HANDBOOKOF CHITINAND CHITOSAN
CHITIN-ANDCHITOSAN-BASED POLYMERMATERIALSFOR VARIOUSAPPLICATIONS
VOLUME3
Editedby
SREERAG GOPI
CenterforInnovationsandTechnologies(CIT), ADSONaturalsPrivateLimited,Bangalore,India
SABU THOMAS
MahatmaGandhiUniversity,Kottayam,India
ANITHA PIUS
TheGandhigramRuralInstitute(DeemedUniversity),Dindigul,India
Elsevier
Radarweg29,POBox211,1000AEAmsterdam,Netherlands
TheBoulevard,LangfordLane,Kidlington,OxfordOX51GB,UnitedKingdom 50HampshireStreet,5thFloor,Cambridge,MA02139,UnitedStates
Copyright©2020ElsevierInc.Allrightsreserved.
Nopartofthispublicationmaybereproducedortransmittedinanyformorbyanymeans, electronicormechanical,includingphotocopying,recording,oranyinformationstorageand retrievalsystem,withoutpermissioninwritingfromthepublisher.Detailsonhowtoseek permission,furtherinformationaboutthePublisher’spermissionspoliciesandourarrangements withorganizationssuchastheCopyrightClearanceCenterandtheCopyrightLicensingAgency, canbefoundatourwebsite: www.elsevier.com/permissions
Thisbookandtheindividualcontributionscontainedinitareprotectedundercopyrightbythe Publisher(otherthanasmaybenotedherein).
Notices
Knowledgeandbestpracticeinthisfieldareconstantlychanging.Asnewresearchandexperience broadenourunderstanding,changesinresearchmethods,professionalpractices,ormedical treatmentmaybecomenecessary.
Practitionersandresearchersmustalwaysrelyontheirownexperienceandknowledgein evaluatingandusinganyinformation,methods,compounds,orexperimentsdescribedherein.In usingsuchinformationormethodstheyshouldbemindfuloftheirownsafetyandthesafetyof others,includingpartiesforwhomtheyhaveaprofessionalresponsibility.
Tothefullestextentofthelaw,neitherthePublishernortheauthors,contributors,oreditors, assumeanyliabilityforanyinjuryand/ordamagetopersonsorpropertyasamatterofproducts liability,negligenceorotherwise,orfromanyuseoroperationofanymethods,products, instructions,orideascontainedinthematerialherein.
BritishLibraryCataloguing-in-PublicationData
AcataloguerecordforthisbookisavailablefromtheBritishLibrary LibraryofCongressCataloging-in-PublicationData
AcatalogrecordforthisbookisavailablefromtheLibraryofCongress ISBN:978-0-12-817966-6
ForInformationonallElsevierpublications visitourwebsiteat https://www.elsevier.com/books-and-journals
Publisher: SusanDennis
EditorialProjectManager: KelseyConnors
ProductionProjectManager: SujathaThirugnanaSambandam
CoverDesigner: ChristianJ.Bilbow
TypesetbyMPSLimited,Chennai,India
Listofcontributors
1. Polymerblends,IPNs,gels,composites,andnanocomposites from chitinandchitosan;manufacturing,andapplications 1
SABRINASULTANA,MD.SHIRAJURRAHMAN,MD.MINHAJULISLAM,
MD.NURUSSAKIBANDMD.SHAHRUZZAMAN
2.
YASIRBEERANPOTTATHARA,HANUMAREDDYTIYYAGURA,
ZAKIAHAHMADANDSABUTHOMAS
4. Investigationintothefunctionalpropertiesofcotton, wool, anddenimtextilematerialsfinishedwithchitosanand theuseofchitosanintextile-reinforcedcompositesandmedical textiles89
NILGUNBECENEN,SEVILERDO ˘ GANANDELIFECEMFINDIK
4.1Introduction
4.3Applicationtechniquesandmethodsofchitosantotextileproducts
4.4Propertiesofthechitosan-treatedtextileproducts
4.6Useofchitosanintextile-reinforcedcomposites
5. Chitinblends,interpenetratingpolymernetworks,gels, composites, andnanocompositesforadsorptionsystems: environmentalremediationandproteinpurification
GABRIELIBRAHINTOVAR-JIMENEZ,DANIELABELE ´ NHIRSCH, MARI ´ AEMILIAVILLANUEVA,NICOLASURTASUN,FEDERICOJAVIERWOLMANAND GUILLERMOJAVIERCOPELLO
5.1Introduction
5.4Optimizingadsorptionperformancebychemicaland
5.5Concludingremarksandfutureconsiderations
6. Functionalpropertiesofchitinandchitosan-based polymer materials
GISOOMALEKIANDJAFARM.MILANI
6.1Introduction
6.5Antioxidantactivity
6.6Flocculentandchelating
6.7Futuretrends
7. Fundamentalsofchitosanforbiomedicalapplications199 MOHAMMADRAHATHOSSAIN,ABULK.MALLIKANDMOHAMMEDMIZANURRAHMAN
7.1Introduction
7.4Modificationsandmodifiedformofchitosaninbiomedicalapplication206
7.5Biomedicalapplicationofchitosananditsderivatives
8. Electrospunchitosanmaterialsandtheirpotentialuse as scaffoldsforboneandcartilagetissueengineering
´ NDEZ-RANGEL,GINAPRADO-PRONE,JOSELINEJ.HIDALGO-MOYLE, PHAEDRASILVA-BERMUDEZANDKEIKOSHIRAI
