]. It

isanaccepted fact thatantibacterialactivityofZnOnanoparticle increaseswithareduction inparticlesize [139]. Inaddition, theshapeofZnOnanoparticlesplaysan importantrole in their toxicbehavior [140].Ata fixedZnO

nanoparticlesizeandsurfacearea,nanorodZnOnanoparticlesaremoretoxicthanthecorrespondingsphericalones[140].InadditiontothetoxicitymechanismcorrelatedwiththenanoscalesizeoftheZnOnanoparticles,itisshown

Figure14–4RepresentationofthreeTiO2polymorphs:(A)anatase,(B)rutile,and(C)brookiteforms.

ReprintedfromLiaoY,QueW,JiaQ,HeY,ZhangJ,ZhongP.Controllablesynthesisofbrookite/anatase/rutileTiO2nanocompositesandsingle-crystallinerutilenanorodsarray.JMaterChem2012;22(16):7937–44,bypermissionofRoyalSocietyofChemistry.

thatreleaseofzincionsisanothertoxicitymechanisminwhichtheseionsshow highertoxicitycomparedwithZnOnanoparticlesthemselves[141].

ThesurfacefunctionalizationisanotherimportantparameterinfluencingthetoxicityofZnOnanoparticles.Inaddition,thecorrelationbetweensurfacefunctionalityandtoxicityofZnOnanoparticlescanbeaneffectivewayto

modify the toxicity ofZnOnanoparticles tohave specific cellular interactionswith thebiologicalmolecules andpreserve their functional properties,whichwill openup several novel applications for this groupof nanomaterials

[142–146].Inthisregard,Ramasamyetal.[147]fabricatedSiO2-coatedZnOnanoparticlesinwhichcoatedZnOnanoparticlesexhibitlesscytotoxicitycomparedwithuncoatedZnOnanoparticles.Thementionedworkcorrelatesthat

thedecreases incytotoxicitywith fewer surface interactionsofZnOnanoparticleswithcellsaftercoatingbySiO2, decreased in the release rateof zinc ion,andchangeson thehydrophilicityof the surfaceafter coatingofZnO

nanoparticles[147].Inanotherstudy,Hsiaoetal. [148]reducedthecytotoxicityofZnOnanoparticlesbycoatingthemwithaTiO2 layerapplyingasol−gelmethodandtheyobservedmoderatetoxicityontheZnO/TiO2 core/shell

structurecomparedwithuncoatedZnOnanoparticles.TheTiO2coatingreducestoxicitybydecreasingthereleaseofzincions,alsorestrictingthecontactareaoftheZnOcoreswiththecell.Luoetal.[149]appliedpolyethyleneglycol

coatingonZnOnanoparticles and reduced the cytotoxicity ofZnOnanoparticles.These findingsbespeak the important role of the surfaceproperties ofZnOnanoparticles on their cytotoxicity.Despite these studies, the toxicity

mechanismofZnOparticles isstillnotwellunderstoodandfurther investigationsarerequiredtounderstandthemechanisms involved inthetoxicityofZnOnanoparticlesanddevelopthesafetyrulesregardingexposuretoZnO

nanoparticles.

Silver(Ag)nanoparticleswithextraordinaryoptical,electronic,catalytic,andmoreimportantlyantibacterialpropertieshavefoundgreatapplicationsinthedevelopmentoffunctionalpolymernanocomposites[150–152].The

widespreaduseofAgnanoparticlesintoys,clothing,andfoodpackagingproductsraisesseriousconcernsabouttheireffectsonhumanhealthandecosystems.Theseconcernsbespeakthenecessityofdetailedsafetyevaluationsand

obtainingaclearunderstandingof the impactofAgnanoparticlesonhumanhealthand theenvironment [152,153].Agnanoparticlesareoneof themosteffectiveand frequentlyusedantimicrobialagents inpolymericproducts

[154,155].ThebroadrangeofAgnanoparticles’applicationsincreasesthepossibilityofexposureandconsequentseveredamageriskstotheecosystem.DespiteseveralproposedmechanismsforthetoxicityofAgnanoparticle,its

exactmechanismsarenotwellunderstoodyet[156].Someoftheproposedmechanisms

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are physical damage and penetration that cause cell malfunction [157], dissolution of Ag+ from the Ag [158], and stimulation of reactive oxygen species [159]. Various factors that can influence the level of toxicity and its

mechanismareparticlesize,surfaceproperties,andshape[160,161].Nevertheless,assilverinitsmetallicstateisconsideredasaninertmetal,itcaneasilyreactwithmoistureandgetionized,andishighlyreactiveandabletobind

toproteins,DNA,andRNA[162].

ItissuggestedthatAgnanoparticlemorphologicalpropertiesindirectlyaffectantimicrobialactivityandtoxicitybyinfluencingtheAg+releaserate[163].Helmlingeretal.[160]correlatedthedissolutionkineticswiththe

particlesizeinwhichparticleswithahigherspecificsurfacearea(finerparticles)showmoretoxicitythanparticleswithsmallerspecificsurfaceareas(largerparticles).ConsideringtheAg+releaseasthemaintoxicitysourceforAg

nanoparticlesantibacterialandtoxicactivity,theseactivitiescanbemanipulatedbycontrollingtheAg+releasethroughtailoringtheparticlesize,shape,appliedcoating,andtheenvironmentalparameters[163].However,thereare

studiessuggestingmorphologicalfactorsofAgnanoparticlesasresponsibleforitstoxicbehaviorratherthanitsionizedstate.ThenanoscalesizeofAgnanoparticlesisabletoproducereactiveoxygenspeciesandoxidativestress,

whichcandamagethecell[164–166].Ontheotherhand,someresearchproposesacombinedeffectinwhichAgnanoparticlesenterthecellsandactasasourceofAg+,leadingtocytotoxicandgenotoxicdamageknownasthe“Trojan

horse”effect[73,167].ThehighproductionintheincreasingutilizationofAgnanoparticlesincommercialproductsraisesseriousconcernsaboutitsenvironmentaleffectsandtheirimpactontheecosysteminrecentyears.Therefore,

moreresearchandinvestigationsareneededtoenhancecurrentunderstandingoftheirtoxicbehaviorandaddresstheseissuesfortheirfurtherdevelopment.

14.3EnvironmentalBenefitsandApplicationofPolymericNanocompositesDespiteseveralstudiesmentioningtheadverseeffectofnanoparticlesandnanocompositesontheenvironmentandtheecosystem, thisclassofmaterialsbringsaboutseveralnovelanduniquebeneficial

applicationstoservenatureandtheecosystem. Inthissection,someof thewell-establishedenvironmentalapplicationsofpolymericnanocomposites thateaseandprotecthuman life,savetheenvironment,and

provide better future ecosystems are discussed. Packaging, membranes, and energy are the selected application areas, among others that nanotechnologies and especially polymeric nanocomposites have

revolutionized.

14.3.1FoodPackagingbyNanotechnologyandNanocomposites

induced

Advancesinthefoodpackagingindustriesasanessentialpartoftoday’seconomyhaveenabledeffectivetransportation,distribution,andpreservationoffoodandensureitsproperphysicalandphysicochemicalconditionsat

thedeliverypoint.Thedesiredpackagingmaterialshouldpossessmechanical,optical,andthermalpropertiesthatpreventthetransferofunwantedsubstancessuchasmicrobialcontamination,moisture,andoxygeninto/fromthe

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package. Over the last few decades, the utilization of polymers for food packaging has increased greatly because of their superior properties such as functionality, light weight, ease of processing, variety, and low cost over

othertraditionalmaterials(metals,ceramics,andpaper).However,pristinepolymer-basedpackagingdoesnotsatisfyindustryneedsforapackagingthatprovidesthecapabilitytokeepthepackagedmaterialsforalongertime.To

addressthementionedlimitations,polymericnanocompositespreparedbyfunctionalizednanoparticlesprovideanopportunitytoproducethenext-generationfoodpackaging.Polymernanocomposite–basedpackagingmaterialshows

severaluniqueandenhancedpropertiessuchashighbarrier,antimicrobialactivities,andthecapability toactasasensor for thedetectionof food-relevantgases,orothermolecules. Inaddition, thepossibility to implement low

amountsofnanoparticlesandachievehigherenhancedpropertiescomparedwithmicrocompositeshasledtoareductionincost.Oneofthenovelpackagingtechnologiesenabledbyfunctionalizednanoparticlesisactiveandintelligent

packaginginwhichthepackagematerialsaredesignedtointeractwiththefoodorthefoodenvironment.Theseinteractionscanbereleasing,absorbing,ormodifyingsubstancesintoorfromthepackagedfoodortheenvironment

surrounding.Fig.14–5representssomeofthenanocomposite-basedactivepackagingtechnologies[168].Thedevelopmentsinthistypeofpackagingmaterialsaremostlyfocusedonlowpermeableandantimicrobialfilms[168–170].

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Asmentionedearlier,oneofthemainlimitationsrestrictingthewidespreadapplicationofpolymericmaterialsinfoodpackagingistheirrelativelyhighpermeabilitytosmallmoleculesandmoisture,whichhasanadverseeffect

on the lifetimeof thepackagedproduct.Oneof theeffectivemethods toenhance thebarrierpropertiesof thepolymericmaterials isblending themwithspecificnanoparticles. Innanocomposites, thegasbarrierperformance is

determinedbynanoparticleproperties,matrixpermeability,nanoparticle–matrixinteractions,andtheorientationofthenanoparticles.Clayandgraphenearethemostcommonnanoparticlesusedforenhancingthebarrierproperties

ofthepolymericcompositesbecauseoftheirhighsurfaceareatothicknessratio,andimpermeabilitytomostofthegasesandwatervapor.Evenrelativelylowadditionsofnanoclaytoapolymermatrixstemsareductionoftransport

crosssection,andalsoincreaseoftransportpathsofpenetrantmoleculesandcausesextremereductionsinpermeability[171].Moreover,theadditionofnanoplateletsresultsinmodificationofpolymerchainmobilityandprovides

Figure14–5Applicationsofnanostructuresinnanocompositepackaging.Activepackagingcanbedevelopedthroughincorporationofnanoparticlesencapsulatingbioactivecompoundswithantimicrobialorantioxidantactivity.Theuseofnanosensorsor

nanochipsfordevelopmentofsmart/intelligentpackagingmayprovideinformationabouttheconditionofpackagedfoodduringtransportandstorage.Nanoreinforcementcanbeachievedbyincludingnanofillersintobiopolymermatrixesintendedfor

packagingpurposes,providingsignificantimprovementsinmechanicalandbarrierproperties.

