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BIOPOLYMERMEMBRANESANDFILMS BIOPOLYMER MEMBRANES ANDFILMS Health,Food,Environment, andEnergyApplications Editedby
PROF.MARIANA AGOSTINIDE MORAES
PROF.CLASSIUS FERREIRADA SILVA
PROF.RODRIGO SILVEIRA VIEIRA
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Contributors VeraAlejandraAlvarez CompositeMaterials Group(CoMP),ResearchInstituteofMaterials ScienceandTechnology(INTEMA),National ScientificandTechnicalResearchCouncil— Argentina(CONICET)—NationalUniversity ofMardelPlata(UNMdP),MardelPlata, Argentina
MarianaAltenhofendaSilva CenterofAgriculturalSciences,FederalUniversityofSao Carlos,Araras,SaoPaulo,Brazil
IoannisAnastopoulos DepartmentofChemistry, UniversityofCyprus,Nicosia,Cyprus
RogerioAparecidoBataglioli SchoolofChemicalEngineering,UniversityofCampinas, Campinas,SP,Brazil
MarisaMasumiBeppu SchoolofChemical Engineering,UniversityofCampinas,Campinas,SP,Brazil
AndreaCristianeKrauseBierhalz Department ofEngineering,FederalUniversityofSanta Catarina,Blumenau,SantaCatarina,Brazil
FernandaCarlaBombaldideSouza Department ofMaterialsEngineeringandBioprocess, SchoolofChemicalEngineering,Universityof Campinas,Campinas,SP,Brazil
RenataFrancielleBombaldideSouza DepartmentofMaterialsEngineeringandBioprocess, SchoolofChemicalEngineering,Universityof Campinas,Campinas,SP,Brazil
Adria ´ nBonilla-Petriciolet Departmentof ChemicalEngineering,AguascalientesInstitute ofTechnology,Aguascalientes,Mexico
JosianeGonc ¸ alvesBorges UniversityofSa ˜ o Paulo,FacultyofAnimalScienceandFood Engineering(FZEA-USP),Pirassununga,Sa ˜ o Paulo,Brazil
TitoRobertoSant’AnnaCadaval,Jr Schoolof ChemistryandFood,FederalUniversityof RioGrande,FURG,RioGrande,RS,Brazil
BrunaGregattideCarvalho SchoolofChemical Engineering,UniversityofCampinas,Campinas,SP,Brazil
RosemaryAparecidadeCarvalho Universityof SaoPaulo,FacultyofAnimalScienceandFood Engineering(FZEA-USP),Pirassununga,Sao Paulo,Brazil
TeciaVieiraCarvalho NucleusofStudiesand ResearchoftheNortheast,NEPEN,Fortaleza, CE,Brazil
PascaleChevallier LaboratoryforBiomaterials andBioengineering,DepartmentofMinMet-MaterialsEngineering,LavalUniversity andUniversityHospitalResearchCenter, QuebecCity,QC,Canada
ViktorOswaldoCa ´ rdenasConcha Instituteof Environmental,ChemicalandPharmaceutical Sciences,FederalUniversityofSaoPaulo— UNIFESP,Diadema,Sa ˜ oPaulo,Brazil
LuanaRolandFerreiraContini InstituteofEnvironmental,ChemicalandPharmaceutical Sciences,FederalUniversityofSa ˜ oPaulo— UNIFESP,Diadema,SaoPaulo,Brazil
RodrigoCue-Sampedro School of Engineering andSciences,MonterreyInstituteofTechnology,Monterrey,Mexico
Joa ˜ oDias-Ferreira DepartmentofPharmaceutical Technology,FacultyofPharmacy,Universityof Coimbra,Coimbra,Portugal
GuilhermeLuizDotto ChemicalEngineering Department,FederalUniversityofSanta Maria–UFSM,SantaMaria,RS,Brazil
MeryemSedefErdal DepartmentofPharmaceuticalTechnology,FacultyofPharmacy,IstanbulUniversity,Istanbul,Turkey
Ju ´ liaVazErnesto DepartmentofPharmaceuticalSciences,InstituteofEnvironmental,ChemicalandPharmaceuticalSciences,Federal UniversityofSaoPaulo,Diadema,Brazil
AnaR.Fernandes DepartmentofPharmaceutical Technology,FacultyofPharmacy,Universityof Coimbra,Coimbra,Portugal
EmanuelM.Fernandes 3B’sResearchGroup, I3Bs—ResearchInstituteonBiomaterials,BiodegradablesandBiomimetics,Universityof Minho,HeadquartersoftheEuropeanInstitute ofExcellenceonTissueEngineeringandRegenerativeMedicine,Guimaraes;ICVS/3B’s—PT GovernmentAssociateLaboratory,Braga/ Guimara ˜ es,Portugal
EduardodePauloFerreira ChemicalEngineeringDepartment—CampusSantaM ^ onica,FederalUniversityofUberl^ andia,Uberl^ andia, MG,Brazil
ClassiusFerreiradaSilva InstituteofEnvironmental,ChemicalandPharmaceuticalSciences, FederalUniversityofSaoPaulo—UNIFESP, Diadema,SaoPaulo,Brazil
RonaldoFerreiradoNascimento TraceAnalysisLaboratory(LAT),DepartmentofAnalytical andPhysicalChemistry,FederalUniversityof Ceara ´ —UFC,Fortaleza,CE,Brazil
LeonardoFernandesFraceto Environmental NanotechnologyLab,ScienceandTechnology InstituteofSorocaba(ICTS),Sa ˜ oPauloState University(UNESP),Sorocaba,Brazil
VitorAugustodosSantosGarcia Universityof SaoPaulo,FacultyofAnimalScienceandFood Engineering(FZEA-USP),Pirassununga,Sa ˜ o Paulo,Brazil
LucimaraGazioladelaTorre SchoolofChemicalEngineering,UniversityofCampinas,Campinas,SP,Brazil
SandyDanielleLucindoGomes Adsorption SeparationResearchGroup,Departmentof ChemicalEngineering,FederalUniversityof Ceara,Fortaleza,CE,Brazil
SevgiGungor DepartmentofPharmaceutical Technology,FacultyofPharmacy,Istanbul University,Istanbul,Turkey
SaartjeHernalsteens CollegeofChemistry, ChemicalEngineeringandMaterialScience, SoochowUniversity,Suzhou,Jiangsu,China; DepartmentofChemicalEngineering,Institute ofEnvironmental,ChemicalandPharmaceuticalSciences,FederalUniversityofSa ˜ oPaulo, Diadema,SP,Brazil
CarmenGuadalupeHerna ´ ndez-Valencia BiotechnologyDepartment,LaboratoryofBiopolymersandPilotPlantofBioprocessingof Agro-IndustrialandFoodBy-Products,AutonomousMetropolitanUniversity,MexicoCity, Mexico
AhmadHosseini-Bandegharaei Departmentof EnvironmentalHealthEngineering,Sabzevar University of MedicalSciences,Tehran,Iran
MohdIkmarNizamMohamadIsa Advanced NanoMaterials(ANoMa)ResearchGroup,AdvancedMaterialsTeam,IonicStateAnalysis (ISA)Laboratory,FacultyofScienceand MarineEnvironment,UniversitiMalaysiaTerengganu,KualaNerus,Terengganu;Frontier MaterialsResearchGroup,AdvancedMaterials Team,Ionic&KineticMaterialsResearch (IKMaR)Laboratory,FacultyofScienceand Technology,UniversitiSainsIslamMalaysia, Nilai,NegeriSembilan,Malaysia