8.1Introduction
8.4Regulatoryissuesofelectrospinningscaffolds
9. Injectablepolymericgelsbasedonchitosanandchitinfor biomedical
9.2Injectablepolymericgelsbasedonchitosanandchitin
10. Preparationandapplicationofbiomimeticandbioinspired membranes basedonchitosan
11. Chitin,chitosan,marinetomarket
G.M.OYATOGUN,T.A.ESAN,E.I.AKPAN,S.O.ADEOSUN,A.P.I.POPOOLA, B.I.IMASOGIE,W.O.SOBOYEJO,A.A.AFONJA,S.A.IBITOYE,V.D.ABERE, A.O.OYATOGUN,K.M.OLUWASEGUN,I.E.AKINWOLEANDK.J.AKINLUWADE
11.4Propertiesofchitinandchitosan
11.5Potentialapplicationsofchitinandchitosan
11.6Economicpotentialofchitinandchitosan
11.7Conclusion
12. Chitin-andchitosan-basedoleogels:rheologicalandthermal
12.5Rheologicalpropertiesofchitin-andchitosan-basedoleogels
12.6Thermogravimetricpropertiesofchitin-andchitosan-basedoleogels400 12.7Thermalbehavior(differentialscanningcalorimetrythermogram) ofchitin-andchitosan-basedoleogels
14.4Preparativemethodsofvariouscarboxymethylchitosan
15. Biomedicalexploitationofchitinandchitosan-based matrices viaionicliquidprocessing
SIMONES.SILVA,JOANAM.GOMES,LUI ´ SAC.RODRIGUESANDRUIL.REIS
15.5Processabilityofchitinandchitosanviaionicliquids
15.7Biomedicalapplicationsofchitinandchitosaninionicliquids
15.8Bonerepair
15.9Drugandgenedelivery
16. Chitinandchitosancompositesforbonetissueregeneration499
E.I.AKPAN,O.P.GBENEBOR,S.O.ADEOSUNANDODILICLETUS
16.1Introduction
16.4Clinicalrequirementsforbonetissueengineeringscaffolds
16.6Chitin/chitosan-basedmaterialsforbonetissueengineering
16.7Methodsoffabricationofchitinandchitosanscaffolds
16.8Thedilemmaofchitosanscaffoldapplicability
16.9Conclusions
17. Drugdeliveryandtissueengineeringapplicationsof chitosan-based biomaterialsystems
17.2Chitosan-basednanosytemsindrugtherapyofneoplasticdiseases
17.3Chitosan-basednanosystemsindrugtherapyofinfectiousdiseases
17.4Blockingthesupplyofessentialelementsformicrobes
17.5Chitosan-basednanosytemsindrugtherapyofinflammatorydiseases570 17.6Tissueengineeringapplicationsofchitosan-basednanosytems573 17.7Conclusion581 References582
18. Futureaspectsofbiomedicalapplicationsofchitinand chitosan indiseasesassociatedwithoxidativestress 589
MAKOTOANRAKU,SHINSUKEIFUKU,DAISUKEIOHARA,FUMITOSHIHIRAYAMA, MASAKIOTAGIRIANDJANUSZM.GEBICKI
18.1Introduction 590
18.2Chitosananditsderivativesasantioxidantswithprotectiveeffects forchronicrenalfailure 591
18.3SDACNFsasamaterialforpharmaceuticalformulationindiseases associatedwithoxidativestress 597
18.4TherapeuticeffectsofPD/NFs-CDsgelinmodelmice 601
18.5Conclusions 604
19. Immunomodulatoryactivitiesofchitinandchitosan microparticles 609
MOSTAFAHAJIMOLLAHOSEINI,SAHARSADEGHI,MAHDIEHAZIZIAND RAMINPOURIRAN
19.1Chitinousmicroparticlesandimmuneresponses
19.2Chitinandchitosanmicroparticlesasadjuvant
19.3Anticancereffectofchitinandchitosanmicroparticles 619
19.4Allergyandchitinousmicroparticles 623
19.5Inflammationandchitin,chitosanmicroparticles 627
19.6Conclusion
20. Chitosan/chitin-basedcompositesforfoodpackaging applications 641
MUHAMMADZUBAIR,MUHAMMADARSHAD,REHANALIPRADHAN ANDAMANULLAH
20.1Introduction 642
20.2Variouschitosan/chitin-basedcompositesforfoodpackagingapplications643
20.3Chitin/chitosanandcarbohydrates-derivedcomposites 652
20.4Chitin/chitosancompositeswithsyntheticpolymer 657
20.5Inorganicmaterials-derivedcomposites 659
20.6Conclusionandfuturetrends 663 References 664
21. Modifiedreleasepropertiesofglutathione-basedchitosan films: Physicalandfunctionalcharacterization 671
YHORSCIRO,JOHNROJAS,CRISTIANJ.YARCEANDCONSTAI ´ NH.SALAMANCA
21.1Introduction
21.3Resultsanddiscussion
21.4Conclusions
22. Chitosan-basedmaterialsastemplatesforessentialoils689 RUTFERNA ´ NDEZ-MARI ´ N,SUSANAC.M.FERNANDES,COLINMCREYNOLDS, JALELLABIDIANDMAA ´ NGELESANDRE ´ SSA ´ NCHEZ
22.1Introduction
22.2Chitosan-basedessentialoilscoatingsandfilms 692
22.3Chitosan-basedessentialoilsemulsionsand(nano)gels 693
22.4Chitosan(nano)capsulesforessentialoilsencapsulation 696
22.5Antioxidantsactivityinchitosanastemplatesforessentialoils 697
22.6Antibacterialactivityinchitosanastemplatesforessentialoils
22.7Conclusionsandfutureperspectives
23. Chitosanandchitosan-basedbiomaterialsforwound