ReprintedfromBrandelliA,BrumLFW,dosSantosJHZ.Nanostructuredbioactivecompoundsforecologicalfoodpackaging.EnvironChemLett2017;15(2):193–204,bypermissionofSpringerNature.

loweravailablefreevolumetodiffusinggasmoleculesandchangesthesolubilityparameters[172,173].Thestateofthedispersionandinterfacequalityarealsoimportantparametersonnanocomposites’permeabilities,andplaya

criticalroleinthebarrierperformanceofnanocomposites,whichcanbeenhancedbypropersurfacemodificationofparticles.However,lowcompatibilitybetweenpolymerandnanoparticlesresultsinapoorinterfacialquality,which

could leadtothepresenceofnarrowgaparoundthenanofiller [174].Thesegapsfacilitatetheflowandpenetrationofgasmoleculesand increasethepermeabilityof thenanocomposite,whichcanhaveanadverseeffectonthe

packagedmaterial[174].Inaddition,thepolymerandnanoparticlecompatibilitystatedeterminesthedispersionstateofthenanoparticlesinthepolymermatrixwhosepossiblemicrostructurescanbeclassifiedasphase-separated

(microcomposite),intercalated,andexfoliatedasshowninFig.14–6[175].Inthecaseofphase-

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separated nanocomposites, nanoplatelet tactoids are formed in the matrix and no separation of nanoplatelets occurs and polymer chains surround clay nanoplatelets without penetration between the layers. In intercalated

nanocomposites,someofthemolecularpolymerpenetratesbetweennanoplateswhiletheoverallorderofthenanoplateletsispreserved.Intheexfoliatednanocomposites,thelayersarecompletelyseparatedanddispersedindividually

withinthecontinuouspolymermatrix.Thehighestbarrierimprovementsareexpectedfromfullyexfoliatedpolymernanocompositesbecauseinthisstatethenanoparticleplateletswillhavethehighestsurfacearea[176].

Antibacterialactivityisanotherdesiredpropertyforfoodpackagingmaterialsthatextendstheshelflifeandsafetyoffoodproductsbyreducingthegrowthrateofmicroorganisms[177,178].Thepolymericnanocomposites

basedonmetalnanoparticlessuchasAgTiO2andZnOasantimicrobialagentsshowedhighantimicrobialperformanceforabroadspectrumofmicroorganisms[179,180].Thepresenceofantibacterialnanoparticles inpolymeric

nanocompositestructurenotonlyinhibitsinitialundesirablemicroorganismsbutalsoavertstheresidualactivityovertimebycontrolledmigrationofthecompoundintothefood[181].Theantibacterialactivityofnanoparticlesstems

fromvariousmechanismsincludingdirectinteractionwiththemicrobialcellsandcausingdamageinthecells’structure,oxidizingcellcomponents,andproducingreactiveoxygenspeciesordissolvedheavymetalions[182,183].Fig.

14–7showsvariousmechanismsofantimicrobialactivitiesexertedbynanomaterials[182].

Figure14–6Schemeofdifferenttypesofcompositearisingfromtheinteractionoflayeredsilicatesandpolymers:(A)phase-separatedmicrocomposite,(B)intercalatednanocomposite,and(C)exfoliatednanocomposite.

ReprintedfromAlexandreM,DuboisP.Polymer-layeredsilicatenanocomposites:preparation,propertiesandusesofanewclassofmaterials.MaterSciEngRep2000;28(1):1–63,bypermissionofElsevier.

14.3.2NanocompositesinMembraneTechnologyMembranetechnologyiswidelyappliedinvariousindustriessuchaswatertreatment,molecularseparations,biomoleculepurification,environmentalremediation,gasseparation,

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petroleum chemicals, and fuel production [184,185]. Polymeric membranes technology is an attractive alternative to inorganic membrane equivalents because of their high flexibility, low energy requirements, relatively low

preparationcost,andenvironmental friendliness[186,187].However,applicationofpolymericmembranes is facingseveralchallengesregardingtheirmechanicalperformance, thermalstability,permeability,andselectivity [188].

Nanomodifications andutilizationof nanoparticles on thepolymeric structures are consideredas an effectiveway to address thementioned challenges toproducemembraneswithhigher reliability. Thesenanoparticlemodified

membranes are categorized into four distinct categories, namely, conventional nanocomposites, thin-film nanocomposites, thin-film composites with nanocomposite substrate, and surface located nanocomposites; these are

schematically shown inFig.14–8[186]. These nanocomposites can enhance the process efficiency and cost for various applications andhave gained considerable attention in the cutting edge applications andhigh-performance

membraneproductioninfuelcells,protonexchangemembrane,sensors,batteries,solvents,andwatertreatment[189].

Figure14–7Variousmechanismsofantimicrobialactivitiesexertedbynanomaterials.

ReprintedfromLiQ,MahendraS,LyonDY,BrunetL,LigaMV,LiD,etal.Antimicrobialnanomaterialsforwaterdisinfectionandmicrobialcontrol:potentialapplicationsandimplications.WaterRes2008;42(18):4591–602,bypermissionofElsevier.

Figure14–8TypicaltypesofnanocompositemembranesTFC,Thin-filmcomposite.

ReprintedfromYinJ,DengB.Polymer–matrixnanocompositemembranesforwatertreatment.JMembSci2015;479:256–75,bypermissionofElsevier.

Thenanocompositestructurecombinesthepropertiesofeachcomponentandoffersnovelanduniquepropertiesthatwerenotavailablepreviously.Oneoftheimportantexamplesofnanocompositetechnologydevelopment’s

effectonmembraneapplicationisthedirectmethanolfuelcell(DMFC).TheconventionalpolymericDMFCmembranes’efficiencyisconstrainedbythehighrateofmethanolpermeationthroughapolymericmembrane,whichcauses

thechemicalreactionofthefuelwithoxygenanddepolarizationofthecathode[190].Therefore,itishighlydesirabletohaveamembranewithreducedmethanol

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permeation. One of the examples of utilization of nanocomposites in this area of application is proposed by Song et al. [190] who used Nafion polymer-layered silicate nanocomposite as a membrane in which the strong

interactionofNafionpolymerchainswithexfoliatedclayssignificantlydecreasedmethanolcrossoverthroughnanocompositemembranesbyonly1wt.%organoclayfillers.Inaddition,nanoclayimprovedthethermaldecomposition

temperatureandmechanicalpropertiesoftheNafion-basedmembrane[190].

Anotherexampleoftheenhancedperformanceofmembranesthroughtheincorporationofnanoparticlesismembranesusedinwaterandwastewatertreatmentinwhichcontaminationofmembranereducesthefluxbythe

time[187,191].Toaddressthisissue,Baeetal.[192]fabricatedTiO2entrappedmembranesfromthreedifferentpolymersofpolysulfone,polyvinylidenefluoride,andpolyacrylonitriletobeusedinfiltrationoftheactivatedsludge.The

TiO2entrappedmembraneshowedlowerfluxdeclinecomparedwithneatpolymericmembraneregardlessofthepolymericmatrix.Inanotherwork,Caoetal.[193]preparedapoly(ethyleneoxide)/grapheneoxideprotonconductive

membranewithenhancedperformancecomparedwithcommerciallyavailableones.ThepresenceofGOinthepoly(ethyleneoxide)matrixincreasestheconductivitythroughtheprotonreleasedfromtheCOOHgroupsontheGO

sheetsasanionconductivitymechanism.Thereareseveralotherexamplesofnanocomposite-basedmembranedesignsintheliteraturethatcanfurtherimprovetheefficiencyandgenerateanewgenerationofmembranesforfuture

applicationsinenergyandvariousenvironmentalapplications,whichcanboostthefutureviewofourecosystem.

14.3.3NanocompositesinEnergyApplicationsSustainable,efficient,andcleanenergystorageisanotherareathatistakentoawholenewlevelbynanocompositematerials.Hydrogenisoneoftherenewable,convenient,safe,versatile,andcleanenergyfuelsources,which

providesasignificantreductioninthegreenhousegasemissionsandfossilfuelsconsumption,andhashighenergyconversionefficiency[194,195].Thehydrogenstoragesystemsareregardedasthekeychallengeinlarge-scaleand

commercialapplicationsofhydrogenenergy[196].Aspressurizedtankandcryogenicliquidhydrogentechniquesfailtosatisfytheprimaryrequirementsforahydrogenstoragesystemsuchasbeinginexpensive,safe,deliveringlow

efficiency,andmaterial-basedstoragesystemsareexpectedtoprovideafinalsolutionforthisissue[196,197].

However,simplematerialsystemswithonlyonecomponentfailedtooperateinambienttemperatureranges,andtheysufferfromlowefficiencyoffuelingandseriousconcernsabouttheirsafetyandslowkinetics[198].The

polymeric nanocomposites are considered to have potential promise for hydrogen storage among other counterparts [199]. Saner Okan et al. [27] combined the beneficial features of polypyrrole (PPy) with those of CNT and

considerablyimprovedthehydrogenstoragecapacityofthenanocompositestructurecomparedwiththeneatpolymerandpureCNT.Inthementionedwork,CNTandPPyadsorbed0.46wt.%and0.14wt.%hydrogenwhiletheir

compositeadsorbed1.66wt.%hydrogen[27].Fig.14–9A–CexhibitthenanostructuresofPPy,CNT,PPy:CNTcomposite,respectively.Furthermore,Fig.14–9DshowshydrogensorptioncurvesofpristineCNT,PPy,oxCNT,and

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Py:CNTcomposite in the rangeof0–9000mbarpressure at room temperature indicating that pristineCNT,PPy, oxCNT, andPy:CNTadsorb0.46, 0.14, 1.03, and1.66wt.%hydrogen, respectively bespeaking that the hydrogen

storagepropertiesoftheproducednanocompositesareconsiderablyhigherthantheindividualcomponents.