EmineKahraman DepartmentofPharmaceuticalTechnology,FacultyofPharmacy,Istanbul University,Istanbul,Turkey
TheoGuenterKieckbusch SchoolofChemical Engineering,UniversityofCampinas,Campinas,SaoPaulo,Brazil
HenrykKoroniak FacultyofChemistry,Adam MickiewiczUniversityinPoznan,Poznan, Poland
Ramo ´ nDı´azdeLeo ´ n DepartmentofPolymerizationProcesses,ResearchCenterofApplied Chemistry,Saltillo,Mexico
EderCla ´ udioLima InstituteofChemistry, FederalUniversityofRioGrandedoSul, UFRGS,PortoAlegre,RS,Brazil
PatriciaSantosLopes DepartmentofPharmaceuticalSciences,InstituteofEnvironmental, ChemicalandPharmaceuticalSciences,Federal UniversityofSaoPaulo,Diadema,Brazil
Vinı´ciusBorgesVieiraMaciel Departmentof FoodEngineering,FacultyofAnimalScience andFoodEngineering,UniversityofSa ˜ oPaulo, Pirassununga,SaoPaulo,Brazil
DiegoMantovani LaboratoryforBiomaterials andBioengineering,DepartmentofMinMet-MaterialsEngineering,LavalUniversity andUniversityHospitalResearchCenter,QuebecCity,QC,Canada
GustavoMartı´nez-Castellanos BiochemicalEngineeringDepartment,MisantlaInstituteof Technology,Veracruz,Mexico
AgnesBatistaMeireles BiomaterialsEvaluationandDevelopmentCenter(BIOMAT)— CampusI,FederalUniversityofJequitinhonha andMucuriValleys,Diamantina,MG,Brazil
EnaydedeAlmeidaMelo DepartmentofConsumerScience,FederalRuralUniversityof Pernambuco,Recife,Brazil
A ˆ ngelaMariaMoraes DepartmentofMaterials EngineeringandBioprocess,SchoolofChemicalEngineering,UniversityofCampinas,Campinas,SP,Brazil
MarianaAgostinideMoraes InstituteofEnvironmental,ChemicalandPharmaceutical Sciences,FederalUniversityofSaoPaulo— UNIFESP,Diadema,Sa ˜ oPaulo,Brazil
Anafta ´ liaFelisminoMorais AdsorptionSeparationResearchGroup,DepartmentofChemicalEngineering,FederalUniversityofCeara, Fortaleza,CE,Brazil
NurHafizaMrMuhamaruesa AdvancedNano Materials(ANoMa)ResearchGroup,Advanced MaterialsTeam,IonicStateAnalysis(ISA)Laboratory,FacultyofScienceandMarineEnvironment,UniversitiMalaysiaTerengganu,Kuala Nerus,Terengganu,Malaysia
RobertoNasser,Jr DepartmentofChemicalEngineering,InstituteofEnvironmental,Chemical andPharmaceuticalSciences,FederalUniversity ofSaoPaulo,Diadema,SP,Brazil
BeatrizC.Naveros DepartmentofPharmacy andPharmaceuticalTechnology,Facultyof Pharmacy,UniversityofGranada,Granada; NanoscienceandNanotechnologyInstitute (IN2UB),UniversityofBarcelona,Barcelona, Spain
DeiseOchi InstituteofEnvironmental,Chemical andPharmaceuticalSciences,FederalUniversity ofSa ˜ oPaulo—UNIFESP,Diadema,Sa ˜ oPaulo, Brazil
RominaPaolaOllier CompositeMaterials Group(CoMP),ResearchInstituteofMaterials ScienceandTechnology(INTEMA),National ScientificandTechnicalResearchCouncil— Argentina(CONICET)—NationalUniversity ofMardelPlata(UNMdP),MardelPlata, Argentina
Yıldız Ozsoy DepartmentofPharmaceutical Technology,FacultyofPharmacy,Istanbul University,Istanbul,Turkey
NeithPacheco CenterforResearchandAssistanceinTechnologyandDesignoftheState ofJalisco,AC,CIATEJ,SoutheastUnit,Merida, Mexico
AndersonEspiritoSantoPereira Environmental Nanotechnology Lab, ScienceandTechnology InstituteofSorocaba(ICTS),SaoPauloState University(UNESP),Sorocaba,Brazil
LauraOliveiraPeres DepartmentofChemistry, InstituteofEnvironmental,ChemicalandPharmaceuticalSciences,FederalUniversityofSao Paulo,Diadema,Brazil
AnaLuizaResendePires PostgraduatePrograminBiotechnology,FederalUniversityof Espı´ritoSanto,Vito ´ ria,ES,Brazil
RuiL.Reis 3B’sResearchGroup,I3Bs— ResearchInstituteonBiomaterials,BiodegradablesandBiomimetics,UniversityofMinho, HeadquartersoftheEuropeanInstituteof ExcellenceonTissueEngineeringandRegenerativeMedicine;TheDiscoveriesCentrefor RegenerativeandPrecisionMedicine,HeadquartersatUniversityofMinho,Guimara ˜ es; ICVS/3B’s—PTGovernmentAssociateLaboratory,Braga/Guimara ˜ es,Portugal
AnsorenaMarı´aRoberta ChemicalEngineering Department,FoodEngineeringGroup,EngineeringFaculty,NationalUniversityofMar delPlata,BuenosAires,Argentina;National ResearchCouncil(CONICET),BuenosAires, Argentina
Joa ˜ oBatistaMaiaRochaNeto SchoolofChemicalEngineering,UniversityofCampinas, Campinas,SP,Brazil
Luı´saC.Rodrigues 3B’sResearchGroup, I3Bs—ResearchInstituteonBiomaterials, BiodegradablesandBiomimetics,University ofMinho,HeadquartersoftheEuropeanInstituteofExcellenceonTissueEngineeringand RegenerativeMedicine,Guimaraes;ICVS/ 3B’s—PTGovernmentAssociateLaboratory, Braga/Guimara ˜ es,Portugal
LauraMabelSanchez CompositeMaterials Group(CoMP),ResearchInstituteofMaterials ScienceandTechnology(INTEMA),National ScientificandTechnicalResearchCouncil— Argentina(CONICET)—NationalUniversity ofMardelPlata(UNMdP),MardelPlata, Argentina
J.A.Sa ´ nchez-Ferna ´ ndez DepartmentofPolymerizationProcesses,ResearchCenterof AppliedChemistry,Saltillo,Mexico
AndrelinaMariaPinheiroSantos Department ofChemicalEngineering,FederalUniversity ofPernambuco,Recife,Brazil
GilbertoDantasSaraiva LaboratoryofSynthesis andCharacterizationofMaterials—LASCAM, DepartmentofPhysics,StateUniversityof Ceara ´ (UECE-FECLESC),Quixada ´ ,CE,Brazil
PatriciaSeverino LaboratoryofNanotechnology andNanomedicine(LNMED),InstituteofTechnologyandResearch(ITP),Universityof Tiradentes,IndustrialBiotechnologyProgram, Aracaju,Brazil
KeikoShirai BiotechnologyDepartment,LaboratoryofBiopolymersandPilotPlantof BioprocessingofAgro-IndustrialandFood By-Products,AutonomousMetropolitanUniversity,MexicoCity,Mexico