MD.SAZEDULISLAM,MD.SHIRAJURRAHMAN,TANVIRAHMED,SHANTABISWAS, PAPIAHAQUEANDMOHAMMEDMIZANURRAHMAN
23.1Introduction
23.2Woundhealinganditsdifferentstages
23.3Propertiesofchitosanadvantageousforwoundmanagement 727
23.4Differentformsofchitosan-basedbiomaterialsinwoundmanagement731
23.5Chitosan-basedbiocompositesforwoundhealing 739
23.6Chitosanderivativesinwoundmanagement 749
23.7Futureaspectsofchitosan-basedmaterialforwoundmanagement
23.8Conclusion
24. Chitinandchitosanaspromisingimmunostimulantfor aquaculture
DIBYENDUKAMILYAANDMD.IDRISHRAJAKHAN
24.1Introduction
24.3Immunostimulatoryeffectofchitinonshellfish
24.4Immunostimulatoryeffectofchitosanonfinfish
24.5Immunostimulatoryeffectofchitosanonshellfish 766
24.6Effectofchitinandchitosanondiseaseresistance 766
24.7Mechanismofactionofchitinandchitosanasanimmunostimulant767
24.8Conclusionsandfutureperspectives 768 References
25. Chitosan-basedmaterialsforwaterandwastewatertreatment773 MUHAMMADZUBAIR,MUHAMMADARSHADANDAMANULLAH
25.1Introduction 774
25.2Variousformsofchitosan-basedsorbentsforwater/wastewaterremediation775
25.3Removalofdifferentpollutantsusingchitosan-basedmaterial 783
25.4Mechanismofadsorption 792
25.5Summaryandfutureperspective
References
ListofContributors
V.D.Abere DepartmentofMineralProcessing,NationalMetallurgical DevelopmentCentre,Jos,Nigeria
S.O.Adeosun DepartmentofMetallurgicalandMaterialsEngineering, UniversityofLagos,Akoka,Nigeria
A.A.Afonja DepartmentofMaterialsScienceandEngineering,Obafemi AwolowoUniversity,Ile-Ife,Nigeria
ZakiahAhmad FacultyofCivilEngineeringandInstituteforInfrastructure EngineeringandSustainableManagement,UniversitiTeknologiMara,Shah Alam,Malaysia
TanvirAhmed DepartmentofAppliedChemistryandChemicalEngineering, FacultyofEngineeringandTechnology,UniversityofDhaka,Dhaka, Bangladesh
K.J.Akinluwade DepartmentofResearchandDevelopment,Prototype EngineeringDevelopmentInstitute(NationalAgencyforScienceand EngineeringInfrastructure,NASENI),Ilesa,Nigeria
I.E.Akinwole DepartmentofMaterialsScienceandEngineering,Obafemi AwolowoUniversity,Ile-Ife,Nigeria
E.I.Akpan InstituteforCompositeMaterials,TechnicalUniversity, Kaiserslautern,Germany
MakotoAnraku FacultyofPharmaceuticalSciences,SojoUniversity, Kumamoto,Japan;DDSResearchInstitute,SojoUniversity,Kumamoto,Japan
NitheeshAntony AmritaSchoolofPharmacy,AmritaVishwaVidyapeetham, AmritaHealthScienceCampus,Kochi,India
MuhammadArshad DepartmentofAgricultural,FoodandNutritional Science,UniversityofAlberta,Edmonton,AB,Canada
MahdiehAzizi DepartmentofImmunology,SchoolofMedicine,Shahid BeheshtiUniversityofMedicalSciences,Tehran,Iran
AnjaliBajpai DepartmentofChemistry,GovernmentScienceCollege, Jabalpur,India
Nilgu ¨ nBecenen TextileTechnologyProgramme,EdirneVocationalCollegeof TechnicalSciences,TrakyaUniversity,Edirne,Turkey
DanielAssumpc¸a˜oBertuol ChemicalEngineeringDepartment,Federal UniversityofSantaMaria—UFSM,SantaMaria,RS,Brazil
ShantaBiswas DepartmentofAppliedChemistryandChemicalEngineering, FacultyofEngineeringandTechnology,UniversityofDhaka,Dhaka, Bangladesh
YhorsCiro DepartmentofPharmacy,SchoolofPharmaceuticalandFood Sciences,UniversityofAntioquia,Medellı´n,Colombia
OdiliCletus DepartmentofMetallurgicalandMaterialsEngineering, UniversityofLagos,Lagos,Nigeria
GuillermoJavierCopello UniversidaddeBuenosAires(UBA),Facultadde FarmaciayBioquı´mica,DepartamentodeQuı´micaAnalı´ticayFisicoquı´mica, Junı´n956,CABA,Argentina;CONICET UniversidaddeBuenosAires (UBA),InstitutodeQuı´micayMetabolismodelFa ´ rmaco(IQUIMEFA), BuenosAires,Argentina
SevilErdo ˘ gan LaborantandVeterinaryHealthProgramme,Ke¸sanVocational College,TrakyaUniversity,Edirne,Turkey
T.A.Esan DepartmentofRestorativeDentistry,ObafemiAwolowoUniversity, Ile-Ife,Nigeria
Ine ˆ sFarinha 73100Lda.,Edifı´cioArcis,RuaIvoneSilva,6,4 piso,Lisboa, Portugal
SusanaC.M.Fernandes CNRS/UnivPau&PaysAdour/E2SUPPA,Institut desSciencesAnalytiquesetdePhysico-Chimiepourl’Environnementetles Materiaux,Anglet,France
RutFerna ´ ndez-Marı ´ n EnvironmentalandChemicalEngineeringDepartament, UniversityoftheBasqueCountryUPV/EHU,Donostia-SanSebastia ´ n,Spain
ElifEcemFındık DepartmentofBiotechnologyandGenetic,Instituteof NaturalSciences,TrakyaUniversity,Edirne,Turkey