InanotherstudyMuthuetal. [200]employedsulfonatedpoly(ether-ether-ketone) (SPEEK)andhexagonalboronnitride (h-BN)nanoparticles, toobtainhigh-performancehydrogenstoragematerialand theyenhanced the

hydrogenstoragefrom0.66wt.%forneatSPEEKto2.98wt.%inSPEEK-BNnanocomposite.Kimetal.[201]reportedhydrogenadsorptioninthepolyaniline–vanadiumoxidenanocompositesofupto~1.8wt%at77Kand~0.16wt%

at298Kwhereasneitherpolyaniline(~0.2wt%at77K)norpristinevanadium

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pentoxide powder (~0.2 wt% at 77 K) were able to adsorb similar amount of hydrogen. Makridis et al. [202] used Mg-nanoparticles produced by laser ablation technique as shown in Fig. 14–10 and observed that Mg-

nanoparticlesinapolymermatrixexhibitmorerapidhydrogenuptakecomparedwithMg-puretypes(<20minutesat250°C)withahighcapacityof6wt.%withexcellentreversibilityundervacuumat250°C,whichisarelativelylow

temperaturewithregardtothenecessary~330°CforMg-bulkmaterials.Thesestudiesbespeakthehighpotentialofnanocompositesforhydrogenstorageinthenearfuture.

Figure14–9SEMimagesof(A)pristinePPy,(B)pristineCNT,(C)Py:CNT=1:1composite,and(D)thecomparisonofadsorptionisothermsofpristineCNT,PPy,oxCNT,andPy:CNT=1:1.

ReprintedfromOkanBS,ZanjaniJSM,Letofsky-PapstI,CebeciFÇ,MencelogluYZ.Morphology-controllablesynthesisandcharacterizationofcarbonnanotube/polypyrrolecompositesandtheirhydrogenstoragecapacities.MaterChemPhys

2015;167(Suppl.C):171–80,bypermissionofElsevier.

14.4ConclusionandOutlookThe rapid development of nanoparticle-based nanocomposites has a huge impact on many technological areas. There are a vast variety of nanoparticles that are used in the preparation of polymeric

nanocompositesinwhichasmallchangeintheirphysicalorchemicalstructureleadstoacompletelydifferentpropertyandasetofnovelapplications.Engineersandresearchersareinaconstantattempttocreate

novelnanomaterialsormodifycurrentonestoachievemanyadvantageouspropertiesthatwerenotavailablebefore.However,someofthesepropertiesthataredesiredfromatechnicalpointofviewareundesirable

andharmfultotheenvironmentandecosystem.Therefore,thereisaneedforextensivetoxicologicalresearchforthisclassofmaterialstoavoidanypossibleriskandfacilitatetheirsafeimplementationinfuture

products.Thefirstpartofthischapterprovidesashortreviewonthe

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toxicity of some of themost important and commercially used nanoparticles utilized in polymeric nanocomposite production.Despite several research attempts focusing on the toxic behavior of nanomaterials,

ithasbeenseenthereisnoclearandsolidunderstandingoftheirmolecularscalemechanismsandproperprocedurestopreventtheiradverseeffectontheenvironment.Ithasbeendiscussedthatfunctionalization

canincreaseordecreasenanomaterials’toxiceffectdependingonthenanomaterials’natureandsurfacefunctionalizationtype.Thecomplexandinseveralcasestheunknowntoxicbehaviorofnanoparticlesraises

seriousconcernabouttheireffectonhumanhealthandecosystemsandsignifiesthenecessityoffurtherscientificexplorationandgovernmentalregulationsontheiruse.Inaddition,nanoparticle-basedpolymeric

nanocomposites are a useful material class for a wide variety of applications that can promote human life and also serve our ecosystem. The replacement of conventional materials with their nanocomposite

counterpartshasincreasedtheefficiency,lifetime,andreliability,andenabledseveralnovelapplicationsinvariousareassuchasfoodpackaging,membranes,andenergystoragesystems,amongothers.Toreiterate,

nanocompositeswiththeiruniquepropertiesarekeyforfurthertechnologicaladvancementinmanyareas.However,furthermultidisciplinaryresearchisneededtoevolvetheunderstandingoftheirenvironmental

effectsandproducenanocompositeswithminimumadverseeffectontheecosystem.

References[1]S.LordanandC.L.Higginbotham,Effectofserumconcentrationonthecytotoxicityofclayparticles,CellBiolInt36(1),2012,57–61.

[2]P.delPino,S.G.MitchellandB.Pelaz,Designandcharacterizationoffunctionalnanoparticlesforenhancedbio-performance,In:J.M.Guisan,(Ed),Immobilizationofenzymesandcells,3rded.,2013,HumanaPress

Totowa,NJ,165–207.

Figure14–10Laser-generatednanoparticlesfornanocomposites.

ReprintedfromMakridisSS,GkanasEI,PanagakosG,KikkinidesES,StubosAK,WagenerP,etal.Polymer-stablemagnesiumnanocompositespreparedbylaserablationforefficienthydrogenstorage.IntJHydrogenEnergy2013;38(26):11530–5,by

permissionofElsevier.

[3]U.Tritschler,S.Pearce,J.Gwyther,G.R.WhittellandI.Manners,50thanniversaryperspective:functionalnanoparticlesfromthesolutionself-assemblyofblockcopolymers,Macromolecules50(9),2017,

3439–3463.

[4]TheEUCommissionRecommendationontheDefinitionofNanomaterialE,EuropeanCommission,Brussels;2011.

[5]SreeprasadTS,PradeepT.Noblemetalnanoparticles.In:VajtaiR,editor.Springerhandbookofnanomaterials.Berlin,Heidelberg;2013.p.303–388.

[6]C.T.Shindu,Harshita,M.PawanKumarandT.Sushama,Ceramicnanoparticles:fabricationmethodsandapplicationsindrugdelivery,CurrPharmDes21(42),2015,6165–6188.

[7]J.SeyyedMonfaredZanjani,B.SanerOkan,I.Letofsky-Papst,M.YildizandY.Z.Menceloglu,Rationaldesignanddirectfabricationofmulti-walledhollowelectrospunfiberswithcontrollablestructureandsurface

properties,EurPolymJ62,2015,66–76.

[8]M.Bangal,S.Ashtaputre,S.Marathe,A.Ethiraj,N.Hebalkar,S.W.Gosavi,etal.,Semiconductornanoparticles,HyperfineInteract160(1),2005,81–94.

[9]ZanjaniJamalSeyyedM,OkanBurcuS,MencelogluY,YildizM.Self-healingthermosettingcomposites:concepts,chemistry,andfutureadvances.

[10]M.Ullah,J.SeyyedMonfaredZanjani,L.HaghighiPoudeh,M.Siddiq,B.SanerOkan,M.Yildiz,etal.,Manufacturingfunctionalizedmono-crystallinediamondcontainingelectrospunfibersreinforcedepoxy

compositeswithimprovedmechanicalcharacteristics,DiamRelatMater76,2017,90–96.

Page449

[11]J.S.MonfaredZanjani,B.S.Okan,M.YildizandY.Menceloglu,Fabricationandmorphologicalinvestigationofmulti-walledelectrospunpolymericnanofibers,MRSProc1621,2014,119–126.

[12]L.HaghighiPoudeh,B.SanerOkan,J.SeyyedMonfaredZanjani,M.YildizandY.Menceloglu,Designandfabricationofhollowandfilledgraphene-basedpolymericspheresviacore-shellelectrospraying,RSCAdv

5(111),2015,91147–91157.

[13]G.Salazar-Alvarez,J.Qin,V.Šepelák,I.Bergmann,M.Vasilakaki,K.N.Trohidou,etal.,Cubicversussphericalmagneticnanoparticles:theroleofsurfaceanisotropy,JAmChemSoc130(40),2008,13234–13239.

[14]Z.Zarghami,M.RamezaniandK.Motevalli,ZnOnanorods/nanoparticles:novelhydrothermalsynthesis,characterizationandformationmechanismforincreasingtheefficiencyofdye-sensitizedsolarcells,JClust

Sci27(4),2016,1451–1462.

[15]J.S.MonfaredZanjani,B.S.Okan,Y.Z.MencelogluandM.Yildiz,Nano-engineereddesignandmanufacturingofhigh-performanceepoxymatrixcompositeswithcarbonfiber/selectivelyintegratedgrapheneas

multi-scalereinforcements,RSCAdv6(12),2016,9495–9506.

[16]D.H.Jo,J.H.Kim,T.G.LeeandJ.H.Kim,Size,surfacecharge,andshapedeterminetherapeuticeffectsofnanoparticlesonbrainandretinaldiseases,Nanomedicine11(7),2015,1603–1611.

[17]W.-T.Liu,Nanoparticlesandtheirbiologicalandenvironmentalapplications,JBiosciBioeng102(1),2006,1–7.

[18]M.Tsoli,H.Kuhn,W.Brandau,H.EscheandG.Schmid,CellularuptakeandtoxicityofAu55clusters,Small1(8–9),2005,841–844.

[19]K.DonaldsonandA.Seaton,Ashorthistoryofthetoxicologyofinhaledparticles,PartFibreToxicol9,2012,13.

[20]K.Donaldson,V.Stone,A.Clouter,L.RenwickandW.MacNee,Ultrafineparticles,OccupEnvironMed58(3),2001,211.