SimoneS.Silva 3B’sResearchGroup,I3Bs— ResearchInstituteonBiomaterials,BiodegradablesandBiomimetics,UniversityofMinho, HeadquartersoftheEuropeanInstituteof ExcellenceonTissueEngineeringandRegenerativeMedicine,Guimara ˜ es;ICVS/3B’s—PT GovernmentAssociateLaboratory,Braga/ Guimara ˜ es,Portugal
MariangeladeFa ´ timaSilva FederalInstituteof Education,ScienceandTechnologyofMato GrossodoSul(IFMS),Coxim,MatoGrosso doSul,Brazil
JacksonWesleySilvadosSantos Instituteof Environmental,ChemicalandPharmaceutical Sciences,FederalUniversityofSa ˜ oPaulo— UNIFESP,Diadema,SaoPaulo,Brazil
VicentedeOliveiraSousaNeto Laboratoryof StudyandResearchinPollutantsRemovalby Adsorption,LERPAD,DepartmentofChemistry,StateUniversityofCeara ´ (UECEFECLESC),Quixada ´ ,CE,Brazil
Joa ˜ oVinı´ciosWirbitzkidaSilveira Institute of Science andTechnology—CampusJK,Federal UniversityofJequitinhonhaandMucuriValleys,Diamantina,MG,Brazil
JoseL.Soriano DepartmentofPharmacyand PharmaceuticalTechnology,FacultyofPharmacy,UniversityofGranada,Granada,Spain
ElianaB.Souto DepartmentofPharmaceutical Technology,FacultyofPharmacy,University ofCoimbra,Coimbra;CEB—CentreofBiologicalEngineering,UniversityofMinho,Braga, Portugal
ClaytonCampelodeSouza LaboratoryforBiomaterialsandBioengineering,Departmentof Min-Met-MaterialsEngineering,LavalUniversityandUniversityHospitalResearchCenter, QuebecCity,QC,Canada
ThiagoBezerraTaketa SchoolofChemicalEngineering,UniversityofCampinas,Campinas, SP,Brazil
BrunoThoriharaTomoda InstituteofEnvironmental,ChemicalandPharmaceuticalSciences, FederalUniversityofSa ˜ oPaulo—UNIFESP, Diadema,SaoPaulo,Brazil
FernandaMariaVanin UniversityofSa ˜ oPaulo, FacultyofAnimalScienceandFoodEngineering(FZEA-USP),Pirassununga,Sa ˜ oPaulo, Brazil
AnnaCeciliaVenturini InstituteofEnvironmental,ChemicalandPharmaceuticalSciences, FederalUniversityofSa ˜ oPaulo—UNIFESP, Diadema,SaoPaulo,Brazil
RodrigoSilveiraVieira AdsorptionSeparation ResearchGroup,DepartmentofChemical Engineering,FederalUniversityofCeara, Fortaleza,CE,Brazil
JustynaWalkowiak-Kulikowska Facultyof Chemistry,AdamMickiewiczUniversityin Poznan,Poznan,Poland
JoannaWolska FacultyofChemistry,Adam MickiewiczUniversityinPoznan,Poznan, Poland
Patrı´ciaHissaeYassue-Cordeiro FederalUniversityofTechnology—Parana ´ ,Londrina, Parana ´ ,Brazil
CristianaMariaPedrosoYoshida Instituteof Environmental,ChemicalandPharmaceutical Sciences,FederalUniversityofSaoPaulo— UNIFESP,Diadema,Sa ˜ oPaulo,Brazil
Prefaceandacknowledgment Biopolymerscanbeprocessedinseveral forms,suchasmicro/nanoparticles,films/ membranes,gels,andsponges.Thebookfocusesontheuseofmembranesorfilms,for example,two-dimensionalsystems,coveringawiderangeoftypesofnaturalpolymers andapplications.Thebookisdividedinto chapterswrittenbyexpertsinthefieldof membraneapplicationsinhealth,environment,energy,andfood.Thisbookcanbe usedasavaluablereferenceforbiopolymer scientistsandresearcherslookingforcutting-edgeapplicationsofnaturalpolymers. Firstofall,thetopicspresentedinthis bookareavant-gardethemes.Oneofthe challengesofthoseworkingwithtwo-dimensionalpolymerdevices(membranes, films,andcoatings)istogetoutofthecomfortzoneandtoknowalittlemoreaboutthe applicationsthatarenotpartoftheirexpertise.Therefore,abroaderviewoftheapplicationhorizonofthesedevicesisstilllacking. Thisbookpresentsthreepartswithverydifferentapplications(Health,Environment andEnergy,andFood);theseapplications werenotchosenrandomly;weintendto showthepublicthatspecificmethodsof preparationandcharacterizationsofagiven applicationcanbeperfectlyadaptedtoanotheruse.Theresearchersoftenfinddifficultiesinthedevelopmentoftwo-dimensional materials(membranes,films,andcoatings); however,theydonotrealizethatmanypublicationsfocusingonotherapplicationspresentsimilarproblemsthathavealready beensolved.Evendisastrousresultsinone applicationmayrepresentagoodresultin
anotherfield.Asanexample,researchers spendalotoftimedevelopingamembrane forapplicationasawounddressingfor burnstreatment;however,sometimesthey findthatthematerialhasinappropriate propertiesfordressings,butthatpresentsexcellentpropertiesforpackaging(theyusuallydonotknowthatsuchdeveloped materialcouldbeusedforpackaging! Wow!Itdoesnotworkasadressingbut wouldbeanexcellentpackaging!).Inthis sense,thisbookisintendedtoshowabroad rangeoftwo-dimensionalbiopolymerapplications,provingthatgoodresultsinoneapplicationcanguidegoodresultsinotheruses aswell.Andwhynotsaybadoutcomesfor oneapplicationcandrivegoodresultsin otherapplications?Thethreekeyfeatures andcontentsreferpreciselytothefactthat theproposedbookfocusonbiopolymers, techniquesforpreparingmembranes,and characterizingthem.Thesecontentsareoften convergentindifferentapplicationsandmay suggestnewpossibilitiesfornovelapplicationsandmaterialsdevelopment.
Wearedeeplygratefultoallchapterauthorsforagreeingtobeapartofthisproject. Authorsusedtheirexperiencefrom researchingandteachingstudentstogive chapterstherelevanceandappropriatecontent.Weworkedcloselywiththem,proposingrevisionstoenhanceharmonybetween thechapters;evenwiththeirfullschedules, fortunately,theauthorswereverycordial andpatientwithus.Wewishtothanktheauthorsofbooksandarticles,aswellasthe publishersfortheirpermissiontoreproduce
materialsusedhere.Wearealsogratefulto allthosecolleaguesthatevennotbeingchapterauthorsdevotedtheirprecioustimeto helpustoreviewthechapters.Thanksare alsoexpressedtoElsevierInc.,especially Mr.EdwardPayne,Mrs.MarianaK € uhl Leme,andMr.VijayarajPurushothaman fortheirsupportduringthisproject.Finally, wehaveappreciatedcontinuedsupportand encouragementfromourfamilies,towhom wecanneverthankenough!