FilomenaFreitas UCIBIO-REQUIMTE,ChemistryDepartment,Facultyof SciencesandTechnology,UniversidadeNOVAdeLisboa,Campusda Caparica,Caparica,Portugal
O.P.Gbenebor DepartmentofMetallurgicalandMaterialsEngineering, UniversityofLagos,Lagos,Nigeria
JanuszM.Gebicki DepartmentofBiologicalSciences,MacquarieUniversity, Sydney,Australia
JoanaM.Gomes 3B’sResearchGroup,I3Bs—ResearchInstituteon Biomaterials,BiodegradablesandBiomimetics,UniversityofMinho, Guimara ˜ es,Portugal;ICVS/3B’s—PTGovernmentAssociateLaboratory, Braga/Guimara ˜ es,Portugal
LaxmiGond DepartmentofChemistry,GovernmentScienceCollege,Jabalpur, India
PapiaHaque DepartmentofAppliedChemistryandChemicalEngineering, FacultyofEngineeringandTechnology,UniversityofDhaka,Dhaka, Bangladesh
AdrianaHerna ´ ndez-Rangel BiotechnologyDepartment,Laboratoryof BiopolymersandPilotPlantofBioprocessingofAgro-IndustrialandFood By-Products,AutonomousMetropolitanUniversity,MexicoCity,Mexico
JoselineJ.Hidalgo-Moyle FacultyofMedicine,NationalAutonomous UniversityofMexico,MexicoCity,Mexico
FumitoshiHirayama FacultyofPharmaceuticalSciences,SojoUniversity, Kumamoto,Japan;DDSResearchInstitute,SojoUniversity,Kumamoto,Japan
DanielaBele ´ nHirsch UniversidaddeBuenosAires(UBA),Facultadde FarmaciayBioquı´mica,Ca ´ tedradeBiotecnologı´a,Junı´n,Argentina; CONICET UniversidaddeBuenosAires,InstitutodeNanobiotecnologı ´ a (NANOBIOTEC),BuenosAires,Argentina
MostafaHajiMollaHoseini DepartmentofImmunology,SchoolofMedicine, ShahidBeheshtiUniversityofMedicalSciences,Tehran,Iran
MohammadRahatHossain DepartmentofAppliedChemistryandChemical Engineering,FacultyofEngineeringandTechnology,UniversityofDhaka, Dhaka,Bangladesh
WeiHuang HangzhouSingcleanMedicalProductsCo.,Ltd.,Hangzhou,P.R. China
S.A.Ibitoye DepartmentofMaterialsScienceandEngineering,Obafemi AwolowoUniversity,Ile-Ife,Nigeria
ShinsukeIfuku GraduateSchoolofEngineering,TottoriUniversity,Tottori, Japan
B.I.Imasogie DepartmentofMaterialsScienceandEngineering,Obafemi AwolowoUniversity,Ile-Ife,Nigeria
DaisukeIohara FacultyofPharmaceuticalSciences,SojoUniversity, Kumamoto,Japan;DDSResearchInstitute,SojoUniversity,Kumamoto,Japan
Md.MinhajulIslam DepartmentofAppliedChemistryandChemical Engineering,FacultyofEngineeringandTechnology,UniversityofDhaka, Dhaka,Bangladesh
Md.SazedulIslam DepartmentofAppliedChemistryandChemical Engineering,FacultyofEngineeringandTechnology,UniversityofDhaka, Dhaka,Bangladesh
XulinJiang KeyLaboratoryofBiomedicalPolymersofMinistryofEducation andDepartmentofChemistry,WuhanUniversity,Wuhan,P.R.China
DibyenduKamilya DepartmentofAquaticHealthandEnvironment,College ofFisheries,CentralAgriculturalUniversity,Lembucherra,Tripura,India
Md.IdrishRajaKhan DepartmentofAquaticHealthandEnvironment,College ofFisheries,CentralAgriculturalUniversity,Lembucherra,Tripura,India
JalelLabidi EnvironmentalandChemicalEngineeringDepartament, UniversityoftheBasqueCountryUPV/EHU,Donostia-SanSebastia ´ n,Spain
PolianaPollizelloLopes ChemicalEngineeringDepartment,Federal UniversityofSantaMaria—UFSM,SantaMaria,RS,Brazil
GisooMaleki DepartmentofFoodScienceandTechnology,Ferdowsi UniversityofMashhad,Mashhad,Iran
AbulK.Mallik DepartmentofAppliedChemistryandChemicalEngineering, FacultyofEngineeringandTechnology,UniversityofDhaka,Dhaka, Bangladesh
ColinMcReynolds CNRS/UnivPau&PaysAdour/E2SUPPA,Institutdes SciencesAnalytiquesetdePhysico-Chimiepourl’Environnementetles Materiaux,Anglet,France
JafarM.Milani DepartmentofFoodScienceandTechnology,Sari AgriculturalSciencesandNaturalResourcesUniversity,Sari,Iran
MohammadHosseinNaeli DepartmentofFoodScienceandTechnology,Sari AgriculturalSciencesandNaturalResourcesUniversity,Sari,Iran
K.M.Oluwasegun DepartmentofMaterialsScienceandEngineering,Obafemi AwolowoUniversity,Ile-Ife,Nigeria
MasakiOtagiri FacultyofPharmaceuticalSciences,SojoUniversity, Kumamoto,Japan;DDSResearchInstitute,SojoUniversity,Kumamoto,Japan
A.O.Oyatogun DepartmentofMaterialsScienceandEngineering,Obafemi AwolowoUniversity,Ile-Ife,Nigeria
G.M.Oyatogun DepartmentofMaterialsScienceandEngineering,Obafemi AwolowoUniversity,Ile-Ife,Nigeria
RajithaPanonnummal AmritaSchoolofPharmacy,AmritaVishwa Vidyapeetham,AmritaHealthScienceCampus,Kochi,India
