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Metal Nanoparticles- Polymer Hybrid Materials Edited by Iole Venditti Printed Edition of the Special Issue Published in Polymers www.mdpi.com/journal/polymers Metal Nanoparticles-Polymer Hybrid Materials Metal Nanoparticles-Polymer Hybrid Materials Editor IoleVenditti MDPI•Basel•Beijing•Wuhan•Barcelona•Belgrade•Manchester•Tokyo•Cluj•Tianjin Editor IoleVenditti RomaTreUniversity Italy EditorialOffice MDPI St.Alban-Anlage66 4052Basel,Switzerland This is a reprint of articles from the Special Issue published online in the open access journal Polymers(ISSN2073-4360) (availableat:https://www.mdpi.com/journal/polymers/specialissues/ MetalNanoPolymers). Forcitationpurposes,citeeacharticleindependentlyasindicatedonthearticlepageonlineandas indicatedbelow: LastName,A.A.;LastName,B.B.;LastName,C.C.ArticleTitle. JournalNameYear,VolumeNumber, PageRange. ISBN978-3-0365-5203-3(Hbk) ISBN978-3-0365-5204-0(PDF) ©2022bytheauthors. ArticlesinthisbookareOpenAccessanddistributedundertheCreative Commons Attribution (CC BY) license, which allows users to download, copy and build upon publishedarticles,aslongastheauthorandpublisherareproperlycredited,whichensuresmaximum disseminationandawiderimpactofourpublications. ThebookasawholeisdistributedbyMDPIunderthetermsandconditionsoftheCreativeCommons licenseCCBY-NC-ND. Contents AbouttheEditor ........................................................................................................................................ vii Prefaceto”MetalNanoparticles-PolymerHybridMaterials” . . . . . . . . . . . . . . . . . . . . ix IoleVenditti MetalNanoparticles–PolymersHybridMaterialsI Reprintedfrom:Polymers2022,14,3117,doi:10.3390/polym14153117 . . . . . . . . . . . . . . . . 1 AndreaFiorati,AriannaBellingeri,CarloPunta,IlariaCorsiandIoleVenditti SilverNanoparticlesforWaterPollutionMonitoringandTreatments:EcosafetyChallengeand Cellulose-BasedHybridsSolution Reprintedfrom:Polymers2020,12,1635,doi:10.3390/polym12081635 . . . . . . . . . . . . . . . 5 Irena Jacukowicz-Sobala, Ewa Stanisławska, Agnieszka Baszczuk, Marek Jasiorski and Elz˙bietaKociołek-Balawejder Size-ControlledTransformationofCu2OintoZeroValentCopperwithintheMatrixofAnion ExchangersviaGreenChemicalReduction Reprintedfrom:Polymers2020,12,2629,doi:10.3390/polym12112629 . . . . . . . . . . . . . . . . 29 GinaM.DiSalvo,AbbyR.Robinson,MohamedS.Aly,EricR.Hoglund,SeanM.O’Malley andJulianneC.Griepenburg Polymersome Poration and Rupture Mediated by Plasmonic Nanoparticles in Response to Single-PulseIrradiation Reprintedfrom:Polymers2020,12,2381,doi:10.3390/polym12102381 . . . . . . . . . . . . . . . . 51 WoongGiLee,YounghyunChoandSangWookKang Effect of Ionic Radius in Metal Nitrate on Pore Generation of Cellulose Acetate in PolymerNanocomposite Reprintedfrom:Polymers2020,12,981,doi:10.3390/polym12040981 . . . . . . . . . . . . . . . . 65 Julia Radwan-Pragłowska, Łukasz Janus, Marek Piątkowski, Dariusz Bogdał and Dalibor Matysek 3D Hierarchical, Nanostructured Chitosan/PLA/HA Scaffolds Doped with TiO2/Au/Pt NPs with Tunable Properties for Guided Bone Tissue Engineering Reprintedfrom:Polymers2020,12,792,doi:10.3390/polym12040792 . . . . . . . . . . . . . . . . 75 MeimeiWu,ChaoZhang,YihanJi,YuanTian,HaonanWei,ChonghuiLi,ZhenLi,Tiying Zhu,QianqianSun,BaoyuanManandMeiLiu 3DUltrasensitivePolymers-PlasmonicHybridFlexiblePlatformforIn-SituDetection Reprintedfrom:Polymers2020,12,392,doi:10.3390/polym12020392 . . . . . . . . . . . . . . . . 