MarianaAgostinideMoraes, ClassiusFerreiradaSilva InstituteofEnvironmental, ChemicalandPharmaceuticalScience, FederalUniversityofSa ˜ oPaulo—UNIFESP, Diadema,SP,Brazil
RodrigoSilveiraVieira DepartmentofChemicalEngineering, FederalUniversityofCeara ´ —UFC, Fortaleza,CE,Brazil
Acknowledgmenttothechapters’ reviewers Prof.Andre ´ BezerradosSantos DepartmentofHydraulicand EnvironmentalEngineering FederalUniversityofCeara ´ Fortaleza,CE,Brazil
Prof.AndreaCristianeKrause Bierhalz DepartmentofEngineering FederalUniversityofSantaCatarina— CampusBlumenau Blumenau,SC,Brazil
Dra.DanieleFarias ToulouseWhiteBiotechnology(UMS INRA/INSA/CNRS) NAPACenterBatB Ramonville-Saint-Agne,France
Prof.ElizamaAguiardeOliveira DepartmentofExactScienceand Technology StateUniversityofSantaCruz Ilhe ´ us,BA,Brazil
Prof.GilcenaradeOliveira Nu ´ cleodePesquisaemBiologia Experimental UniversidadedeFortaleza Fortaleza,CE,Brazil
Prof.JoaoVinı´ciosWirbitzkidaSilveira InstituteofScienceandTechnology FederalUniversityofJequitinhonhaand MucuriValleys—CampusJK Diamantina,MG,Brazil
Prof.JudithPessoadeAndradeFeitosa DepartmentofOrganicandInorganic Chemistry FederalUniversityofCeara ´ Fortaleza,CE,Brazil
Prof.JulioCesarSerafimCasini DepartmentofControlandAutomation Engineering FederalInstituteofSaoPaulo SaoJose ´ dosCampos,SP,Brazil
Prof.MelissaGurgelAdeodatoVieira DepartmentofChemicalProcesses SchoolofChemicalEngineering— UNICAMP Campinas,SP,Brazil
Prof.OdairP.Ferreira LaboratoryofAdvancedFunctional Materials DepartmentofPhysics FederalUniversityofCeara ´ Fortaleza,CE,Brazil
Prof.RinaldoAraujo DepartmentofChemistryand Environmental FederalInstituteofCeara ´ Fortaleza,CE,Brazil
Prof.RoqueMachadodeSenna InstituteofEnvironmental,Chemicaland PharmaceuticalSciences FederalUniversityofSaoPaulo Diadema,SP,Brazil
Fundamentalsonbiopolymersand globaldemand SimoneS.Silvaa,b,Luı´saC.Rodrigues a,b , EmanuelM.Fernandesa,b,RuiL.Reisa,b,c
a3B’sResearchGroup,I3Bs—ResearchInstituteonBiomaterials,Biodegradablesand Biomimetics,UniversityofMinho,HeadquartersoftheEuropeanInstituteofExcellenceonTissue EngineeringandRegenerativeMedicine,Guimara ˜ es,Portugal bICVS/3B’s—PTGovernment AssociateLaboratory,Braga/Guimara ˜ es,Portugal cTheDiscoveriesCentreforRegenerativeand PrecisionMedicine,HeadquartersatUniversityofMinho,Guimara ˜ es,Portugal
Nomenclature
AV Aloevera
BC bacterialcellulose
CAGR compoundannualgrowthrate
CNCs cellulosenanocrystals
2D two-dimensional
3D three-dimensional
EC ethylenecarbonate
ECM extracellularmatrix
HA hyaluronicacid
IL ionicliquid
MB methyleneblue
TA ambientaltemperature
Tg glasstransitiontemperature
SPEs drysolidpolymerelectrolytes
SF silkfibroin
SPI soyproteinisolate
1Introduction Thegrowingconcernsforasustainableenvironmentandenhancementofthequalityof people’sliveshavebeenthestartingpointstoevaluatethepotentialofnaturalpolymersfrom renewableresourcestocreategreenerwaystoaddresstheproblemsofshortageoffossilfuel, healthhazards,environmentalissues,andsolidwastemanagement.Biopolymerscanbeclassifiedaspolysaccharides(e.g.,chitin/chitosan,alginate,agarose,cellulose-basedpolymers, starch,andcarrageenan)orproteins(e.g.,soyprotein,fibroin,sericin,gelatin,andcollagen) andhavebeenusedaloneorcombinedtoproducemembranesformultipleapplications. However,large-scalecommercializationbiopolymermembranesarestillachallenge.Thereforemanyprocessingtechniquesareavailabletoproducemembranes,andthechoiceofthe appropriateonewilldependnotonlyonthefeaturesofthematerialitselfbutalsooneach particularapplication.Althoughthefeasibilityoftheuseofbiopolymermembranesindifferentfieldssuchasbiomedical,food,energy,andtheenvironmenthasbeendescribedinseveralstudies,itsusesometimesimpliesitsmodificationand/orblendingwithotherpolymers (eithernaturalorsynthetic)toachieveadequatefeaturesforitsapplication.
Thischapteraddressesfundamentalfeaturesintermsofintrinsiccharacteristics,main properties,andapplicationsofbiopolymersasmembranes.Moreover,alookatthemarket trendisalsodiscussed.
2Polysaccharidesandproteins:Generalcharacteristics 2.1Polysaccharides Rangingfromlineartohighlybranchedstructures,polysaccharidesare,fromageneral pointofview,polymericcarbohydratescomposedoflongmonosaccharideunitsbounded byglycosidiclinkages.Asaconsequenceoftheirstructure,theymayassumedifferentpropertiesfromtheirmonosaccharidebuildingblocks.Generally,polysaccharidesfromnatural originsaresimplecarbohydrateswithauniquemonosacchariderepeatunit,whichmay beobtainedorsynthesizedfromaplethoraofrenewableresources.Naturalpolysaccharides arenontoxicandbiodegradable,whichincreasestheirpotentialapplication.Themostused biopolysaccharidessummarizedin Table1 areobtainedorsynthesizedfromalgaeorigin (e.g.,alginate,agarose,carrageenan,fucoidan,andulvan),plantorigin(e.g.,acemannan,cellulose,andstarch),microbialorigin(bacterialcellulose[BC],dextran,andgellangum),and animalorigin(e.g.,chitin/chitosan,chondroitinsulfate,glycosaminoglycans,heparin,and hyaluronan).
Moreover,thesenaturalderivativespresentaconsiderablenumberofreactivefunctional groups(e.g.,hydroxyl,carboxyl,andaminogroups),whichsignificantlyincreasetheirapplicabilitythroughchemicalmodificationorphysicalblend.
Inthefollowingsectionsadetaileddescriptionofselectedpolysaccharides’physicochemicalandbiologicalpropertiesispresented.
2.1.1Alginate Alginicacid,alsocalledalginate,isananionicpolysaccharidethatispresentinnature, mostlyasoneoftheconstituentsofbrownalgae(Phaeophyceae) [88].Itisalinearunbranched
2Polysaccharidesandproteins:Generalcharacteristics
TABLE1 Generalcharacteristicsofthenaturalbiomacromolecules.