A.P.I.Popoola DeparmentofChemical,MetallurgicalandMaterials Engineering,TshwaneUniversityofTechnology,Pretoria,SouthAfrica
YasirBeeranPottathara FacultyofMechanicalEngineering,Universityof Maribor,Maribor,Slovenia
RaminPouriran SchoolofMedicine,ShahidBeheshtiUniversityofMedical Sciences,Tehran,Iran
PreetiPradhan DepartmentofChemistry,GovernmentScienceCollege, Jabalpur,India
RehanAliPradhan DepartmentofAgricultural,FoodandNutritionalScience, UniversityofAlberta,Edmonton,AB,Canada
GinaPrado-Prone PostgraduateStudiesandResearchDivision,Facultyof Dentistry,NationalAutonomousUniversityofMexico,MexicoCity,Mexico
Md.ShirajurRahman DepartmentofAppliedChemistryandChemical Engineering,FacultyofEngineeringandTechnology,UniversityofDhaka, Dhaka,Bangladesh
MohammedMizanurRahman DepartmentofAppliedChemistryand ChemicalEngineering,FacultyofEngineeringandTechnology,Universityof Dhaka,Dhaka,Bangladesh
RuiL.Reis 3B’sResearchGroup,I3Bs—ResearchInstituteonBiomaterials, BiodegradablesandBiomimetics,UniversityofMinho,Guimaraes,Portugal; ICVS/3B’s—PTGovernmentAssociateLaboratory,Braga/Guimaraes, Portugal;TheDiscoveriesCentreforRegenerativeandPrecisionMedicine, Guimara ˜ es,Portugal
Luı´saC.Rodrigues 3B’sResearchGroup,I3Bs—ResearchInstituteon Biomaterials,BiodegradablesandBiomimetics,UniversityofMinho, Guimaraes,Portugal;ICVS/3B’s—PTGovernmentAssociateLaboratory, Braga/Guimaraes,Portugal
JohnRojas DepartmentofPharmacy,SchoolofPharmaceuticalandFood Sciences,UniversityofAntioquia,Medellı´n,Colombia
M.Sabitha AmritaSchoolofPharmacy,AmritaVishwaVidyapeetham, AmritaHealthScienceCampus,Kochi,India
SaharSadeghi DepartmentofMedicalBiotechnology,SchoolofAdvanced TechnologiesinMedicine,ShahidBeheshtiUniversityofMedicalSciences, Tehran,Iran
Md.NurusSakib DepartmentofAppliedChemistryandChemical Engineering,FacultyofEngineeringandTechnology,UniversityofDhaka, Dhaka,Bangladesh
Constaı´nH.Salamanca LaboratoriodeDisenoyFormulacio ´ ndeProductos Quı´micosyDerivados,DepartamentodeCienciasFarmace ´ uticas,Facultadde CienciasNaturales,UniversidadICESI,Cali,Colombia
MaA ´ ngelesAndre ´ sSa ´ nchez EnvironmentalandChemicalEngineering Departament,UniversityoftheBasqueCountryUPV/EHU,Donostia-San Sebastia ´ n,Spain
Md.Shahruzzaman DepartmentofAppliedChemistryandChemical Engineering,FacultyofEngineeringandTechnology,UniversityofDhaka, Dhaka,Bangladesh
KeikoShirai BiotechnologyDepartment,LaboratoryofBiopolymersandPilot PlantofBioprocessingofAgro-IndustrialandFoodBy-Products,Autonomous MetropolitanUniversity,MexicoCity,Mexico
SimoneS.Silva 3B’sResearchGroup,I3Bs—ResearchInstituteon Biomaterials,BiodegradablesandBiomimetics,UniversityofMinho, Guimara ˜ es,Portugal;ICVS/3B’s—PTGovernmentAssociateLaboratory, Braga/Guimara ˜ es,Portugal
PhaedraSilva-Bermudez TissueEngineering,CellularTherapyand RegenerativeMedicineUnit,NationalInstituteofRehabilitation“Luis GuillermoIbarraIbarra”,MexicoCity,Mexico
W.O.Soboyejo FacultyofEngineering,WisconsinPolytechnicInstitute, Menomonie,WI,UnitedStates
SabrinaSultana DepartmentofArtsandSciences,AhsanullahUniversityof ScienceandTechnology,Dhaka,Bangladesh
WeiqingSun HangzhouSingcleanMedicalProductsCo.,Ltd.,Hangzhou, P.R.China
EduardoHiromitsuTanabe ChemicalEngineeringDepartment,Federal UniversityofSantaMaria—UFSM,SantaMaria,RS,Brazil
SabuThomas InternationalandInteruniversityCentreforNanoscienceand Nanotechnology,MahatmaGandhiUniversity,Kottayam,India
HanumaReddyTiyyagura FacultyofMechanicalEngineering,Universityof Maribor,Maribor,Slovenia
GabrielIbrahinTovar-Jimenez UniversidaddeBuenosAires(UBA),Facultad deFarmaciayBioquı´mica,DepartamentodeQuı´micaAnalı´ticay Fisicoquı´mica,Junı´n956,CABA,Argentina;CONICET Universidadde BuenosAires(UBA),InstitutodeQuı´micayMetabolismodelFa ´ rmaco (IQUIMEFA),BuenosAires,Argentina
AmanUllah DepartmentofAgricultural,FoodandNutritionalScience, UniversityofAlberta,Edmonton,AB,Canada
Nicola ´ sUrtasun CONICET UniversidaddeBuenosAires,Institutode Nanobiotecnologı´a(NANOBIOTEC),BuenosAires,Argentina;Universidad deBuenosAires(UBA),FacultaddeCienciasExactasyNaturales, DepartamentodeFisiologı´a,Biologı´aMolecularyCelular,Junı´n,Argentina