91 JorgeARoacho-Pe´rez,FernandoGRuiz-Hernandez,ChristianChapa-Gonzalez,HerminiaG Mart´ınez-Rodr´ıguez, Israel A Flores-Urquizo, Florencia E Pedroza-Montoya, ElsaN Garza-Trevinõ, Minerva Bautista-Villareal, Perla E Garcıá-Casillas and Celia N S ańchez-Dom´ınguez Magnetite Nanoparticles Coated with PEG 3350-Tween 80: In Vitro Characterization Using PrimaryCellCultures Reprintedfrom:Polymers2020,12,300,doi:10.3390/polym12020300 . . . . . . . . . . . . . . . . . 105 PeiyuanShao,PengXu,LeiZhang,YunXue,XihuiZhao,ZichaoLiandQunLi Non-ChlorideinSituPreparationofNano-CuprousOxideandItsEffectonHeatResistanceand CombustionPropertiesofCalciumAlginate Reprintedfrom:Polymers2019,11,1760,doi:10.3390/polym11111760 . . . . . . . . . . . . . . . . 119 v About the Editor IoleVenditti Iole Venditti is Associate Professor of Inorganic Chemistry at the Science Department of the Roma Tre University of Rome, Italy. She holds an international Ph.D. in Materials Science from SapienzaUniversityofRome.Herresearchfocusesonmicroandnanostructuredmaterials,basedon noblemetals(goldplatinumsilver,copper)onpolymersandhybridsystems. Thesematerialshave foundapplicationinoptoelectronicdevices,indrugdeliveryandinthedetectionofenvironmental pollutants.Shehascollaboratedwithmanyresearchersaroundtheworldonvariousresearchprojects onthesetopics. SheisEditorforseveralhigh-levelinternationaljournals,includingNanomaterials, Polymers,Chemosensors. Shecurrentlyhas4patents,hascollaboratedon2books,haspublished morethan100scientificarticles,withmorethan3000citationsandhasanh-indexof36,according toScopus. vii Preface to ”Metal Nanoparticles-Polymer Hybrid Materials” Thiscollectionfocusesonatopicofgreatinterest,hybridmetal-polymernanomaterials.Infact, hybridnanostructuredsystemsbasedonpolymersandmetalsarehighlycompetitiveandefficient andarestartingtobepresentontheglobalmarket. ThisiswhyIfounditstimulatingtoopena specialissueonthistopicandtofilltheroleofGuestEditor. Thebookopenswithaneditorialthat presents the various works and their common threads. What results is characterized by a broad multidisciplinarity and boasts international contributions, with authors from different countries (Italy, Poland, USA,Korea, CzechRepublic, China, Mexico,) tounderlinehowsciencecanalways representabridgebetweenpeoplesandcultures. Allcontributionsrepresentworksfromleading universitiesandresearchcentersaroundtheworld. I,asGuestEditor,andtheMDPIstaffarevery pleasedtoofferthisspecialissuetoallreadersinterestedinthevastworldofhybridnanomaterials. IoleVenditti Editor ix polymers Editorial Metal Nanoparticles–Polymers Hybrid Materials I IoleVenditti SciencesDepartment,RomaTreUniversity,ViadellaVascaNavale79,00146Rome,Italy; [email protected];Tel.:+39-06-5733-3388 Importantdiscoverieshavecharacterizedthelastdecade,highlightingtheimpor- tanceofinvestmentinresearchinfieldssuchasmedicine,biology,computerscience,and physics[1–9]. Hybridnanosystems,inwhichdifferentcomponentssynergisticallycontributeto peculiarproperties,areanimportantexampleofhowmultidisciplinarityisnowessential fordevelopinginnovativeideasandmaterials.Inparticular,thestudyanddevelopment ofhybridmaterialsbasedonmetalnanoparticlesandpolymersrequirestudiesonthe structure–propertyrelationships,andwillallowadvancedapplicationsinsectorssuchas energy,optoelectronics,andenvironmentalprotection[10–16]. Therefore,thisSpecialIssuewasborn,collectingcontributionsfromdifferentsectors suchaschemistry,engineering,physics,andbiology.Thegreatgoalachievedwiththiscol- lectioniscertainlytheabilitytoprovideanupdatedoverviewofboththegreatopportunities andthechallengesthathybridmaterialsbasedonmetal–polymernanoparticlescreate. Oneofthekeytopicsofthelastdecadeconcernstheuseofsilvernanoparticles(AgNPs) andtheirincreasingintegrationintoenvironmentalapplications,includingthemonitoring andtreatmentofwaterpollution,whichisraisingconcernsabouttheirenvironmental impact. ThereviewbyFioratietal.