[21]A.A.Shvedova,E.Kisin,A.R.Murray,V.J.Johnson,O.Gorelik,S.Arepalli,etal.,Inhalationvs.aspirationofsingle-walledcarbonnanotubesinC57BL/6mice:inflammation,fibrosis,oxidativestress,and

mutagenesis,AmJPhysiolLungCellMolPhysiol295(4),2008,L552–L565.

[22]K.Donaldson,V.Stone,C.L.Tran,W.KreylingandP.J.A.Borm,Nanotoxicology,OccupEnvironMed61(9),2004,727.

[23]C.L.TranandDBRTCASADJKD,Inhalationofpoorlysolubleparticles.II.influenceofparticlesurfaceareaoninflammationandclearance,InhalToxicol12(12),2000,1113–1126.

[24]L.E.Ogden,Nanoparticlesintheenvironment:tinysize,largeconsequences?,Bioscience63(3),2013,236.

[25]A.M.Knaapen,P.J.A.Borm,C.AlbrechtandR.P.F.Schins,Inhaledparticlesandlungcancer.PartA:Mechanisms,IntJCancer109(6),2004,799–809.

[26]K.Donaldson,R.Aitken,L.Tran,V.Stone,R.Duffin,G.Forrest,etal.,Carbonnanotubes:areviewoftheirpropertiesinrelationtopulmonarytoxicologyandworkplacesafety,ToxicolSci92(1),2006,5–22.

[27]B.S.Okan,J.S.M.Zanjani,I.Letofsky-Papst,F.Ç.CebeciandY.Z.Menceloglu,Morphology-controllablesynthesisandcharacterizationofcarbonnanotube/polypyrrolecompositesandtheirhydrogenstorage

capacities,MaterChemPhys167(Suppl.C),2015,171–180.

[28]M.Yumura,Carbonnanotubeindustrialapplications,AISTToday(IntEd)10,2003,8–9.

[29]F.Lu,L.Gu,M.J.Meziani,X.Wang,P.G.Luo,L.M.Veca,etal.,Advancesinbioapplicationsofcarbonnanotubes,AdvMater21(2),2009,139–152.

[30]R.Ding,G.Lu,Z.YanandM.Wilson,Recentadvancesinthepreparationandutilizationofcarbonnanotubesforhydrogenstorage,JNanosciNanotechnol1(1),2001,7–29.

[31]Z.Tang,L.Zhang,N.Wang,X.Zhang,G.Wen,G.Li,etal.,Superconductivityin4angstromsingle-walledcarbonnanotubes,Science292(5526),2001,2462–2465.

Page450

[32]R.H.Baughman,A.A.ZakhidovandW.A.deHeer,Carbonnanotubes—theroutetowardapplications,Science297(5582),2002,787.

[33]M.Kaseem,K.HamadandY.G.Ko,Fabricationandmaterialspropertiesofpolystyrene/carbonnanotube(PS/CNT)composites:areview,EurPolymJ79,2016,36–62.

[34]H.Dai,Carbonnanotubes:synthesis,integration,andproperties,AccChemRes35(12),2002,1035–1044.

[35]H.Dai,Nanotubegrowthandcharacterization,In:M.S.Dresselhaus,G.DresselhausandP.Avouris,(Eds.),Carbonnanotubes:synthesis,structure,properties,andapplications,2001,Springer,Berlin,Heidelberg,

29–53.

[36]C.-W.Lam,J.T.James,R.McCluskeyandR.L.Hunter,Pulmonarytoxicityofsingle-wallcarbonnanotubesinmice7and90daysafterintratrachealinstillation,ToxicolSci77(1),2004,126–134.

[37]Y.Wu,J.S.Hudson,Q.Lu,J.M.Moore,A.S.Mount,A.M.Rao,etal.,Coatingsingle-walledcarbonnanotubeswithphospholipids,JPhysChemB110(6),2006,2475–2478.

[38]A.Helland,P.Wick,A.Koehler,K.SchmidandC.Som,Reviewingtheenvironmentalandhumanhealthknowledgebaseofcarbonnanotubes,CiênciaSaúdeColetiva13(2),2008,441–452.

[39]S.Liu,T.H.Zeng,M.Hofmann,E.Burcombe,J.Wei,R.Jiang,etal.,Antibacterialactivityofgraphite,graphiteoxide,grapheneoxide,andreducedgrapheneoxide:Membraneandoxidativestress,ACSNano5(9),

2011,6971–6980.

[40]O.V.Kharissova,B.I.KharisovandE.G.deCasasOrtiz,Dispersionofcarbonnanotubesinwaterandnon-aqueoussolvents,RSCAdv3(47),2013,24812–24852.

[41]H.F.Lecoanet,J.-Y. BotteroandM.R.Wiesner,Laboratoryassessmentofthemobilityofnanomaterialsinporousmedia,EnvironSciTechnol38(19),2004,5164–5169.

[42]P.E.Díaz-Flores,J.A.Arcibar-Orozco,N.V.Perez-Aguilar,J.R.Rangel-Mendez,V.M.OvandoMedinaandJ.A.Alcalá-Jáuegui,Adsorptionoforganiccompoundsontomultiwallandnitrogen-dopedcarbonnanotubes:

insightsintotheadsorptionmechanisms,WaterAirSoilPollut228(4),2017,133.

[43]M.Shen,S.H.Wang,X.Shi,X.Chen,Q.Huang,E.J.Petersen,etal.,Polyethyleneimine-mediatedfunctionalizationofmultiwalledcarbonnanotubes:synthesis,characterization,andinvitrotoxicityassay,JPhys

ChemC113(8),2009,3150–3156.

[44]K.Pulskamp,S.DiabatéandH.F.Krug,Carbonnanotubesshownosignofacutetoxicitybutinduceintracellularreactiveoxygenspeciesindependenceoncontaminants,ToxicolLett168(1),2007,58–74.

[45]A.Jos,S.Pichardo,M.Puerto,E.Sánchez,A.GriloandA.M.Cameán,CytotoxicityofcarboxylicacidfunctionalizedsinglewallcarbonnanotubesonthehumanintestinalcelllineCaco-2,ToxicolInVitro23(8),

2009,1491–1496.

[46]R.K.Saxena,W.Williams,J.K.McGee,M.J.Daniels,E.BoykinandM.IanGilmour,Enhancedinvitroandinvivotoxicityofpoly-dispersedacid-functionalizedsingle-wallcarbonnanotubes,Nanotoxicology1(4),

2007,291–300.

[47]C.M.Sayes,F.Liang,J.L.Hudson,J.Mendez,W.Guo,J.M.Beach,etal.,Functionalizationdensitydependenceofsingle-walledcarbonnanotubescytotoxicityinvitro,ToxicolLett161(2),2006,135–142.

[48]J.SeyyedMonfaredZanjani,B.SanerOkanandY.Menceloglu,Manufacturingofmultilayergrapheneoxide/poly(ethyleneterephthalate)nanocompositeswithtunablecrystallinity,chainorientationsandthermal

transitions,MaterChemPhys176(Suppl.C),2016,58–67.

[49]B.S.Okan,A.Marset,J.SeyyedMonfaredZanjani,P.A.Sut,O.Sen,M.Çulha,etal.,Thermallyexfoliatedgrapheneoxidereinforcedfluorinatedpentablockpoly(L-lactide-co-ε-caprolactone)electrospunscaffolds:

insightintoantimicrobialactivityandbiodegradation,JApplPolymSci133(22),2016,n/a-n/a.

[50]SeyyedMonfaredZanjaniJ,SanerOkanB,PappasP-N,GaliotisC,ZiyaMencelogluY,YildizM.Tailoringviscoelasticresponse,self-heatinganddeicingpropertiesofcarbon-fibrereinforcedepoxycompositesbygraphenemodification.ComposPartAApplS.106(2018),pp.1-10

Page451

[51]V.Dhand,K.Y.Rhee,H.JuKimandD.HoJung,Acomprehensivereviewofgraphenenanocomposites:researchstatusandtrends,JNanomater2013,2013,14.

[52]S.F.Kiew,L.V.Kiew,H.B.Lee,T.ImaeandL.Y.Chung,Assessingbiocompatibilityofgrapheneoxide-basednanocarriers:areview,JControlRelease226,2016,217–228.

[53]M.Segal,Sellinggraphenebytheton,NatNanotechnol4,2009,612.

[54]B.Mas,J.P.Fernández-Blázquez,J.Duval,H.BunyanandJ.J.Vilatela,ThermosetcuringthroughJouleheatingofnanocarbonsforcompositemanufacture,repairandsoldering,CarbonNY63(Suppl.C),2013,

523–529.

[55]K.Zhang,K.C.KempandV.Chandra,HomogeneousanchoringofTiO2nanoparticlesongraphenesheetsforwastewatertreatment,MaterLett81(Suppl.C),2012,127–130.

[56]H.Chung,M.J.Kim,K.Ko,J.H.Kim,H.-A.Kwon,I.Hong,etal.,Effectsofgrapheneoxidesonsoilenzymeactivityandmicrobialbiomass,SciTotalEnviron514(Suppl.C),2015,307–313.

[57]P.BegumandB.Fugetsu,InductionofcelldeathbygrapheneinArabidopsisthaliana(Columbiaecotype)T87cellsuspensions,JHazardMater260(Suppl.C),2013,1032–1041.

[58]G.Eda,G.FanchiniandM.Chhowalla,Large-areaultrathinfilmsofreducedgrapheneoxideasatransparentandflexibleelectronicmaterial,NatNanotechnol3,2008,270.

[59]D.A.Jasim,H.Boutin,M.Fairclough,C.Ménard-Moyon,C.Prenant,A.Bianco,etal.,Thicknessoffunctionalizedgrapheneoxidesheetsplayscriticalroleintissueaccumulationandurinaryexcretion:apilot

PET/CTstudy,ApplMaterToday4(Suppl.C),2016,24–30.

[60]O.AkhavanandE.Ghaderi,Toxicityofgrapheneandgrapheneoxidenanowallsagainstbacteria,ACSNano4(10),2010,5731–5736.