Marı´aEmiliaVillanueva UniversidaddeBuenosAires(UBA),Facultadde FarmaciayBioquı´mica,DepartamentodeQuı´micaAnalı´ticayFisicoquı´mica, Junı´n956,CABA,Argentina;CONICET UniversidaddeBuenosAires (UBA),InstitutodeQuı´micayMetabolismodelFa ´ rmaco(IQUIMEFA), BuenosAires,Argentina
FedericoJavierWolman UniversidaddeBuenosAires(UBA),Facultadde FarmaciayBioquı´mica,Ca ´ tedradeBiotecnologı´a,Junı´n,Argentina; CONICET UniversidaddeBuenosAires,InstitutodeNanobiotecnologı ´ a (NANOBIOTEC),BuenosAires,Argentina
CongXie KeyLaboratoryofBiomedicalPolymersofMinistryofEducation andDepartmentofChemistry,WuhanUniversity,Wuhan,P.R.China;NonpowerNuclearTechnologyResearchandDevelopmentCenter,Hubei UniversityofScienceandTechnology,Xianning,P.R.China;Hangzhou SingcleanMedicalProductsCo.,Ltd.,Hangzhou,P.R.China
CristianJ.Yarce LaboratoriodeDisen ˜ oyFormulacio ´ ndeProductosQuı´micos y Derivados,DepartamentodeCienciasFarmace ´ uticas,FacultaddeCiencias Naturales,UniversidadICESI,Cali,Colombia
MuhammadZubair DepartmentofAgricultural,FoodandNutritional Science,UniversityofAlberta,Edmonton,AB,Canada
Polymerblends,IPNs,gels, composites,andnanocomposites fromchitinandchitosan; manufacturing,andapplications
SabrinaSultana1,Md.ShirajurRahman2, Md.MinhajulIslam2,Md.NurusSakib2 and Md.Shahruzzaman2
1DepartmentofArtsandSciences,AhsanullahUniversityofScienceand Technology,Dhaka,Bangladesh, 2DepartmentofAppliedChemistryand ChemicalEngineering,FacultyofEngineeringandTechnology,University ofDhaka,Dhaka,Bangladesh
OUTLINE
1.1Introduction2
1.2Chemicalstructureandpreparationofchitinandchitosan4
1.2.1Chemicalstructureandpreparationofchitin4
1.2.2Chemicalstructureandpreparationofchitosan5
1.3Polymerblendsfromchitinandchitosan6
1.3.1Blendswithsyntheticpolymers7
1.3.2Blendswithnaturalpolymers8
1.3.3Applicationsofchitinandchitosanblends8
1.4Interpenetratingpolymernetworksfromchitin/chitosan9
1.4.1Chitosan-basedfull-interpenetratingpolymernetworkandsemiinterpenetratingpolymernetworksystems10
1.4.2Interpenetratingpolymernetworkhydrogelsbasedonchitosanand syntheticionicmatrices11
1.4.3Interpenetratingpolymernetworkhydrogelsbasedonchitosanand syntheticnonionicmatrices12
1.4.4Interpenetratingpolymernetworkcryogelsbasedonchitosanand syntheticmatrices12
1.4.5Applicationsofchitin/chitosan-basedInterpenetratingpolymer networks13
1.5Chitin-andchitosan-basedgels14
1.5.1Physicallyassociatedgels14
1.5.2Polyelectrolytecomplexation17
1.5.3Covalentlycross-linkedgels18
1.5.4Applicationsofchitin-andchitosan-basedgels19
1.6Chitin-andchitosan-basedcomposites22
1.6.1Compositesfromsyntheticfillers22
1.6.2Compositesfromnaturalfillers23
1.6.3Applicationsofchitin-andchitosan-basedcomposites25
1.7Chitin-andchitosan-basednanocomposites27
1.7.1Nanocompositesfromchitinandchitosan28
1.7.2Applicationsofchitin-andchitosan-basednanocomposites29
1.8Conclusionsandfutureprospective32 References33
1.1Introduction
Naturalpolymersarethemostwidespreadandeffectivematerials, mainlyduetotheirabundance,environmentalconcerns(renewability andbiodegradability),andwideapplicability.Thedemandofnatural polymericmaterialshasbeenincreasingoverthelasttwodecades becausenaturalpolymershavebetterbiocompatibilityandlesstoxic effectsthanmostsyntheticpolymers.Thishasledtotheutilizationof theirusefulinherentpropertiesforawiderangeofapplicationsindifferentfields [1,2].Manystudieshavebeencarriedoutonthe manufacturingofadvancedpolymericmaterials,suchasblends,gels, composites,andnanocomposites,bymixingnaturalpolymerswith othernaturalorsyntheticpolymersandfillers.
Amongthenaturalpolymers,chitinandchitosanoccupyadistinctpositionduetotheirabundance,versatility,easeofmodification,andunique
propertiesincludingbiodegradability, biocompatibility,nontoxicity,antibacterialandantifungalproperties,hydrophilicity [3 5],etc.Inaddition, thestructuralunitsofchitinandchitosancontainareactiveaminogroup thatmakesthemmucheasiertobemodifiedbychemicalreactionsthan cellulose.Thesehavemadechitinandchitosanveryusefulandoutstandingcandidatesforabroadrangeofapplicationsinbiomedical,pharmaceutical,chemical,agricultural,cosmetics,andenvironmentalfields.Thereare manyreviewsfocusingontheproperties,modifications,andapplications ofchitinandchitosan [6,7].