[17]analyzesthesituationbasedonthemostrecent literatureandproposesadesignstrategythatcombinesbetterperformancewiththeabsence ofrisksforecosystems.Thereview,startingwithanoverviewoftherecentpreparations ofAgNPsandtheiruses,indicatespotentialsolutionsbasedonAgNPs–cellulosehybrid materialsthatwouldbeefficientandeco-compatibleformonitoringandtreatingwater Citation:Venditti,I.Metal pollution.Thedevelopmentofthesehybridmaterialsfollowinganeco-designapproach Nanoparticles–PolymersHybrid canrepresentawinningstrategyforexploitingAgNP-basednanotechnologiesforthe MaterialsI.Polymers2022,14,3117. monitoringandtreatmentofwaterpollution. https://doi.org/10.3390/ I. Jacukowicz-Sobala et al. [18] presented the preparation of composite materials polym14153117 containingzero-valentcopper(ZVC)dispersedinamatrixoftwocommerciallyavailable, Received:11July2022 stronglybasicanionexchangerswithamacroreticular(AmberliteIRA900Cl)andgel- Accepted:27July2022 like(AmberliteIRA402OH)structure.TheCu0particlesappearedintheresinousphase Published:30July2022 asaproductofthereductionoftheprecursor,i.e.,copper(I)oxideparticlespreviously Publisher’sNote:MDPIstaysneutral depositedinthetwosupportmaterials. Asaresult,macroporousandgel-typehybrid withregardtojurisdictionalclaimsin productscontainingZVCwereobtained,withtotalcoppercontentsof7.7and5.3%by publishedmapsandinstitutionalaffil- weight,respectively.X-raydiffractionandFourier-transforminfraredspectroscopy(FTIR) iations. confirmed the successful transformation of the starting oxide particles into a metallic deposit.Ascanningelectronmicroscopy(SEM)studyshowedthatthemorphologyofthe depositismainlyinfluencedbythetypeofmatrixexchanger.Consideringthatboththe reactionparametersandtheoperatingtechniquesinfluencethesize,shape,anddistribution Copyright: © 2022 by the author. ofCu0,aswellastheporousstructureofthepolymermatrix,thecompositematerials Licensee MDPI, Basel, Switzerland. obtainedcanhavepromisingapplications,includingincatalyticorphotocatalyticchemical Thisarticleisanopenaccessarticle reactionsinvolvingbothgaseousorliquidreagents,aswellasshowingantibacterialactivity. distributed under the terms and G.M.DiSalvoetal.[19]studiedtheself-assemblyofamphiphilicdiblockcopolymers conditionsoftheCreativeCommons intopolymericvesicles,commonlyknownaspolymersomes,resultinginaversatilesystem Attribution(CCBY)license(https:// foravarietyofapplicationsincludingdrugdeliveryandmicroreactors.Inthisstudy,the creativecommons.org/licenses/by/ 4.0/). incorporationofhydrophobicplasmonicnanoparticleswithinapolymersomemembrane Polymers2022,14,3117.https://doi.org/10.3390/polym14153117 1 https://www.mdpi.com/journal/polymers Polymers2022,14,3117 facilitatedthelight-stimulatedreleaseofvesicleencapsulants.Thisworksoughttoachieve tunable,triggeredreleasewithnon-invasive,spatiotemporalcontrolusingsingle-pulse irradiation.Goldnanoparticles(AuNPs)wereincorporatedasphotosensitizersintothe hydrophobicmembranesofmicron-scalepolymersomes, andthecargo-releaseprofile wascontrolledbyvaryingthepulseenergyandnanoparticleconcentration. Thestudy demonstratedtheabilitytoachieveimmediatevesicleruptureaswellasvesicleporation resultingincargodiffusion.Additionally,changingthepulseduration,fromfemtosecond tonanosecond,providedmechanisticinsightintothephotothermalandphotomechanical contributorsthatgovernmembranedisruptioninthispolymer–nanoparticlehybridsystem. W.G.Leeetal.