[61]M.Venza,M.Visalli,C.Beninati,G.V.DeGaetano,D.TetiandI.Venza,Cellularmechanismsofoxidativestressandactioninmelanoma,OxidMedCellLongev2015,2015,481782.

[62]M.Hirtz,A.Oikonomou,T.Georgiou,H.FuchsandA.Vijayaraghavan,Multiplexedbiomimeticlipidmembranesongraphenebydip-pennanolithography,NatCommun4,2013,2591.

[63]S.Liu,M.Hu,T.H.Zeng,R.Wu,R.Jiang,J.Wei,etal.,Lateraldimension-dependentantibacterialactivityofgrapheneoxidesheets,Langmuir28(33),2012,12364–12372.

[64]B.Zhang,P.Wei,Z.ZhouandT.Wei,Interactionsofgraphenewithmammaliancells:molecularmechanismsandbiomedicalinsights,AdvDrugDelivRev105(PartB),2016,145–162.

[65]J.Zhao,Z.Wang,J.C.WhiteandB.Xing,Grapheneintheaquaticenvironment:adsorption,dispersion,toxicityandtransformation,EnvironSciTechnol48(17),2014,9995–10009.

[66]L.Guardia,S.Villar-Rodil,J.I.Paredes,R.Rozada,A.Martínez-AlonsoandJ.M.D.Tascón,UVlightexposureofaqueousgrapheneoxidesuspensionstopromotetheirdirectreduction,formationofgraphene–metal

nanoparticlehybridsanddyedegradation,CarbonNY50(3),2012,1014–1024.

[67]O.AkhavanandE.Ghaderi,PhotocatalyticreductionofgrapheneoxidenanosheetsonTiO2thinfilmforphotoinactivationofbacteriainsolarlightirradiation,JPhysChemC113(47),2009,20214–20220.

[68]X.Ye,Q.Zhou,C.Jia,Z.Tang,Y.ZhuandZ.Wan,Producinglarge-area,foldablegraphenepaperfromgraphiteoxidesuspensionsbyin-situchemicalreductionprocess,CarbonNY114(Suppl.C),2017,424–434.

[69]R.Kurapati,J.Russier,M.A.Squillaci,E.Treossi,C.Ménard-Moyon,A.E.DelRio-Castillo,etal.,Dispersibility-dependentbiodegradationofgrapheneoxidebymyeloperoxidase,Small11(32),2015,3985–3994.

[70]M.Chen,X.QinandG.Zeng,Biodegradationofcarbonnanotubes,graphene,andtheirderivatives,TrendsBiotechnol35(9),2017,836–846.

[71]G.P.Kotchey,B.L.Allen,H.Vedala,N.Yanamala,A.A.Kapralov,Y.Y.Tyurina,etal.,Theenzymaticoxidationofgrapheneoxide,ACSNano5(3),2011,2098–2108.

Page452

[72]G.Modugno,F.Ksar,A.Battigelli,J.Russier,P.Lonchambon,E.EletodaSilva,etal.,Acomparativestudyontheenzymaticbiodegradabilityofcovalentlyfunctionalizeddouble-andmulti-walledcarbon

nanotubes,CarbonNY100(Suppl.C),2016,367–374.

[73] TimothyV.Duncan,Applicationsofnanotechnologyinfoodpackagingandfoodsafety:Barriermaterials,antimicrobialsandsensors,JournalofColloidandInterfaceScience,363,1,2011,1-24

[74]OkadaA,KawasumiM,KurauchiT,KamigaitoO.Synthesisandcharacterizationofanylon6-clayhybrid.AbstractsofpapersoftheAmericanChemicalSociety,Washington,DC;1987.p.10-MACR.

[75]A.OkadaandA.Usuki,Twentyyearsofpolymer-claynanocomposites,MacromolMaterEng291(12),2006,1449–1476.

[76]S.SinhaRayandM.Okamoto,Polymer/layeredsilicatenanocomposites:areviewfrompreparationtoprocessing,ProgPolymSci28(11),2003,1539–1641.

[77]E.Manias,A.Touny,L.Wu,K.Strawhecker,B.LuandT.C.Chung,Polypropylene/montmorillonitenanocomposites.reviewofthesyntheticroutesandmaterialsproperties,ChemMater13(10),2001,3516–3523.

[78]S.Lordan,J.E.KennedyandC.L.Higginbotham,CytotoxiceffectsinducedbyunmodifiedandorganicallymodifiednanoclaysinthehumanhepaticHepG2cellline,JApplToxicol31(1),2011,27–35.

[79]S.Jayrajsinh,G.Shankar,Y.K.AgrawalandL.Bakre,Montmorillonitenanoclayasamultifaceteddrug-deliverycarrier:areview,JDrugDelivSciTechnol39(Suppl.C),2017,200–209.

[80]S.Hong,J.A.Hessler,M.M.BanaszakHoll,P.Leroueil,A.MeckeandB.G.Orr,Physicalinteractionsofnanoparticleswithbiologicalmembranes:theobservationofnanoscaleholeformation,JChemHealthSaf13

(3),2006,16–20.

[81]N.K.Verma,E.Moore,W.Blau,Y.VolkovandP.RameshBabu,CytotoxicityevaluationofnanoclaysinhumanepithelialcelllineA549usinghighcontentscreeningandreal-timeimpedanceanalysis,JNanoparticle

Res14(9),2012,1137.

[82]M.Baek,J.-A.LeeandS.-J.Choi,Toxicologicaleffectsofacationicclay,montmorilloniteinvitroandinvivo,MolCellToxicol8(1),2012,95–101.

[83]E.J.Murphy,E.Roberts,D.K.AndersonandL.A.Horrocks,Cytotoxicityofaluminumsilicatesinprimaryneuronalcultures,Neuroscience57(2),1993,483–490.

[84]A.Wagner,R.Eldawud,A.White,S.Agarwal,T.A.Stueckle,K.A.Sierros,etal.,Toxicityevaluationsofnanoclaysandthermallydegradedbyproductsthroughspectroscopicalandmicroscopicalapproaches,

INVALIDCITATION.

BiochimBiophysActa1861(1PtA),2017,3406–3415.

[85]Y.Xia,M.RubinoandR.Auras,Releaseofnanoclayandsurfactantfrompolymer–claynanocompositesintoafoodsimulant,EnvironSciTechnol48(23),2014,13617–13624.

[86]L.A.Sd.A.Prado,C.S.Karthikeyan,K.Schulte,S.P.NunesandI.L.deTorriani,Organicmodificationoflayeredsilicates:structuralandthermalcharacterizations,JNon-CrystSolids351(12),2005,970–975.

[87]M.Zhang,Y.Lu,X.Li,Q.Chen,L.Lu,M.Xing,etal.,StudyingthecytotoxicityandoxidativestressinducedbytwokindsofbentoniteparticlesonhumanBlymphoblastcellsinvitro,ChemBiolInteract183(3),

2010,390–396.

[88]T.Yoshida,Y.Yoshioka,K.Matsuyama,Y.Nakazato,S.Tochigi,T.Hirai,etal.,Surfacemodificationofamorphousnanosilicaparticlessuppressesnanosilica-inducedcytotoxicity,ROSgeneration,andDNAdamage

invariousmammaliancells,BiochemBiophysResCommun427(4),2012,748–752.

[89]Q.Liu,H.Yu,Z.Tan,H.Cai,W.Ye,M.Zhang,etal.,Invitroassessingtheriskofdrug-inducedcardiotoxicitybyembryonicstemcell-basedbiosensor,SensActuatorsBChem155(1),2011,214–219.

[90]G.Janer,E.Fernández-Rosas,E.MasdelMolino,D.González-Gálvez,G.Vilar,C.López-Iglesias,etal.,Invitrotoxicityoffunctionalisednanoclaysismainlydrivenbythepresenceoforganicmodifiers,

Nanotoxicology8(3),2014,279–294.

Page453

[91]K.Sachin,M.AnupamandC.Kaushik,Effectoforganicallymodifiedclayonmechanicalproperties,cytotoxicityandbactericidalpropertiesofpoly(ϵ-caprolactone)nanocomposites,MaterResExpress1(4),2014,

045302.

[92]S.Maisanaba,N.Ortuño,M.Jordá-Beneyto,S.AucejoandÁ.Jos,Development,characterizationandcytotoxicityofnovelsilane-modifiedclaymineralsandnanocompositesintendedforfoodpackaging,ApplClay

Sci138(Suppl.C),2017,40–47.

[93]S.Maisanaba,S.Pichardo,M.Puerto,D.Gutiérrez-Praena,A.M.CameánandA.Jos,Toxicologicalevaluationofclaymineralsandderivednanocomposites:areview,EnvironRes138(Suppl.C),2015,233–254.

[94]H.Abdizadeh,A.R.Atilgan,C.AtilganandB.Dedeoglu,Computationalapproachesfordecipheringtheequilibriumandkineticpropertiesofirontransportproteins,Metallomics9(11),2017,1513–1533.

[95]Z.Wang,L.Zhang,J.ZhaoandB.Xing,Environmentalprocessesandtoxicityofmetallicnanoparticlesinaquaticsystemsasaffectedbynaturalorganicmatter,EnvironSciNano3(2),2016,240–255.

[96]Y.-F.LiandC.Chen,Fateandtoxicityofmetallicandmetal-containingnanoparticlesforbiomedicalapplications,Small7(21),2011,2965–2980.

[97]H.Abdizadeh,A.R.AtilganandC.Atilgan,DetailedmoleculardynamicssimulationsofhumantransferrinprovideinsightsintoironreleasedynamicsatserumandendosomalpH,JBiolInorgChem20(4),2015,

705–718.

[98]A.Cox,P.Venkatachalam,S.SahiandN.Sharma,Reprintof:silverandtitaniumdioxidenanoparticletoxicityinplants:areviewofcurrentresearch,PlantPhysiolBiochem110(Suppl.C),2017,33–49.