PolymerSource
AgaroseDerivedfromagarandfoundinred seaweeds
Characteristicfeatures References
•Composedofrepeatingunitsof (1 ! 3)-β-D-galactopyranose-(1 ! 4)3,6-anhydro-β-L-galactopyranose
•Water-solubleandneutral polysaccharide
•Lowgellingtemperature(32°C) [1,2]
AlginateBrownalgae(Phaeophyceae)•Gelformationinthepresenceof divalentcations(e.g.,Ca2+,Mg2+)
•Composedof β(1 ! 4)-linked D-mannuronicacidand α(1 ! 4)linked L-guluronicacid
•Processedashydrogels,membranes, capsules,fibers,orscaffolds [3–9]
Bacterial cellulose Gluconacetobacterxylinus or Acetobacter xylinum
•Glucanchainsboundtogetherby hydrogenbonds
•Crystallinenanofibrillarstructure
•Conjugatedwithchitosan,alginate, gelatin,hyaluronicacid,and xyloglucantoimproveperformance [10–16]
CarrageenanRedalgae•Madeupofrepeatinggalactoseunits and3,6-anhydrogalactose,both sulfatedandnonsulfated
•Threemaintypesofcarrageenancan beobtained:kappa(κ),iota(ι),and lambda(λ) [17–19]
CelluloseWoods•Highdegreeofcrystallinityandrigid intra/intermolecularhydrogen bonds
•Constitutedby β-1,4glycosidic-linked D-glucoseunits
•Insolubleinwaterandmostorganic solvents
•Solubilityandprocessability achievedbyusingionicliquids
•Undergoeschemicalmodification throughesterification,graft copolymerization,orselective oxidation [20–25]
CollagenCornea,bloodvessels,skin,cartilage, bone,tendon,ligament,marinesponges, andfishskin
•Maincomponentoftheextracellular matrixandthemostabundant proteinpresentinmammaliantissues
•Providesmechanicalstrengthto tissuesandstimulatescelladhesion andproliferation [26–29] Continued
TABLE1 Generalcharacteristicsofthenaturalbiomacromolecules—cont’d
PolymerSource
ChitinCellwallsoffungi,exoskeletonsof arthropodssuchascrustaceansand insects,radulasofmollusks,andbeaks ofcephalopods
Characteristicfeatures References
•Canbechemicallymodifiedor combinedwithpolysaccharidesand/ orbioactivemoleculestoimprove theirphysicochemicalpropertiesand biologicalperformance
•Strongintermolecularbonding
•Insolubleincommonsolvents
•Solubilizationusingionicliquids
•Moldedintodifferentforms(e.g., gels,beads,membranes,sponges, tubes,andfibers)
Chitosan N-Deacetylatedderivativeofchitin•Solubilizationinaqueousacidic solutions
•Designedas2D-and3D-based architecturessuchasfibers,particles, membranes,andcompositesat micro/nanolevel
DextranProducedbyseveralmicroorganisms•Composedof(1 ! 6)-linked α-Dglucopyranosylunits
•Solubleinwaterandorganicsolvents
•Biocompatibleandbiodegradable
[9,30–48]
[31,37,39,41, 49–68]
[27,46,69]
GellangumBacterium Sphingomonaselodea
•Anionicexopolysaccharide
•Consistsofarepeatingunitofa tetrasaccharide:1,3-linked-D-glucose, 1,4-linked-D-glucuronicacid,1,4linked-D-glucose,and1,4-linked-Lrhamnose
•Thermallyreversiblegelwith excellentstabilityandhighgel strength
•Formsgelsinthepresenceofmetal cations
[15,70–75]
Hyaluronic acid Roostercombsoraqueoushumorsof cow’seyes
•Composedof D-glucuronicacidand N-acetyl-D-glucosamine
•Water-solublepolysaccharide
•Lowshapestabilityandpoor mechanicalproperties
[18,19,49, 76–84]
PectinStructuralmaterialofallland-based plants
•Composedofpoly-D-galacturonic acidmolecules
•Water-solublebiopolymer
•Abilitytoformgels
[27,47,85]
SericinWasteduringsilkprocessing•Solubleprotein [86]
2Polysaccharidesandproteins:Generalcharacteristics
TABLE1 Generalcharacteristicsofthenaturalbiomacromolecules—cont’d
PolymerSource
SilkfibroinNonmulberryandmulberrysilkworm
Bombyxmori,insects,andspiders
SoyproteinSoybeans
Characteristicfeatures References
•Antioxidant,moisturizingability,pH responsiveness,andmitogeniceffect onmammaliancells
•Betasheetformationaftermetanol/ watersolutiontreatment [1,2]
•Lowprice,nonanimalorigin, relativelylongstoragetime,and stability [87]
StarchCorn,wheat,potato,andricestarch•Composedofamyloseand amylopectin
•Starchcanbetransformedinto thermoplasticmaterialsorblended withsyntheticpolymers [80–83]
polysaccharidecomposedofdifferentamountsof β(1 ! 4)-linked D-mannuronicacidand α(1 ! 4)-linked L-guluronicacid [89].Oneofthemostrelevantfeaturesofalginateisitsability toformgelsinthepresenceofvariousdivalentcations,e.g.,Ca2+,Mg2+,duetothecarboxylate groupsoftheguluronatecross-linkingonthepolymerbackbone.Alginateisabiocompatible andantimicrobialpolymerwithimmunogenicity,lowtoxicity,andstabilityinphysiological conditions [3,4,90–92].Thispolysaccharidemaybeprocessedindifferentformsashydrogels, membranes,capsules,fibers,orscaffolds [5,6,93–96],whichsignificantlyenlargethescopeof application [6,7,76,77,91,93,94,97–100].
Furthermore,tooptimizethephysicalpropertiesofhydrogels,alginatehasbeencovalentlycross-linkedandoxidized [8,101];however,anassociateddrawbackisthelimiteddegradationofthecovalentlycross-linkedalginategels,sincecellsdonotsecretethenecessary enzymesforpolymercleavage.Nevertheless,alginatepropertiescanbetailoredorenhanced usingotherstrategiesbasedonconventionalchemicalmodificationsuchasgraftpolymerization,sulfation,oresterification [20,102,103].
2.1.2Cellulose Celluloseisthemostabundantpolysaccharidefromnaturaloriginintheworld,andis mostlyproducedbyplants.Itisapolydisperselinearpolysaccharideconstitutedby β-1,4glycosidiclinked D-glucoseunits(so-calledanhydroglucoseunits) [21] givingorigintoarigid straightchainduetothemanyinter-andintramolecularhydrogenbondsestablishedamong themanyhydroxylgroupstoformwhatisknownasacellulosemicrofibril,orsimplyfibril. Thisclosepackagingofthecellulosechainsleadstoareasofhighcrystallinitywithinthe polymerandtohighstabilitystructures,whichasaconsequencepromoteconsiderable strength,remarkableinertness,andinsolubilityinwaterandcommonorganicsolvents. Significanteffortshavebeenmadetoovercomethesedrawbacks,suchasthechemical
modificationofcellulosethroughesterification,graftcopolymerization,orselectiveoxidation [104–107] toimproveresistancetoheatorabrasion [108–110],mechanicalstrength [111,112], wateroroilrepellency [113–115],orantibacterialactivity [116].Moreover,mostofthechemicalfunctionalizationproceduresarebasedonhydroxylgroups.Todate,severalstudieshave reporteddifferentdesigns,fabrications,andprocessingofcellulose.Graftedcellulosecopolymerspresentawell-definedarchitecture,whichpromotespotentialapplicabilityinbroader fields.Moreover,whenstimuli-responsivesidepolymerchainsweregraftedintothepolymericchain [10,22,49,117],itgavefoundationtocellulose-basedsmartmaterials [11,105]. Amorerecentapproachallowsahomogeneousmodificationandfunctionalizationofcellulosethroughtheuseofionicliquids(ILs),whichmayrepresentagreenapproachtocellulose processing,enlargingitsrangeofapplicability [12,118].