Alotofderivativesofchitinwithdifferentfunctionalpropertieshave beensynthesizedbychemicalmodifications.Shalumonetal. [8] reportedthesynthesisofwater-solublecarboxymethylchitinandpoly (vinylalcohol)(PVA)blendbyanelectrospinningmethodwhichwas usedfortissueengineeringapplications.MorinandDufresne [9] reportedthepreparationofnanocompositesfromacolloidalsuspension ofchitinwhiskersandpoly(e-caprolactone)asthematrix.Inanother study,Madhumathietal.developednovelchitin/nanosilvercomposite scaffoldsthathaveexcellentantibacterialactivityagainst Staphylococcus aureus and Escherichiacoli aswellasgoodblood-clottingability [10].The resultsoftheirstudysuggestedthat α-chitin/nanosilvercompositescaffoldscouldbeusedforwound-healingapplications.Inaddition,SiO2chitin/carbonnanotubes(CNTs)bionanocompositeshavealsobeen reportedbymanyresearchers [11].
Recently,muchattentionhasbeenpaidtochitosanasapotentialbiopolymerduetoitsremarkableintrinsicproperties [12,13].Huangetal. reportedthesynthesisofvariousmetal chitosannanocomposites includingsilver(Ag),gold(Au),platinum(Pt),andpalladium(Pd)in aqueoussolutions [14].Inanotherwork,Bergerandhiscoworkerspreparedchitosanhydrogelsbyblendingchitosanwithotherwater-soluble nonionicpolymerssuchasPVA [15]
Chitinandchitosaninherentlyhavepoormechanicalpropertiesthat resultsindifficultiesfortheiruseinbonerepairandreconstruction. Thereforethemechanicalpropertiesofchitinandchitosancanbe improvedonlywhentheadditionofbiomaterialslikehydroxyapatite (HAp),bioactiveglassceramic(BGC),etc.ispossible.Recently,our groupreportedthepreparationofchitosan/nanohydroxyapatitebioceramicscaffoldforspongyboneregeneration [16].BGCareagroupof osteoconductivesilicate-basedmaterialsusedforbonerepair.Wheeler etal.reportedBGCcoatingonthesurfaceoftitaniumwhichwasused forosteointegration [17].
Differenttypesofpreparationtechniquesforthemanufactureof advancedpolymericmaterialswithchitinandchitosanhavebeendiscussedbyPailletandDufresne.Theseincludecastingandevaporating technique,freeze-dryingandhot-pressingtechniques,polymergrafting,
nonaqueoussolventdispersiontechnique,extrusion,impregnation,and electrospinning.Thischapterintendstofocusonthebasicfundamentalsof chitinandchitosanincludingtheirstructure,preparation,andapplications.
1.2Chemicalstructureandpreparationofchitinandchitosan
Chitinisanaturallyoccurringpolysaccharidefoundintheshellsof livingorganismssuchascrabs,lobsters,tortoise,shrimps,andinsects [18] oritcanbegeneratedviafungalfermentationprocesses.Andchitosanisauniquebiobasedpolymerthatisaderivativeofchitinandforms theexoskeletonofarthropods.Itisobtainedbypartialdeacetylationof chitinusingachemicalmethodorbyenzymatichydrolysis.Ingeneral, chitinwithadegreeofdeacetylationof70%oraboveisconsideredto bechitosan [19].
1.2.1Chemicalstructureandpreparationofchitin
Chitinisanaturallyoccurringpolymerconsistingof2-acetamido-2deoxy-D-glucoseviaa β(1-4)linkage(Fig.1.1).Threeformsofchitinare available,namely α-, β-,and γ-chitin,however,thestructureof α-chitin hasbeeninvestigatedmoreextensivelythanthatofeitherthe β-or γ-form.Veryfewstudieshavebeencarriedouton γ-chitinbecause γ-chitinmaybeadistortedversionofeither α-or β-chitin [20].
Asuspensionofchitincrystalliteparticleswasfirstpreparedby Marchessaultetal. [21] in1959.Inthismethod,2.5Nhydrochloricacid solutionwasusedtotreatpurifiedchitinunderrefluxfor1h.Afterthe reflux,theexcessacidwasseparatedbyadecantationprocessandthen distilledwaterwasaddedtoobtainthesuspension.Itwasobserved fromtheirmethodthattheacid-hydrolyzedchitinspontaneouslydispersedintorod-likeparticlesthatcouldbeconcentratedtoaliquid
FIGURE1.1
crystallinephaseandself-assembledtoacholestericliquidcrystalline phaseaboveacertainconcentration [22].Thoughchitinsarepresent withinnumeroustaxonomicgroups,onthecommercialscaletheyare usuallyextractedfrommarinecrustaceans,mainlybecausealarge amountofwasteisavailableasaby-productoffoodprocessing.
1.2.2Chemicalstructureandpreparationofchitosan
Asthesecondmostabundantnaturalbiopolymeraftercellulose, chitosanconsistsof β(1-4)-linked D-glucosaminewithrandomlylocated N-acetylglucosaminegroupsdependinguponthedegreeofdeacetylationofthepolymer(Fig.1.2).Deacetylationisnormallyconductedby repetitionsofalkalinehydrolysisduetotheresistanceofsuchgroups owingtothetransarrangementoftheC2-C3substituentsinthesugar ring [23].Theconditionsduringdeacetylationmustbeproperlycontrolledsothatthechitinmaybedeacetylatedtochitosanresultingina betteryield.
Generally,twodifferentmethodsareknownforthepreparationof chitosanfromchitinwithvaryingdegreesofacetylation.Oneofthemis heterogeneousdeacetylationofsolidchitinandtheotherishomogeneousdeacetylationofpreswollenchitinundervacuuminanaqueous medium.Inbothcases,concentratedalkalisolutionsandlongprocessingtimesarerequiredforthedeacetylationreactionwhichmayvary dependingontheheterogeneousorhomogeneousconditionsfrom1to nearly80h.