[20]presentedthepreparationofporouscelluloseacetate(CA)for applicationasabatteryseparator.Cd(NO3)2·4H2Owasutilized,withwaterpressureasan externalphysicalforce.WhentheCAwascomplexedwithCd(NO3)2·4H2Oandexposed toexternalwaterpressure,thewaterfluxthroughtheCAwasobserved,indicatingthe generationofporesinthepolymer.Furthermore,asthehydraulicpressureincreased,the waterfluxincreasedproportionally,indicatingthepossibilityofthecontroloftheporosity andporesize.Surprisingly,thefluxvalue,above250LMH(L/m2h),observedattheratioof 1:0.35(molarratioofCA:Cd(NO3)2·4H2O)washigherthanthefluxesofCA/othermetal nitratesalt(Ni(NO3)2andMg(NO3)2)complexes.Thehighervalueindicatedthatlargerand abundantporesweregeneratedinthecelluloseacetateatthesamewaterpressure.Thus,it couldbepostulatedthattheCd(NO3)2·4H2Osaltplayedaroleasastrongerplasticizerthan theothermetalnitratesaltssuchasNi(NO3)2andMg(NO3)2.Thecoordinativeinteractions betweentheCAandCd(NO3)2·4H2OwereinvestigatedbyIRspectroscopy.Thechangein ionicspeciesinCd(NO3)2·4H2OwasanalyzedbyRamanspectroscopy. Tissueengineeringisanareainwhichbiomedicalresearchisinvestingheavily[21,22]. Tissueengineeringrepresentsanalternativetoautologousgrafts.Itsapplicationrequires three-dimensionalscaffolds,whichmimicthehumanbody’senvironment.Thistopicisdis- cussedbytheworkofJ.Radwan-Pragłowskaetal.[23]regardingbone-tissueengineering. Infact,boneisthesecondtissuetobereplaced,andannually,overfourmillionsurgical treatmentsareperformed.Bonetissuehasahighlyorganizedstructureandcontainsmostly inorganiccomponents.Thescaffoldsofthelatestgenerationshouldnotonlybebiocompat- iblebutalsopromoteosteoconduction.Poly(lacticacid)(PLA)nanofibersarecommonly usedforthispurpose;however,theylackbioactivityanddonotprovidegoodcelladhesion. Chitosanisacommonlyusedbiopolymerthatpositivelyaffectsosteoblasts’behavior.The aimofthisstudywastopreparenovelhybrid3Dscaffoldscontainingnanohydroxyapatite capableofstimulatingcellresponses.MatricesweresuccessfullyobtainedbyPLAelectro- spinningandmicrowave-assistedchitosancrosslinking,followedbydopingwiththree typesofmetallicnanoparticles(Au,Pt,andTiO2). Theproductsandsemi-components werecharacterizedintermsoftheirphysicochemicalproperties,suchaschemicalstructure, crystallinity,andswellingdegree.Thenanoparticles’andreadybiomaterials’morphologies wereinvestigatedbySEMandTEMmethods.Finally,thescaffoldswerestudiedfortheir bioactivityonMG-63andeffectsoncurrent-stimulatedbiomineralization.Theobtained resultsconfirmedthepreparationoftunablebiomimickingmatricesthatmaybeusedasa promisingtoolforbone-tissueengineering. M. Wu et al. [24] introduced a three-dimensional (3D) pyramid to the polymer– plasmonichybridstructureofpolymethylmethacrylate(PMMA)compositeAgNPsasa higher-quality,flexiblesurface-enhancedRamanscattering(SERS)substrate. Theeffec- tiveoscillationoflightinsidethepyramidvalleycouldprovidewidedistributionsof3D “hotspots”inalargespace. Theinclinedsurfacedesignofthepyramidstructurecould facilitatetheaggregationofprobemolecules,enablingthehighlysensitivedetectionof rhodamine6G(R6G)andcrystalviolet(CV).Inaddition,theAgNPsandPMMAcomposite structuresprovidedauniformspacedistributionforanalytedetectioninadesignated hotspotzone. TheincidentlightcouldpenetratetheexternalPMMAfilmtotriggerthe localizedplasmonresonanceoftheencapsulatedAgNPs,achievinganenormousenhance- mentfactor(~6.24×108).Afteritunderwentmechanicaldeformation,theflexibleSERS 2 Polymers2022,14,3117 substratestillmaintainedhighmechanicalstability,whichwasprovedbyexperimentsand theory.Forpracticalapplications,thepreparedflexibleSERSsubstratewasadaptedforthe insituRamandetectionofadenosineaqueoussolutionandmethylene-blue(MB)molecule detectionontheskinofafish,providingadirectandnondestructiveactiveplatformfor detectiononsurfaceswithanyarbitrarymorphologyandaqueoussolution. Magneticnanoparticles(MNPs)arelargelyinvestigatedforbiomedicalapplications. However,ifnotproperlydesigned,MNPscancauseseveralproblems,suchascytotoxicity orhemolysis.J.A.Roacho-Pérezetal.