2.1.3Bacterialcellulose BC,similarlytoplant-derivedcellulose,isanaturalpolymercomposedofmicrofibrils containingglucanchainsboundtogetherbyhydrogenbonds.BCisproducedextracellularly byGram-negativebacterialcultures,mostefficientlysecretedfrom Gluconacetobacterxylinus (Acetobacterxylinum).Itisahighlypure,biocompatible,andversatilematerialthatcanbeutilizedinseveralapplications.Biosynthesizedasapelliclecomprisedofarandommicrofibrillarnetworkofcellulosechainsalignedinparallel,BCpresentsalargesurfaceareacapableof retainingalargeamountofliquid [23]
However,likeplant-derivedcellulose,BCisquiteinert,anditsinteraction(e.g.,entrapmentorgrafting)withseveralbioactivecompoundssignificantintissueregeneration,such asdrugs,polyelectrolytes,orproteins,isdifficult.ToovercomeBCinertness,several functionalizationtechniqueswereperformedaswellasseveralconjugationswithchitosan [13,119],alginate [14],gelatin [120],hyaluronicacid(HA) [15],andxyloglucan [78].
2.1.4Chitinandchitosan Chitinisabiopolymerof N-acetylglucosaminewithsomeglucosamine,whichisthemain componentofthecellwallsoffungi,exoskeletonsofarthropodssuchascrustaceansand insects,radulasofmollusks,andbeaksofcephalopods;itisconsideredthesecondmost abundantnaturalpolymeraftercellulose.Chemically,chitinismadeofmonomerunitsof 2-acetamido-2-deoxy-β-D-glucoseconnectedthrough β(1 ! 4)linkages.Becauseofitshighly crystallinestructureandstronginter-andintramolecularbondsbetweenthepolymerchains, chitinisinsolubleincommonsolvents.Onitsglucosering,chitinhasacetamidogroupsthat undergoincompletehydrolysisintoprimaryaminegroups, N-deacetylationofchitin,which leadstotheformationofchitosanthatcanbeeasilydissolvedinaqueousacidicsolutions, whichmakesitsuitableforvariousapplications.Moreover,chitinisalsowidelyusedforcontrolleddrugdeliverysystems,proteinandenzymecarriers,andpackagingmaterialbasedon itsnaturalantimicrobialactivity [121]
Chitinanditsderivatives(e.g.,chitosan)havemanyusefulpropertiesthatmakethemsuitableforawidevarietyofapplications.Chitinandchitosancanbemoldedintodifferentforms (e.g.,gels,beads,membranes,sponges,tubes,andfibers).Also,theirproductsareknownto beantibacterial,antifungal,antiviral,nontoxic,andnonallergic [16,30–32,122–124]
Chitinstructuremodificationandcombinationwithotherpolymersandbioactivemoleculesarebeingstudiedtoenhanceitsmechanicalandchemicalproperties.
FIG.1 Schematicdiagramshowingstepsforchitinporousmembranepreparationinspiredbythemethodology proposedin [127]
Furthermore,ILs,whicharelow-melting-pointmoltensalts,areidentifiedasgoodsolvents fornaturalpolysaccharidesandaccordinglyresearchconcerningthedissolutionofchitin withproperILshasattractedattentiontofabricatenewchitin-basedfunctionalmaterials [33,34,125,126].ManyILshavebeenusedtodissolvechitin;however,ithasbeenshownthat chitindissolutionrequiresamorebasicanion,suchasacetate,duetotheincreasednumberof hydrogenbonddonorsandacceptors [35,127].However,littlehasbeenreportedregarding thechemicalmodificationofchitinintheILs [36,125,128]
ChitinmembranesweresuccessfullypreparedbyusingtheIL 1-ethyl-3-methylimidazoliumacetate([C2mim][OAc])assolventmedia [127],accordingto Fig.1,whichincludesaschematicrepresentationofthelaboratorymethodologyemployed. Thestudyprovedthatthechitin/ILsolutioncouldbeefficientlyusedtoproduceporous chitinmembraneswithtunableproperties,actingasanenvironmentallyfriendlyprocess toapplyitasabiomaterial.Chitinmembraneswerepreparedinarangeofconcentrations comprisingbetween2%and3%with <2%chitinsolutionsappearingtobeverythinandunstableandeasilybrokenintopieces [26].Forthosewith >2%,thetensilestrengthandelongationpercentageincreasedwithwt%chitinsolution,whichissupposedtoberelatedtothe porositypercentageofmembranesthatincreasetolowerconcentrations [127].Theporosity andporedistributionpatterninthemembranealsoaffectedmechanicalstrength,enthalpy, andwaterabsorptioncapacity.Thestudyalsoreportedtheexistenceofapositivecorrelation betweenenthalpyandtensilestrengthforthechitinmembranes.Thesechitinmembraneshad aporosity >80%andporousinterconnectivity.
Chitosancanbedesignedas2D-and3D-basedarchitecturessuchasfibers,particles,membranes,andcompositesatthemicro/nanolevel.Chitosanmembranesdevelopedusingsolventcastingmethodologypresentswellingability,cytocompatibility,oxygenpermeability, moisturetransmission,controlledrelease,antibacterialpotential,epithelialization,andcontrolledwaterevaporationrate,enlargingtherangeoftheirapplication [50–53,129,130].When combinedwithalginatetoformapolyelectrolytecomplex,theobtainedmembranespresent improvedtensilestrengthandadequateelongationatbreak,greaterstabilityconcerning changesinpH,andamoreeffectivecontrolledreleasethanthatobtainedfortheindividual polysaccharides [37,123,131].Alongthisline,chitosan,togetherwithothermacromolecules, isbeingusedinthedevelopmentofvariousbionanocomposites [132–136]
2.1.5Gellangum Gellangumisanexopolysaccharidewithananionicnaturethatconsistsofarepeatingunit ofatetrasaccharide:1,3-linked-D-glucose,1,4-linked-d-glucuronicacid,1,4-linked-D-glucose,
and1,4-linked-L-rhamnose.Likealginate,gellangumformsgelsinthepresenceofmetalcationsandiseasilyprocessedintotransparentgelsthatareresistanttoheat [137].
Gellangumgels,fromarheologicalpointofview,areslightlysoft,whichisdifficultfor extrusion;however,thiscanbemodulatedthroughitscombinationwithalginateorother polymers.Goodresultshavealreadybeenreportedusinga3%gellangum/2%alginate blend,whichwascross-linkedwithstrontiumionsafterextrusion [70].Despitetheadvantagesofgellangum,puregellangumfilmcanbeextremelybrittle,andtheincorporation ofhoneyorvirgincoconutoilappearstobeanalternativepathwaytoreinforcetheirmechanicalproperties [71,72].
2.1.6Hyaluronicacid Hyaluronan(HA)(adisaccharidecomposedof D-glucuronicacidand N-acetyl-D-glucosamine)isanelastoviscousfluidcontaininghyaluronanderivatives.Itisanaturallyoccurring complexsugarthatformsasmallpartoftheextracellularmatrix(ECM)andistherefore nonallergic,whichisanadvantageofstructuralconservationregardlessofthesource.Itis areadilywater-solublemolecule,andthereofHAuseinitsnativeformintissueengineering anddrugdeliverysolutionsislimited.Severalcross-linkingmethodologieswereemployedto enlargeHAstability [73,74,138–140] asacovalentcross-linkingtechnique,whichprovidethe opportunitytocombineHAwithmechanicallystrongerpolymers [11].HAcanproducegels withalubricantandwater-absorbingbehavior,addingtotheirhygroscopicandhomeostatic properties.
2.1.7Carrageenan Carrageenansarelinearpolymersmadeupofrepeatinggalactoseunitsand3,6anhydrogalactose,bothsulfatedandnonsulfated.Carrageenancanbeobtainedfromsome speciesofredalgae [17,18].Dependingonthesourceandconditionsfromwhichcarrageenan isextracted,threemaintypesofcarrageenancanbeobtained:kappa(κ),iota(ι),andlambda (λ)thatcorrespondtoone,two,andthreesulfategroupsperdisaccharide,respectively.Only ι-and λ-carrageenancanformphysicalgels,while κ-carrageenanhydrogelsexhibitpHand temperaturesensitiveness [19].