[99]F.Hong,X.Yu,N.WuandY.-Q.Zhang,Progressofinvivostudiesonthesystemictoxicitiesinducedbytitaniumdioxidenanoparticles,ToxicolRes6(2),2017,115–133.

[100]S.Mallakpour,Production,characterization,andsurfacemorphologyofnovelaromaticpoly(amide-ester-imide)/functionalizedTiO2nanocompositesviaultrasonicationassistedprocess,PolymBull74(7),2017,

2465–2477.

[101]A.Kubacka,C.Serrano,M.Ferrer,H.Lünsdorf,P.Bielecki,M.L.Cerrada,etal.,High-performancedual-actionpolymer−TiO2nanocompositefilmsviameltingprocessing,NanoLett7(8),2007,2529–2534.

[102]G.Fu,P.S.VaryandC.-T.Lin,AnataseTiO2nanocompositesforantimicrobialcoatings,JPhysChemB109(18),2005,8889–8898.

[103]P.Dutilleul,L.Han,F.ValladaresandC.Messier,Crowntraitsofconiferoustreesandtheirrelationtoshadetolerancecandifferwithleaftype:abiophysicaldemonstrationusingcomputedtomography

scanningdata,FrontPlantSci6,2015,172.

[104]G.KukuandM.Culha,InvestigatingtheoriginsoftoxicresponseinTiO2nanoparticle-treatedcells,Nanomaterials7(4),2017,83.

[105]C.Jin,Y.Liu,L.Sun,T.Chen,Y.Zhang,A.Zhao,etal.,Metabolicprofilingrevealsdisorderofcarbohydratemetabolisminmousefibroblastcellsinducedbytitaniumdioxidenanoparticles,JApplToxicol33(12),

2013,1442–1450.

[106]C.-Y. Jin,B.-S.Zhu,X.-F.WangandQ.-H.Lu,Cytotoxicityoftitaniumdioxidenanoparticlesinmousefibroblastcells,ChemResToxicol21(9),2008,1871–1877.

[107]E.Demir,N.KayaandB.Kaya,GenotoxiceffectsofzincoxideandtitaniumdioxidenanoparticlesonrootmeristemcellsofAlliumcepabycometassay,TurkJBiol38(1),2014,31–39.

[108]N.Golbamaki,B.Rasulev,A.Cassano,R.L.M.Robinson,E.Benfenati,J.Leszczynski,etal.,Genotoxicityofmetaloxidenanomaterials:reviewofrecentdataanddiscussionofpossiblemechanisms,Nanoscale7

(6),2015,2154–2198.

[109]Q.Yu,H.Wang,Q.Peng,Y.Li,Z.LiuandM.Li,DifferenttoxicityofanataseandrutileTiO2nanoparticlesonmacrophages:involvementofdifferenceinaffinitytoproteinsandphospholipids,JHazardMater335,

2017,125–134.

Page454

[110]Y.Liao,W.Que,Q.Jia,Y.He,J.ZhangandP.Zhong,Controllablesynthesisofbrookite/anatase/rutileTiO2nanocompositesandsingle-crystallinerutilenanorodsarray,JMaterChem22(16),2012,7937–7944.

[111]H.J.Johnston,G.R.Hutchison,F.M.Christensen,S.Peters,S.HankinandV.Stone,IdentificationofthemechanismsthatdrivethetoxicityofTiO(2)particulates:thecontributionofphysicochemical

characteristics,PartFibreToxicol6,2009,33-.

[112]C.Jin,Y.Tang,F.G.Yang,X.L.Li,S.Xu,X.Y.Fan,etal.,CellulartoxicityofTiO2nanoparticlesinanataseandrutilecrystalphase,BiolTraceElemRes141(1),2011,3–15.

[113]J.-R.Gurr,A.S.S.Wang,C.-H.ChenandK.-Y. Jan,Ultrafinetitaniumdioxideparticlesintheabsenceofphotoactivationcaninduceoxidativedamagetohumanbronchialepithelialcells,Toxicology213(1),2005,

66–73.

[114]E.Fabian,R.Landsiedel,L.Ma-Hock,K.Wiench,W.WohllebenandB.vanRavenzwaay,Tissuedistributionandtoxicityofintravenouslyadministeredtitaniumdioxidenanoparticlesinrats,ArchToxicol82(3),

2008,151–157.

[115]J.Chen,X.Dong,J.ZhaoandG.Tang,Invivoacutetoxicityoftitaniumdioxidenanoparticlestomiceafterintraperitionealinjection,JApplToxicol29(4),2009,330–337.

[116]J.Wang,G.Zhou,C.Chen,H.Yu,T.Wang,Y.Ma,etal.,Acutetoxicityandbiodistributionofdifferentsizedtitaniumdioxideparticlesinmiceafteroraladministration,ToxicolLett168(2),2007,176–185.

[117]Y.Ze,R.Hu,X.Wang,X.Sang,X.Ze,B.Li,etal.,Neurotoxicityandgene-expressedprofileinbrain-injuredmicecausedbyexposuretotitaniumdioxidenanoparticles,JBiomedMaterResA102(2),2014,

470–478.

[118]F.Pflücker,V.Wendel,H.Hohenberg,E.Gärtner,T.Will,S.Pfeiffer,etal.,Thehumanstratumcorneumlayer:aneffectivebarrieragainstdermaluptakeofdifferentformsoftopicallyappliedmicronised

titaniumdioxide,SkinPharmacolPhysiol14(Suppl.1),2001,92–97.

[119]A.O.Gamer,E.LeiboldandB.vanRavenzwaay,Theinvitroabsorptionofmicrofinezincoxideandtitaniumdioxidethroughporcineskin,ToxicolInVitro20(3),2006,301–307.

[120]N.Sadrieh,A.M.Wokovich,N.V.Gopee,J.Zheng,D.Haines,D.Parmiter,etal.,Lackofsignificantdermalpenetrationoftitaniumdioxidefromsunscreenformulationscontainingnano-andsubmicron-sizeTiO2

particles,ToxicolSci115(1),2010,156–166.

[121]M.üllerG.Bennat,SkinpenetrationandstabilizationofformulationscontainingmicrofinetitaniumdioxideasphysicalUVfilter,IntJCosmetSci22(4),2000,271–283.

[122]J.G.Rouse,J.Yang,J.P.Ryman-Rasmussen,A.R.BarronandN.A.Monteiro-Riviere,Effectsofmechanicalflexiononthepenetrationoffullereneaminoacid-derivatizedpeptidenanoparticlesthroughskin,Nano

Lett7(1),2007,155–160.

[123]M.T.Ramesan,P.Jayakrishnan,T.SampreethandP.P.Pradyumnan,Temperature-dependentACelectricalconductivity,thermalstabilityanddifferentDCconductivitymodellingofnovelpoly(vinyl

cinnamate)/zincoxidenanocomposites,JThermAnalCalorim129(1),2017,135–145.

[124]Y.Qi,J.Zhang,S.Qiu,L.Sun,F.Xu,M.Zhu,etal.,Thermalstability,decompositionandglasstransitionbehaviorofPANI/NiOcomposites,JThermAnalyCalorim98(2),2009,533.

[125]J.L.Castro-Mayorga,M.J.Fabra,A.M.Pourrahimi,R.T.OlssonandJ.M.Lagaron,Theimpactofzincoxideparticlemorphologyasanantimicrobialandwhenincorporatedinpoly(3-hydroxybutyrate-co-3-

hydroxyvalerate)filmsforfoodpackagingandfoodcontactsurfacesapplications,FoodBioprodProcess101(Suppl.C),2017,32–44.

[126]Y.Zhang,S.Zhuang,X.XuandJ.Hu,TransparentandUV-shieldingZnO@PMMAnanocompositefilms,OptMater36(2),2013,169–172.

[127]J.AndersonandG.Vd.W.Chris,Fundamentalsofzincoxideasasemiconductor,RepProgPhys72(12),2009,126501.

Page455

[128]S.R.Choudhury,J.Ordaz,C.-L.Lo,N.P.Damayanti,F.ZhouandJ.Irudayaraj,Fromthecover:zincoxidenanoparticles-inducedreactiveoxygenspeciespromotesmultimodalcyto-andepigenetictoxicity,Toxicol

Sci156(1),2017,261–274.

[129]C.T.Ng,L.Q.Yong,M.P.Hande,C.N.Ong,L.E.Yu,B.H.Bay,etal.,ZincoxidenanoparticlesexhibitcytotoxicityandgenotoxicitythroughoxidativestressresponsesinhumanlungfibroblastsandDrosophila

melanogaster,IntJNanomed12,2017,1621–1637.

[130]P.Venkatachalam,M.Jayaraj,R.Manikandan,N.Geetha,E.R.Rene,N.C.Sharma,etal.,Zincoxidenanoparticles(ZnONPs)alleviateheavymetal-inducedtoxicityinLeucaenaleucocephalaseedlings:a

physiochemicalanalysis,PlantPhysiolBiochem110(Suppl.C),2017,59–69.

[131]J.Hou,Y.Wu,X.Li,B.Wei,S.LiandX.Wang,Toxiceffectsofdifferenttypesofzincoxidenanoparticlesonalgae,plants,invertebrates,vertebratesandmicroorganisms,Chemosphere193(Suppl.C),2018,

852–860.

[132]R.Guan,T.Kang,F.Lu,Z.Zhang,H.ShenandM.Liu,Cytotoxicity,oxidativestress,andgenotoxicityinhumanhepatocyteandembryonickidneycellsexposedtoZnOnanoparticles,NanoscaleResLett7(1),

2012,602.

[133]A.Król,P.Pomastowski,K.Rafińska,V.Railean-PlugaruandB.Buszewski,Zincoxidenanoparticles:synthesis,antisepticactivityandtoxicitymechanism,AdvColloidInterfaceSci249(Suppl.C),2017,37–52.

[134]M.Heinlaan,A.Ivask,I.Blinova,H.-C.DubourguierandA.Kahru,ToxicityofnanosizedandbulkZnO,CuOandTiO2tobacteriaVibriofischeriandcrustaceansDaphniamagnaandThamnocephalusplatyurus,

Chemosphere71(7),2008,1308–1316.

