14.2.1 carbon nanotubes -...
TRANSCRIPT
PolymerCompositeswithFunctionalizedNanoparticles
Shorttitle:Chapter14PolymerCompositesContainingFunctionalizedNanoparticles
14
Page429
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
Page430
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
Page431
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,
Page432
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
Page433
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
Page434
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
Page435
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
Page436
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
Page437
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
Page438
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
Page439
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
Page440
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
Page441
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].
Page442
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-
Page443
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,
Page444
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
Page445
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
Page446
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
Page447
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
Page448
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.