2.1.8Starch Starchisacarbohydratepolymercomposedoftwomacromolecules,namelyamylose, alinearpolysaccharide,andamylopectin,abranchingpolysaccharide [79].Amyloseforms acolloidaldispersioninhotwater,whereasamylopectiniscompletelyinsoluble.Starch canbeobtainedfrommanybotanicalspecies,e.g.,corn,wheat,potato,andricestarch.Then, starchmoleculesproducedbyeachplantspecieshavespecificstructuresandcompositions; thereforethepropertiesandmodeofinteractionsofstarchwithotherpolymersdiffer dependingonthesource [80].Moreover,starchmaybechemically,enzymatically,orphysicallymodifiedtoenhanceitspropertiesandfunctionalitysuchassolubility,viscosity,and thermalstability.Besides,starchhasbeentransformedintoathermoplasticorblendedwith syntheticpolymerstoimproveitsproperties [81–83].
2.1.9Dextran Dextranisabiodegradableneutralbacterialexopolysaccharidefromtheglucansfamily composedof(1 ! 6)-linked α-D-glucopyranosylunits.Itisobtainedbythepolymerization ofthe α-D-glucopyranosylmoietyofsucroseinareactioncatalyzedbytheenzyme dextransucrase [27].Severalmicroorganismscanproduceit,presentingdifferentmolecular weights,rangingbetween1000and40,000,000Da),andstructuresvaryingfromslightlyto highlybranched.Dextranisabiocompatibleandbiodegradablebiopolymerthatissoluble inwaterandorganicsolvents.Dextranchemicallyreactivehydroxylgroupsareusefulpoints forchemicalconjugationorfunctionalization,whichenablethepreparationofdifferentstructuresthroughblendingdextranwithbioactiveagentsorhydrophobicmoietiesforming,for example,dextran-basedamphiphiles [69].Thedevelopmentofnovelfunctionalscaffolds resultingfrommodificationwithdifferentfunctionalgroupsachievesspherical,tubular, and3Dnetworkstructures [69].
2.1.10Agarose Agaroseisanaturalpolysaccharidederivedfromagarandfoundinredseaweeds [1,2].It isawater-soluble,neutralpolysaccharidecomposedofrepeatingunitsof(1 ! 3)-β-Dgalactopyranose-(1 ! 4)-3,6-anhydro-β-L-galactopyranose [2,141].Agarosehasbeenusedas abioinkduetoitslowgellingtemperatureof32°C,biocompatibility,andmechanicalstrength [1].Agarosealsohastheadvantageofenablingtheprintingofcomplexstructuresduetoits uniquegellingpropertiesthatdonotrequirethepresenceofacross-linker [141].Numerous agarosederivativeshavebeenpreparedwithdifferentfeaturesandmeltingpoints,andfrom thesethelow-meltingderivativesallowtheformationofgelswiththinfibersforenhanced sieving.
2.1.11Pectin
Pectin,alsoknownaspecticpolysaccharide,isacomplexmixtureofpolysaccharides, mostlycomposedofpoly-D-galacturonicacidmoleculescorrespondingtoanaveragemolecularweightrangingfrom50,000to180,000Da,includingmainlycarboxylgroupsinitschains [85].Pectinisawater-solublebiopolymerfoundinallland-basedplantsasastructuralmaterialandinitsutmostconcentrationisfoundinthecentrallamellacellwall.Pectincanform gels;however,itisdependentonitsmolecularsizeanddegreeofesterification.
2.2Proteins Proteinsaremacromoleculesexistinginlivingsystems,composedofstructuralunitscalled aminoacidsthatareattachedinlongchains.Containingmostlycarbon,hydrogen,oxygen, nitrogen,andusuallysulfurandphosphorus,proteinsdifferinthenumberandtypeofamino acidsthatassembletoformthepolypeptidechainandintheir3Dstructure,whichdefinesthe proteins’functionalproperties [142].Proteinsaregenerallyself-assembledsystemsduetothe presenceofdifferentintermolecularinteractionssuchashydrogenbonds,disulfidebridges, saltbridges,andhydrophobicandhydrophilicinteractions.Asso,proteinsarelarge-sized moleculesthat,whendispersedinsuitablesolvents,formcolloids,whichisapropertythat distinguishesproteinsfromsolutionscontainingsmall-sizedmolecules.
Principalcompoundsinallcellproteinsareoftwotypes:bioactiveornotbioactive.The bioactiveproteinsarealsoknownasenzymesandareresponsibleforcelllifecycleand themetabolismandsynthesisofothercompounds.Thenotbioactiveones,calledstorageproteins,areverystable,haveexcellentphysicalandchemicalproperties,andareusedas biobasedpolymersformanyapplications [143].Mainlyduetotheirhighavailabilityinnature,lowcost,biodegradability,andexcellentbiocompatibility,proteinshavebeenusedin thedevelopmentofdifferentarchitectures,includingfilms,capsules,foams,composites, andgels [86,144].
Inthefollowingsections,someofthemostfrequentlyusedproteins,namelysilkfibroin (SF),sericin,collagen,gelatin,andsoyproteins,aredescribed.Themaincharacteristicsof thelistedproteinsaresummarizedin Table1.
2.2.1Collagenandgelatin Collagen isthemaincomponentoftheECM,andisthemostabundantproteinpresentin mammaliantissues(cornea,bloodvessels,skin,cartilage,bone,tendon,andligament),which providesmechanicalstrengthtotissuesandstimulatescelladhesionandproliferation [145]. Gelatinisacollagenderivativeobtainedbyanincompletedenaturalizationofcollagen extractedfromporcineskinandconnectivetissues;however,marinesources,e.g.,marine sponges,fishskin,arealsorecognizedascollagensources [18].Bothcollagenandgelatinhave beenemployedtoproducemembranes,sponges,nanofibers,andmicrospheresforawide rangeofapplications [87,146,147].Dependingonthepurpose,theseproteinscanbechemicallymodifiedorcombinedwithpolysaccharidesand/orbioactivemoleculestoimprove theirphysicochemicalpropertiesandbiologicalperformance.
2.2.2Silkfibroin Silk isaclassofproteinscomposedoffibroin,thestructuralproteinofsilkfibers,andsericin,thewater-solubleglue-likeproteinthatkeepsthefibroinfiberstogether. SF iscomposed ofglycine,alanine,andserineindifferentpercentages.Silkproteins(fibroinandsericin)producedbysilkwormsareclassifiedintononmulberryandmulberry(Bombyxmori).Besides,SF canalsobefoundininsectsandspiders [148].Givenitsfavorablebiocompatibility,elasticity, toughness,andmechanicalproperties,SFhasbeenexploitedintheproductionofmatricesfor differentapplicationsfromtissueengineeringandregenerativemedicinetotextilesoroptoelectronics [149–151].Bycontrollingtheproteinsecondarystructurefrom α-helicalchainarrangementsinto β-sheetsviaalcoholtreatmentorwatervaporannealing,thebiodegradation rate,mechanicalproperties,andreleaseofbioactivemoleculescanbetuned [152].Beyond that,atphysiologicalpH,thesilkisnegativelycharged,providingsitesforinitialelectrostatic interactionswithcationicmacromoleculesandsmallmolecules.Thoseactivemoleculescan beattachedtoSF,promotingthemodulationoftheSFproteinsallowingadjustmenttothe requirementsoftheenvisionedapplication [151].