[135]M.Premanathan,K.Karthikeyan,K.JeyasubramanianandG.Manivannan,SelectivetoxicityofZnOnanoparticlestowardgram-positivebacteriaandcancercellsbyapoptosisthroughlipidperoxidation,

Nanomedicine7(2),2011,184–192.

[136]V.Sharma,R.K.Shukla,N.Saxena,D.Parmar,M.DasandA.Dhawan,DNAdamagingpotentialofzincoxidenanoparticlesinhumanepidermalcells,ToxicolLett185(3),2009,211–218.

[137]A.S.Anand,D.N.Prasad,S.B.SinghandE.Kohli,ChronicexposureofzincoxidenanoparticlescausesdeviantphenotypeinDrosophilamelanogaster,JHazardMater327(Suppl.C),2017,180–186.

[138]D.Guo,C.Wu,H.Jiang,Q.Li,X.WangandB.Chen,SynergisticcytotoxiceffectofdifferentsizedZnOnanoparticlesanddaunorubicinagainstleukemiacancercellsunderUVirradiation,JPhotochemPhotobioB

Bio93(3),2008,119–126.

[139]S.Nair,A.Sasidharan,V.V.DivyaRani,D.Menon,S.Nair,K.Manzoor,etal.,RoleofsizescaleofZnOnanoparticlesandmicroparticlesontoxicitytowardbacteriaandosteoblastcancercells,JMaterSciMater

Med20(1),2008,235.

[140]I.L.HsiaoandY.-J.Huang,EffectsofvariousphysicochemicalcharacteristicsonthetoxicitiesofZnOandTiO2nanoparticlestowardhumanlungepithelialcells,SciTotalEnviron409(7),2011,1219–1228.

[141]S.Hackenberg,A.Scherzed,A.Technau,M.Kessler,K.Froelich,C.Ginzkey,etal.,Cytotoxic,genotoxicandpro-inflammatoryeffectsofzincoxidenanoparticlesinhumannasalmucosacellsinvitro,ToxicolIn

Vitro25(3),2011,657–663.

[142]Z.Zhou,J.Son,B.Harper,Z.ZhouandS.Harper,Influenceofsurfacechemicalpropertiesonthetoxicityofengineeredzincoxidenanoparticlestoembryoniczebrafish,BeilsteinJNanotechnol6,2015,

1568–1579.

[143]D.Bartczak,M.O.Baradez,S.Merson,H.Goenaga-InfanteandD.Marshall,SurfaceliganddependenttoxicityofzincoxidenanoparticlesinHepG2cellmodel,JPhysConfSer429(1),2013,012015.

[144]V.S.Nguyen,D.Rouxel,B.Vincent,L.Badie,F.D.D.Santos,E.Lamouroux,etal.,InfluenceofclustersizeandsurfacefunctionalizationofZnOnanoparticlesonthemorphology,thermomechanicaland

piezoelectricpropertiesofP(VDF-TrFE)nanocompositefilms,ApplSurfSci279(Suppl.C),2013,204–211.

Page456

[145]A.F.Jaramillo,R.Baez-Cruz,L.F.Montoya,C.Medinam,E.Pérez-Tijerina,F.Salazar,etal.,EstimationofthesurfaceinteractionmechanismofZnOnanoparticlesmodifiedwithorganosilanegroupsbyRaman

spectroscopy,CeramInt43(15),2017,11838–11847.

[146]A.Abdelhay,T.Carmen-Mihaela,M.Christophe,M.Cédric,G.Hélène,M.Ghouti,etal.,Physicochemicalpropertiesandcellulartoxicityof(poly)aminoalkoxysilanes-functionalizedZnOquantumdots,

Nanotechnology23(33),2012,335101.

[147]M.Ramasamy,M.Das,S.S.A.AnandD.K.Yi,Roleofsurfacemodificationinzincoxidenanoparticlesanditstoxicityassessmenttowardhumandermalfibroblastcells,IntJNanomed9,2014,3707–3718.

[148]I.L.HsiaoandY.-J.Huang,TitaniumoxideshellcoatingsdecreasethecytotoxicityofZnOnanoparticles,ChemResToxicol24(3),2011,303–313.

[149]M.Luo,C.Shen,B.N.Feltis,L.L.Martin,A.E.Hughes,P.F.A.Wright,etal.,ReducingZnOnanoparticlecytotoxicitybysurfacemodification,Nanoscale6(11),2014,5791–5798.

[150]P.Krystosiak,W.TomaszewskiandE.Megiel,High-densitypolystyrene-graftedsilvernanoparticlesandtheiruseinthepreparationofnanocompositeswithantibacterialproperties,JColloidInterfaceSci498

(Suppl.C),2017,9–21.

[151]T.HuangandX.-H.N.Xu,Synthesisandcharacterizationoftunablerainbowcoloredcolloidalsilvernanoparticlesusingsingle-nanoparticleplasmonicmicroscopyandspectroscopy,JMaterChem20(44),2010,

9867–9876.

[152]W.L.Oliani,D.F.Parra,L.G.H.Komatsu,N.Lincopan,V.K.RangariandA.B.Lugao,Fabricationofpolypropylene/silvernanocompositesforbiocidalapplications,MaterSciEng,C75(Suppl.C),2017,845–853.

[153]K.Kawata,M.OsawaandS.Okabe,InvitrotoxicityofsilvernanoparticlesatnoncytotoxicdosestoHepG2humanhepatomacells,EnvironSciTechnol43(15),2009,6046–6051.

[154]C.Vaquero,C.Gutierrez-Cañas,N.GalarzaandJ.L.LópezdeIpiña,Exposureassessmenttoengineerednanoparticleshandledinindustrialworkplaces:thecaseofalloyingnano-TiO2innewsteelformulations,J

AerosolSci102(Suppl.C),2016,1–15.

[155]S.Kim,J.E.Choi,J.Choi,K.-H.Chung,K.Park,J.Yi,etal.,Oxidativestress-dependenttoxicityofsilvernanoparticlesinhumanhepatomacells,ToxicolInVitro23(6),2009,1076–1084.

[156]A.M.ElBadawy,R.G.Silva,B.Morris,K.G.Scheckel,M.T.SuidanandT.M.Tolaymat,surfacecharge-dependenttoxicityofsilvernanoparticles,EnvironSciTechnol45(1),2011,283–287.

[157]J.Fabrega,S.R.Fawcett,J.C.RenshawandJ.R.Lead,Silvernanoparticleimpactonbacterialgrowth:effectofpH,concentration,andorganicmatter,EnvironSciTechnol43(19),2009,7285–7290.

[158]O.Choi,T.E.Clevenger,B.Deng,R.Y.Surampalli,L.RossandZ.Hu,Roleofsulfideandligandstrengthincontrollingnanosilvertoxicity,WaterRes43(7),2009,1879–1886.

[159]O.Choi,K.K.Deng,N.-J.Kim,L.Ross,R.Y.SurampalliandZ.Hu,Theinhibitoryeffectsofsilvernanoparticles,silverions,andsilverchloridecolloidsonmicrobialgrowth,WaterRes42(12),2008,3066–3074.

[160]J.Helmlinger,C.Sengstock,Gro,C.Mayer,T.A.Schildhauer,M.Koller,etal.,Silvernanoparticleswithdifferentsizeandshape:equalcytotoxicity,butdifferentantibacterialeffects,RSCAdv6(22),2016,

18490–18501.

[161]M.Ahamed,M.Karns,M.Goodson,J.Rowe,S.M.Hussain,J.J.Schlager,etal.,DNAdamageresponsetodifferentsurfacechemistryofsilvernanoparticlesinmammaliancells,ToxicolApplPharmacol233(3),

2008,404–410.

[162]M.Rai,A.YadavandA.Gade,Silvernanoparticlesasanewgenerationofantimicrobials,BiotechnolAdv27(1),2009,76–83.

[163]Z.-M.Xiu,Q.-B.Zhang,H.L.Puppala,V.L.ColvinandP.J.J.Alvarez,Negligibleparticle-specificantibacterialactivityofsilvernanoparticles,NanoLett12(8),2012,4271–4275.

Page457

[164]P.V.Asharani,W.YiLian,G.ZhiyuanandV.Suresh,Toxicityofsilvernanoparticlesinzebrafishmodels,Nanotechnology19(25),2008,255102.

[165]J.E.Choi,S.Kim,J.H.Ahn,P.Youn,J.S.Kang,K.Park,etal.,Inductionofoxidativestressandapoptosisbysilvernanoparticlesintheliverofadultzebrafish,AquatToxicol100(2),2010,151–159.

[166]K.M.Newton,H.L.Puppala,C.L.Kitchens,V.L.ColvinandS.J.Klaine,SilvernanoparticletoxicitytoDaphniamagnaisafunctionofdissolvedsilverconcentration,EnvironToxicolChem32(10),2013,2356–2364.

[167]E.Navarro,F.Piccapietra,B.Wagner,F.Marconi,R.Kaegi,N.Odzak,etal.,ToxicityofsilvernanoparticlestoChlamydomonasreinhardtii,EnvironSciTechnol42(23),2008,8959–8964.

[168]A.Brandelli,L.F.W.BrumandJ.H.Z.dosSantos,Nanostructuredbioactivecompoundsforecologicalfoodpackaging,EnvironChemLett15(2),2017,193–204.

[169]D.Dainelli,N.Gontard,D.Spyropoulos,E.Zondervan-vandenBeukenandP.Tobback,Activeandintelligentfoodpackaging:legalaspectsandsafetyconcerns,TrendsFoodSciTechnol19(Suppl.1),2008,

S103–S112.

[170]M.Vanderroost,P.Ragaert,F.DevlieghereandB.DeMeulenaer,Intelligentfoodpackaging:thenextgeneration,TrendsFoodSciTechnol39(1),2014,47–62.