[25]comparedbaremagnetitenanoparticlesagainst magnetitenanoparticlescoatedwithacombinationofpolyethyleneglycol3350(PEG3350) andpolysorbate80(Tween80). Thephysicalcharacteristicsofthenanoparticleswere evaluated. Aprimarycultureofsheepadiposemesenchymalstemcellswasdeveloped tomeasurethenanoparticlecytotoxicity.Asampleoferythrocytesfromahealthydonor wasusedforthehemolysisassay.Theresultsshowedthesuccessfulobtentionofmagnetite nanoparticlescoatedwithPEG3350–Tween80,withasphericalshape.Biologicalstudies showedalackofcytotoxicityatdoseslowerthan1000μg/mLformesenchymalstemcells, andalackofhemolyticactivityatdoseslowerthan100μg/mLforerythrocytes. AttheendofthisSpecialIssue,wehavetheworkofP.Shaoetal.[26]addressing theeffectsofcuprousnano-oxideontheflame-retardantpropertiesofcalciumalginate. − NanocuprousoxidewaspreparedonasodiumalginatetemplatefromwhichCl was excludedandbasedonwhichcalciumalginate/nanocuprousoxidehybridmaterialswere preparedbyaCa2+-crosslinkingandfreeze-dryingprocess.Thethermaldegradationand combustionbehaviorofthematerialswerestudiedbyrelatedcharacterizationtechniques usingpurecalciumalginateforcomparison. Theresultsshowthattheweightlossrate, heatreleaserate, peakheatreleaserate, totalheatreleaserate, andspecificextinction areaofthehybridmaterialswereremarkablylowerthanthoseofpurecalciumalginate, andtheflame-retardantperformancewassignificantlyimproved. Infact,nanocuprous oxideformedadenseprotectivelayerofcopperoxide,calciumcarbonate,andcarbonby loweringtheinitialdegradationtemperatureforthepolysaccharidechainduringthermal degradationandcatalyticallydehydratingtocharinthecombustionprocess;thereby,it couldisolatecombustiblegases,increasecarbonresidualrates,andnotablyreduceheat releaseandsmokeevacuation. Inconclusion,astheeditorofthisSpecialIssue,Iamawarethatthediversityand innovationofnewcompoundsandtoolsthatarerapidlydevelopinginthefieldofmulti- disciplinaryresearchrelatedtonanomaterialsbasedonnoblemetalscannotallbecollected inasinglevolume.However,Iamcertainthatthiscollectionwillcontributetotheinterest intheresearchinthisarea,providingourreaderswithabroadandupdatedoverviewof thistopic. Funding:Thisresearchreceivednoexternalfunding. Acknowledgments:Aspecialthankyougoestoalltheauthorsforsubmittingtheirstudiestothe presentSpecialIssue.Moreover,theGrantofExcellenceDepartments,MIUR-Italy(ARTICOLO1, COMMI314337LEGGE232/2016)andRegioneLazio(ProgettiGruppidiRicerca2020—protocollo GeCoWEBn.A0375-2020-36521,CUPE85F21002440002)aregratefullyacknowledged. ConflictsofInterest:Theauthordeclaresnoconflictofinterest. References 1. Gnecco,G.;Pammolli,F.;Tuncay,B.Welfareandresearchanddevelopmentincentiveeffectsofuniformanddifferentialpricing schemes.Comput.Manag.Sci.2022,19,229–268.[CrossRef] 2. Piddock,L.J.V.;Paccaud,J.-P.;O’Brien,S.;Childs,M.;Malpani,R.;Balasegaram,M.ANonprofitDrugDevelopmentModelIsPart oftheAntimicrobialResistance(AMR)Solution.Clin.Infect.Dis.Off.Publ.Infect.Dis.Soc.Am.2022,74,1866–1871.[CrossRef] [PubMed] 3. Linaza,R.V.;Genovezos,C.;Garner,T.;Panford-Quainoo,E.;Roberts,A.P.Globalantimicrobialstewardshipandtheneedfor pharmaceuticalsystemstrengtheningforantimicrobialswithinaOneHealthapproach.Int.J.Pharm.Pract.2022,30,175–179. [CrossRef][PubMed] 3