Toreducethelongprocessingtimesandtherequirementforlarge amountsofalkalitodeacetylatechitin,severalalternative-processing methodshavebeendeveloped.Examplesoftheseincludetheuseof successivealkalitreatmentsusin gthiophenolinDMSO;thermomechanicalprocessesusingacascadereactoroperatedunderlowalkali concentration;flashtreatment undersaturatedsteam;theuseof microwavedielectricheating;and intermittentwaterwashing.There isevidencethatincertainbacteriaandfungi,enzymaticdeacetylation
cantakeplace [24] .Recently,amicrowavetechniqueforefficientdeacetylationofchitinnanowhiskerstoachitosannanoscaffoldhasalso beenreported [5] .Bothchitinandchitosancanbepreparedusing commonprocesses,whicharegivenin Fig.1.3 .
1.3Polymerblendsfromchitinandchitosan
Toimprovethepropertiesofchitin/chitosanandfurtherdiversify theirapplications,variousstrategieshavebeenadopted,suchascrosslinking,copolymerization,chemicalmodification,blending,andsoon. Inparticular,modificationofchitin/chitosanbymeansofblendingis anattractivemethodthatiscommonlyusedforprovidingdesirable polymericmaterialswithcombinedpropertiesforparticularapplications [25].Recently,blendsofchitinandchitosanhaveattractedmuch attentionduetotheirstrongpotentialforreplacingsyntheticpolymers inmanyapplications,inadditiontobeingrenewableresources,nontoxic,inexpensive,andleavingbehindbiodegradablewaste.Generally, twomethodsareavailableforblendingchitosan:(1)solutionblending [26] (dissolvinginasolventfollowedbyevaporation);and(2)melt blending [27] (mixingunderfusionconditions).Ofthetwomethods, solutionblendingisthemostappliedmethodaccordingtotheliterature duetoitssimplicityandsuitability.
Crustaceans (shrimp, crab, lobster, krill, and squid)
Decalicification in dil. Aqueous HCLsolution (3–5% HCI w/v at room temperature)
Deproteination in dil. aqueous NaOH solution (3–5% w/v NaOH, 80°C to 900°C for a few hrs. or at room temperature overnight)
Decolarization in 0.5% KMnO aqueous and oxalic acid aqueous or sunshine
Deacetylation in hot conc. NaOH solution (40–50% w/v NaOH, at 90°C to 120°C for 4 to 5hrs.)
FIGURE1.3 Commonprocessforthepreparationofchitinandchitosan.
Chitin
Chitosan
1.3.1Blendswithsyntheticpolymers
Toproducesyntheticbiodegradablepolymerswithgoodwaterabsorbencyandenhancedmechanicalproperties,blendingofchitinandchitosan withsyntheticpolymersisthemostconvenientmethodnowadays. Amongthesyntheticpolymers,PVAandpolyethyleneglycol(PEG)are thetwofrequentlyblendedpolymers [28] thatpossessbetterhydrophilicity,mechanicalproperties,andbiocompatibility.Engelbergreportedthe preparationofbiodegradablehomogeneousfilmsofchitosanblendsby mixingPEGorPVAwithasolutionofchitosanacetateusingafilmcasting method [29].Moreover,Wilesetal.reportedanotherfilmwhichwaspreparedbyblendingchitosanandPEGtogether.
InanotherstudyGongetal.evaluatedthemechanicalpropertiesof blendsofchitosanwithpolyurethane,preparedbyasolventcasting method [30].Chitosanhybridmaterialsweregeneratedbymixingchitosanandviscoserayonusingamechanicalblendingmethod.Muzzarelli etal.reportedchitin/chitosanblendsbymixingchitinandchitosan with1,6-diisocyanatohexane(polyurea(urethanes))inDMA-LiClsolutions [31].Also,Butleretal. [32] preparedchitosan-blendedfilmscontainingglycerol(0.25%and0.5%).
Inanotherstudy,thepreparationandcharacterizationofchitosan/ N-methylolnylon6blendsintheformofmembraneswerereportedfor theseparationofethanol watermixturesbythepervaporationmethod [33].Toenhancetheseparationperformance,theblendmembranes weremixedwithH2SO4.However,theblendingcompositionplaysa vitalrolethataffectstheperformanceofthemembranes.Srinivasaetal. studiedthemechanicalpropertiesofchitosanfilmspreparedbyblendingchitosanwithpolyols [34].Inanotherattempt,Nugrahaetal.preparedchitosanfilmsbyblendingchitosanwithpoly(lacticacid)(PLA).
Chitosanblendswithpolyvinylpyrrolidone(PVP)andPEGwere reportedbyZengetal. [35].TheydidFTIR,wide-angleX-raydiffraction (WAXD),anddifferentialscanningcalorimeter(DSC)toprovethecompatibilityofthechitosan/PVAblends.Sandovaletal. [36] studiedthe compatibilityoftwochitosanblendswithPVAandpoly(2-hydroxyethyl methacrylate)(P2HEM)throughmoleculardynamicsimulations. Furthermore,SarasamandMadihally [37] havereportedthesynthesis ofchitosan/polycaproactone(PCA)blends.Itwasrevealedfromtheir studythatthetwopolymersweresuccessfullyblendedandusedfortissueengineeringapplications.
Chitosanwasmeltblendedwithpolycaprolactone(PCL),poly(butylenesuccinate)(PBS),PLA,poly(butyleneterephthalateadipate)(PBTA), andpoly(butylenesuccinateadipate)(PBSA) [27].Thebiodegradability ofchitosan/nylon11wasinvestigatedbyKuoetal. [38].Fromtheir studyitwasrevealedthattheadditionofchitosanwithnylon11greatly