[171]B.TanandN.L.Thomas,Areviewofthewaterbarrierpropertiesofpolymer/clayandpolymer/graphenenanocomposites,JMembSci514(Suppl.C),2016,595–612.

[172]Y.Cui,S.Kumar,B.RaoKonaandD.vanHoucke,Gasbarrierpropertiesofpolymer/claynanocomposites,RSCAdv5(78),2015,63669–63690.

[173]H.-D.Huang,P.-G.Ren,J.-Z.Xu,L.Xu,G.-J.Zhong,B.S.Hsiao,etal.,Improvedbarrierpropertiesofpoly(lacticacid)withrandomlydispersedgrapheneoxidenanosheets,JMembSci464(Suppl.C),2014,

110–118.

[174]P.-G.Ren,H.Wang,H.-D.Huang,D.-X.YanandZ.-M.Li,Characterizationandperformanceofdodecylaminefunctionalizedgrapheneoxideanddodecylaminefunctionalizedgraphene/high-densitypolyethylene

nanocomposites:acomparativestudy,JApplPolymSci131(2),2014,n/a-n/a.

[175]M.AlexandreandP.Dubois,Polymer-layeredsilicatenanocomposites:preparation,propertiesandusesofanewclassofmaterials,MaterSciEngR28(1),2000,1–63.

[176]A.Kalendova,D.Merinska,J.F.GerardandM.Slouf,Polymer/claynanocompositesandtheirgasbarrierproperties,PolymCompos34(9),2013,1418–1424.

[177]A.Emamifar,M.Kadivar,M.ShahediandS.Soleimanian-Zad,EvaluationofnanocompositepackagingcontainingAgandZnOonshelflifeoffreshorangejuice,InnovFoodSciEmergTechnol11(4),2010,

742–748.

[178]A.Emamifar,M.Kadivar,M.ShahediandS.Soleimanian-Zad,EffectofnanocompositepackagingcontainingAgandZnOoninactivationofLactobacillusplantaruminorangejuice,FoodControl22(3),2011,

408–413.

[179]C.Damm,M.NeumannandH.Münstedt,Propertiesofnanosilvercoatingsonpolymethylmethacrylate,SoftMater3(2–3),2005,71–88.

[180]Q.Chaudhry,M.Scotter,J.Blackburn,B.Ross,A.Boxall,L.Castle,etal.,Applicationsandimplicationsofnanotechnologiesforthefoodsector,FoodAddContamPartA25(3),2008,241–258.

[181]G.Mauriello,E.DeLuca,A.LaStoria,F.VillaniandD.Ercolini,Antimicrobialactivityofanisin-activatedplasticfilmforfoodpackaging,LettApplMicrobiol41(6),2005,464–469.

[182]Q.Li,S.Mahendra,D.Y.Lyon,L.Brunet,M.V.Liga,D.Li,etal.,Antimicrobialnanomaterialsforwaterdisinfectionandmicrobialcontrol:potentialapplicationsandimplications,WaterRes42(18),2008,

4591–4602.

[183]A.Emamifar,Applicationsofantimicrobialpolymernanocompositesinfoodpackaging,In:A.Hashim,(Ed),Advancesinnanocompositetechnology,2011,InTech,Rijeka,[chapter13].

Page458

[184]M.B.ShiflettandH.C.Foley,Ultrasonicdepositionofhigh-selectivitynanoporouscarbonmembranes,Science285(5435),1999,1902–1905.

[185]T.C.Merkel,B.D.Freeman,R.J.Spontak,Z.He,I.Pinnau,P.Meakin,etal.,Ultrapermeable,reverse-selectivenanocompositemembranes,Science296(5567),2002,519–522.

[186]J.YinandB.Deng,Polymer–matrixnanocompositemembranesforwatertreatment,JMembSci479,2015,256–275.

[187]L.Y.Ng,A.W.Mohammad,C.P.LeoandN.Hilal,Polymericmembranesincorporatedwithmetal/metaloxidenanoparticles:acomprehensivereview,Desalination308,2013,15–33.

[188]H.Cong,M.Radosz,B.F.TowlerandY.Shen,Polymer–inorganicnanocompositemembranesforgasseparation,SepPurifTechnol55(3),2007,281–291.

[189]M.Ulbricht,Advancedfunctionalpolymermembranes,Polymer(Guildf)47(7),2006,2217–2262.

[190]M.-K.Song,S.-B.Park,Y.-T.Kim,K.-H.Kim,S.-K.MinandH.-W.Rhee,Characterizationofpolymer-layeredsilicatenanocompositemembranesfordirectmethanolfuelcells,ElectrochimActa50(2),2004,

639–643.

[191]K.Jian,P.N.PintauroandR.Ponangi,Separationofdiluteorganic/watermixtureswithasymmetricpoly(vinylidenefluoride)membranes,JMembSci117(1),1996,117–133.

[192]T.-H.BaeandT.-M.Tak,EffectofTiO2nanoparticlesonfoulingmitigationofultrafiltrationmembranesforactivatedsludgefiltration,JMembSci249(1),2005,1–8.

[193]Y.-C.Cao,C.Xu,X.Wu,X.Wang,L.XingandK.Scott,Apoly(ethyleneoxide)/grapheneoxideelectrolytemembraneforlowtemperaturepolymerfuelcells,JPowerSources196(20),2011,8377–8382.

[194]M.Pumera,Graphene-basednanomaterialsforenergystorage,EnergyEnvironSci4(3),2011,668–674.

[195]M.U.Niemann,S.S.Srinivasan,A.R.Phani,A.Kumar,D.Y.GoswamiandE.K.Stefanakos,Nanomaterialsforhydrogenstorageapplications:areview,JNanomater2008,2008,9.

[196]C.Liu,F.Li,L.-P.MaandH.-M.Cheng,Advancedmaterialsforenergystorage,AdvMater22(8),2010,E28–E62.

[197]A.S.Aricò,P.Bruce,B.Scrosati,J.-M.TarasconandW.vanSchalkwijk,Nanostructuredmaterialsforadvancedenergyconversionandstoragedevices,NatMater4,2005,366.

QueriesandAnswersQuery:Pleasechecktheeditsmadetothesentence:"Furthermore,itisobserved…effectoncells"andamendifnecessary.Answer:Modificationshavebeenmade.

Query:Pleasechecktheeditsmadetothesentence:"Inadditiontothetoxicity…withZnOnanoparticlesthemselves"andamendifnecessary.Answer:Modificationshavebeenmade.

Query:Pleasechecktheeditsmadetothesentence:Thestateofthedispersion…modificationofparticles"andamendifnecessary.Answer:itseemsOK.

Query:PleaseprovidefullreferencedetailsforRefs.[9,50].Answer:[9]J.S.M.Zanjani,S.OkanBurcu,Y.Menceloglu,M.YildizM.Delville,A.Taubert(Eds.),Self‐HealingThermosettingComposites:Concepts,Chemistry,andFutureAdvances,HybridOrganic‐InorganicInterfaces:TowardsAdvancedFunctionalMaterials,Wiley(2017).(CH3)DOI:10.1002/9783527807130.ch3

Query:PleaseprovidefullreferencedetailsforRef.[73].Else,deleteandrenumbertherest.Answer:updated.

Query:Therearefiveparts(a)to(e)ofFigure14-2,butthesearenotdefinedinthecaption.Pleaseprovideadefinitionforeachpart.Answer:updated.

Query:Pleaseprovidebetterqualityimagesforfigures14-1,14-3,14-5,14-6,14-7,14-10.Answer:Thebestavailablequalityimagesareattached.

[198]M.DincăandJ.R.Long,Hydrogenstorageinmicroporousmetal–organicframeworkswithexposedmetalsites,AngewChemIntEd47(36),2008,6766–6779.

[199]Q.Zhang,E.Uchaker,S.L.CandelariaandG.Cao,Nanomaterialsforenergyconversionandstorage,ChemSocRev42(7),2013,3127–3171.

[200]R.NareshMuthu,S.RajashabalaandR.Kannan,Synthesisandcharacterizationofpolymer(sulfonatedpoly-ether-ether-ketone)basednanocomposite(h-boronnitride)membraneforhydrogenstorage,IntJ

HydrogenEnergy40(4),2015,1836–1845.

[201]B.H.Kim,W.G.Hong,S.M.Lee,Y.J.Yun,H.Y.Yu,S.-Y. Oh,etal.,Enhancementofhydrogenstoragecapacityinpolyaniline–vanadiumpentoxidenanocomposites,IntJHydrogenEnergy35(3),2010,1300–1304.

[202]S.S.Makridis,E.I.Gkanas,G.Panagakos,E.S.Kikkinides,A.K.Stubos,P.Wagener,etal.,Polymer-stablemagnesiumnanocompositespreparedbylaserablationforefficienthydrogenstorage,IntJHydrogen

Energy38(26),2013,11530–11535.

Abstract

Inthepastdecade,therehasbeenadramaticincreaseintheproductionandapplicationofengineerednanomaterialsandtheirpolymericnanocomposites.Thissteepincreaseinthequantitiesofnanomaterials

raisesthequestionofwhethertheunknownrisksofengineerednanoparticlesoutweightheirbenefitsandwhatarethepotentialrisksofsuchmaterialsonourhealthandtheenvironment.Thereareseveralresearch

resultsavailablefocusingonthenanomaterials’harmfulpotentialsuchasthetoxicologicaleffectonlivingorgans,andotheradverseenvironmentaleffects.However,noclearguidelinesexisttoquantifytheseeffects

andtopreventunplannedenvironmentalcosts.

Therefore, it is necessary for research and industrial communities to engage in nanotoxicological research, risk assessment protocol development, and safe handling guidelines preparation tominimize the

environmentalconsequencesofnanoparticles.Thischapterwillfocusontheenvironmentaleffectsofnanomaterials,nanotoxicology,andtheirnovelandinnovativeenvironmentallyfriendlyapplications.

Keywords:Nanoparticles;polymericnanocomposites;nanotoxicology;environment;nanocompositesapplication.