2.2.3Sericin
Sericin isagummingproteinthatbindssilkfiberstogether.Itiscomposedofserine,glycine,glutamicacid,asparticacid,threonine,andtyrosine.Sericinhasattractiveproperties, namelyantioxidant,moisturizing,collagenproduction,andpHresponsivenessabilities [24].
Sericinitselfcanformfilms,hydrogels,andsponges,butthosematricescouldhavepoor mechanicalperformance.Stablesericin-basedmatricesareproducedusingethanolprecipitation,cross-linkingorblendingwithnaturalpolymersandsyntheticones [25,28,29].Forinstance,silk/agarblendmembraneshavegoodmechanicalpropertiesandantimicrobial ability [25].
2.2.4Soyprotein Soyprotein isaglobularproteinisolatedfromsoybeans.Soyproteinhasadvantagesover thevarioustypesofnaturalproteins,namelylowprice,nonanimalorigin,relativelylongstoragetime,andstability.Besides,thecombinationofitspropertieswithitsreducedsusceptibilitytothermaldegradationmakessoyproteinaplant-derivedmacromoleculeofhigh interest [38–41,144].Soyproteinisolate(SPI)hasfilm-formingability;however,SPImembranescouldhavepoormechanicalpropertiesandrelativelyhighmoisturesensitivity,thus limitingtheirapplications [42].Thereforemanyeffortshavebeenmadetoenhancethemechanicalperformanceofsoyprotein-basedmembranesthroughtheadditionofaplasticizer, cross-linkingagent,oreventheassociationofsoyproteinwithotherbiomacromolecules(e.g., chitosan,agar),whicharemethodsthatenhancethemechanicalperformanceofthesoy protein-basedmembranes,expandingtheirapplications [42–45].
3Applicationsofthemembranesofbiopolymers 3.1Biomedicalapplications Biopolymer-basedmembranesmadeofnaturalpolymersseemtobeparticularlyattractive forbiomedicalapplicationsduetotheirdiversityandeasyprocessing.Inthisresearchline, someprogresshasbeenmadeinextendingtheiruseinwoundrepair,boneguideregeneration,drugdelivery,andothers.Asanexample,chitinorchitosanacetate/formatepolymer hasbeenappliedtoproducechitin-reinforcednonwovenfabrics,usedasartificialskinadheredtothebodystimulatingnewskinformation,whichacceleratesthehealingrateandreducespain [124].
Besides,severalstudiesonblendedmembranesderivedfromnaturalsourcesforbiomedicalapplicationshavealsobeendescribedintheliterature [48,54–56],wheretheircomposition andprocessingtechniquesareimportantparameterstodeterminetheirfeatures.Infact,the combinationofpolysaccharidesandproteinsisamethodfrequentlyusedtodesignblended materialswithimprovedperformanceregardingswelling,mechanicalresistance,andbiocompatibility,amongotherfeatures.Plentyofattentionhasbeenfocusedonmembranes basedonchitosanblendedwithotherbiomacromoleculessuchasalginate,BC,cellulose,collagen,gelatin,keratin,sericin,andsoyprotein,amongothers.Recentstudiesalsosuggesta positiveinteractionbetweenchitosanandplantextracts,e.g., Aloevera (AV),amedicinal plant,canpromotetheimprovementofantimicrobialaction,waterabsorption,andbiological performanceoftheblendedmembranes [45];inotherapproaches,theinteractionsbetween chitosanandalginate [57,58] orgelatin [55,56,59,60] havealsobeenemployedinthepreparationofpolyelectrolytecomplexes.Theseblendedmembraneshavebeenmainlyproposed
asdrugdeliverysystemsandwounddressings,andforskinregenerationandguidedbone regeneration.
Besidesthekeenattentiongiventochitosanandchitosan-blendedmembraneapplications forbiomedicalsolutions,thereareothernaturalpolymersthatarealsoadvantageous alternatives.
Alginate presentslimitationsregardingmechanicalproperties,degradation,andlackofcell recognition;however,alginatemembraneshavebeenwidelyusedascellcarriersintissue engineeringandforwound-dressing/healingandprotein/drugdeliverydevices [7,8,76,93,100,101].
Gellangum isanoncytotoxicthermoreversiblehydrogel [61] thatcanbeinjectedintotissues andusedfortheencapsulationandinvitrocultureofcells [62].Nowadays,severalmedical andpharmaceuticalapplicationsofgellangumhavebeenreportedsuchas“duallayer membranes” [63],bioinksubstratesforlivingcellprinting [64],dressingmaterials [65],or asavehicleforophthalmicdrugs [66].
Fromanothersource,wefound cellulose andtheirenhancedderivatives.Oneofthoseis relatedtooxidizedcellulose,which,becauseofitsbiodegradable,bactericidal,andhemostaticproperties,hasbeenusedasatopicalhemostaticwounddressinginavarietyofsurgical proceduresandskinandsubcutaneoustissueprocedures [112].Graftedcellulosecopolymers havefoundapplicabilityasmicellesanddrugcarriers,duetotheirintrinsic,adsorbent,proteinadsorption-resistant,andantibacterialproperties.Moreover,whencellulosewasgrafted withstimuli-responsivesidepolymerchains [113–115],itgavefoundationtocellulose-based smartmaterialsthatmayfindapplicationinactivepackaging,biosensors,tissueengineering, antimicrobialsurfaces,separation,anddetectionorsmartclothing [20,116]
Currently, BC membranesarealreadycommerciallyavailableaswound-dressingmaterials [10,22,117] basedontheirintrinsicpropertiessuchashighinvivobiocompatibility [11],optimal3Dcellattachmentsubstrate,flexibility,highwaterretention,andgasexchange capabilities [12].Additionally,BCmembranesactasaphysicalbarrierreducingpain,bacterialinfection,andallowingdrugtransferintothewoundedregion [22,118],displayingacceleratedepithelializationandtissueregenerationratesinseveralwound-healingtreatments, likediabeticfootwounds,chronicwounds,andburns [67,68].TheconjugationofBCwith chitosanresultedinacombinationofpropertiesofthetwobiopolymerssuchasbioactivity, biocompatibility,biodegradability,creatinganexcellentdressingmaterialcapableofisolatingthewoundfromtheenvironment,andhealingstimulation [121,122].BC/chitosanwound dressingisconsideredtobeaninnovativesolutionconsideringtheirgoodantibacterialand barrierpropertiesaswellasadequatemechanicalpropertiesand,inthewetstate,highmoistureretentionthatmaybeappliedasadressingmaterialfortreatingvariouskindsofwounds, burns,andulcers [16]. BC/HA intheformofmembranesdemonstratedthepotentialapplicationofthesesystemsintissueengineeringandboneregeneration [68,75,84].ResearchonBC intheformofmembraneshasbeenappliedforguidedboneregenerationinbonedefectsof criticalandnoncriticalsize [84];inperiodontallesions [153];andasaresorbablebarriermembraneforpreventingtheinvasionoffibroblastcellsandfibrousconnectivetissueintobone defects [75]
HA hasfoundapplicabilityinawidevarietyofmedicalfieldsfromneurosurgerytocutaneouswoundhealingandevencosmeticpracticewhereitisusedasadermalfiller.HAgels foundapplicabilityinosteoarthritistreatmentbeingusedasajointvisco-supplementon
