Polymeric Cryogels: Macroporous Gels with Remarkable Properties PDF
Preview Polymeric Cryogels: Macroporous Gels with Remarkable Properties
Advances in Polymer Science 263 Oguz Okay Editor Polymeric Cryogels Macroporous Gels with Remarkable Properties 263 Advances in Polymer Science Editorial Board: A. Abe, Tokyo, Japan A.-C. Albertsson, Stockholm, Sweden G.W. Coates, Ithaca, NY, USA J. Genzer, Raleigh, NC, USA S. Kobayashi, Kyoto, Japan K.-S. Lee, Daejeon, South Korea L. Leibler, Paris, France T.E. Long, Blacksburg, VA, USA I. Manners, Bristol, UK M. Möller, Aachen, Germany O. Okay, Istanbul, Turkey V. Percec, Pennsylvania, USA B.Z. Tang, Hong Kong, China E.M. Terentjev, Cambridge, UK M.J. Vicent, Valencia, Spain B. Voit, Dresden, Germany U. Wiesner, Ithaca, NY, USA X. Zhang, Beijing, China For furthervolumes: http://www.springer.com/series/12 Aims and Scope TheseriesAdvancesinPolymerSciencepresentscriticalreviewsofthepresentand futuretrendsinpolymerandbiopolymerscience.Itcoversallareasofresearchin polymerandbiopolymerscienceincludingchemistry,physicalchemistry,physics, materialscience. The thematic volumes are addressed to scientists, whether at universities or in industry,whowishtokeepabreastoftheimportantadvancesinthecoveredtopics. AdvancesinPolymerScienceenjoysalongstandingtraditionandgoodreputa- tioninitscommunity.Eachvolumeisdedicatedtoacurrenttopic,andeachreview critically surveys one aspect of that topic, to place it within the context of the volume.Thevolumestypicallysummarizethesignificantdevelopmentsofthelast 5to10yearsanddiscussthemcritically,presentingselectedexamples,explaining and illustrating the important principles, and bringing together many important referencesofprimaryliterature.Onthatbasis,futureresearchdirectionsinthearea canbediscussed.AdvancesinPolymerSciencevolumesthusareimportantrefer- ences for every polymer scientist, as well as for other scientists interested in polymerscience-asanintroductiontoaneighboringfield,orasacompilationof detailedinformationforthespecialist. Review articles for the individual volumes are invited by the volume editors. Singlecontributionscanbespeciallycommissioned. Readership:Polymerscientists,orscientistsinrelatedfieldsinterestedinpoly- merandbiopolymerscience,atuniversitiesorinindustry,graduatestudents. Specialoffer: For all clients with a standing order we offer the electronic form of Advances in PolymerSciencefreeofcharge. Oguz Okay Editor Polymeric Cryogels Macroporous Gels with Remarkable Properties With contributions by (cid:1) (cid:1) (cid:1) F. Auriemma A.D. Bannerman C. De Rosa (cid:1) (cid:1) (cid:1) (cid:1) R. Di Girolamo V.I. Lozinsky H. Mak B. Mattiasson (cid:1) (cid:1) (cid:1) (cid:1) O. Okay P.D. Petrov O.A. Shlyakhtin C.B. Tsvetanov (cid:1) W. Wan L. Yang Editor OguzOkay DepartmentofChemistry IstanbulTechnicalUniversity Istanbul,Turkey ISSN0065-3195 ISSN1436-5030(electronic) ISBN978-3-319-05845-0 ISBN978-3-319-05846-7(eBook) DOI10.1007/978-3-319-05846-7 SpringerChamHeidelbergNewYorkDordrechtLondon LibraryofCongressControlNumber:2014941110 ©SpringerInternationalPublishingSwitzerland2014 Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpart of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation,broadcasting,reproductiononmicrofilmsorinanyotherphysicalway,andtransmissionor informationstorageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilar methodologynowknownorhereafterdeveloped.Exemptedfromthislegalreservationarebriefexcerpts inconnectionwithreviewsorscholarlyanalysisormaterialsuppliedspecificallyforthepurposeofbeing enteredandexecutedonacomputersystem,forexclusiveusebythepurchaserofthework.Duplication ofthispublicationorpartsthereofispermittedonlyundertheprovisionsoftheCopyrightLawofthe Publisher’s location, in its current version, and permission for use must always be obtained from Springer.PermissionsforusemaybeobtainedthroughRightsLinkattheCopyrightClearanceCenter. ViolationsareliabletoprosecutionundertherespectiveCopyrightLaw. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publicationdoesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexempt fromtherelevantprotectivelawsandregulationsandthereforefreeforgeneraluse. While the advice and information in this book are believed to be true and accurate at the date of publication,neithertheauthorsnortheeditorsnorthepublishercanacceptanylegalresponsibilityfor anyerrorsoromissionsthatmaybemade.Thepublishermakesnowarranty,expressorimplied,with respecttothematerialcontainedherein. Printedonacid-freepaper SpringerispartofSpringerScience+BusinessMedia(www.springer.com) Preface Cryogelationisasimplestrategythatallowsthepreparationofmacroporousgels, so-calledcryogels,ofhightoughnessandsuperfastresponsivity.Theterm“cryogel” wasmentionedintheliteratureforthefirsttimein1984byVladimirI.Lozinskyto designatepolymericgelsformed infrozenmedia. Cryogelshave attractedintense attention in the last 10 years due to their extraordinary properties, which have resulted in numerous biotechnological and biomedical applications. The present volumeentitledPolymericCryogels:MacroporousGelswithRemarkableProper- tiesisintendedtoreviewtheprinciplesofcryotropicgelationprocessesaswellas theadvancesmadeduringthepasttwodecadesinthepreparationandapplicationof cryogels based on both synthetic and natural polymers. It is my great pleasure to haveVladimirI.Lozinskyasoneoftheauthorsofthisvolume.Iverymuchenjoyed discussingmanyaspectsofcryogelsandsomesecretsofcryogelationprocesseswith him,bothinIstanbulandatcryogenictemperaturesinMoscow(Fig.1). The history of polymeric cryogels and mechanisms of their formation are reviewed in the first chapter. Chapters “Basic Principles of Cryotropic Gelation” and “Synthesis and Structure-Property Relationships of Cryogels” cover the basic principlesofcryotropicgelation,the synthesis–structure–propertyrelationshipsof cryogels,andsomeoftheirnovelapplications.Aqueouspoly(vinylalcohol)(PVA) solutionsformphysicalgelsbycryogenictreatments,whichareofgreatinterestdue totheiroutstandingproperties.FormationofPVAcryogelsundervariousconditions isdiscussedindetailinchapters“ABriefHistoryofPolymericCryogels,”“Basic Principles of Cryotropic Gelation,” “Kinetic Analysis of Cryotropic Gelation of Poly(vinylalcohol)/watersolutionsbySmall-AngleNeutronScattering,”and“Poly (vinyl alcohol) Cryogels for Biomedical Applications.” The structure of PVA cryogels and the principal processes taking place during their formation are discussed in chapter “Kinetic Analysis of Cryotropic Gelation of Poly(vinyl alco- hol)/watersolutionsbySmall-AngleNeutronScattering”.Aneffectivemethodfor thesynthesisofpolymercryogelsistheinitiationofcryogelationreactionsusingUV irradiation, which is reviewed in chapter “Cryogels via UV Irradiation”. Chapter“InorganicCryogels”coversrecentadvancesininorganiccryogels.Ihave tomentionthat,althoughtheterm“inorganiccryogel”hasbeenusedasthegeneric v vi Preface Fig.1 Lowtemperatureis aprerequisiteforobtaining cryogels.O.Okay(left)and V.I.Lozinsky(right) discussingthecontentof thisvolumeat(cid:3)23(cid:4)Cin Moscow(1February2014) name for freeze-dried products of inorganic gels, precipitates, and colloidal solu- tions, it is more correct to call such freeze-dried products “cryostructurates” or “cryotexturates” rather than cryogels. However, as the term “cryogel” is most commonly used for inorganic materials obtained by free-drying, it will also be usedinchapter“InorganicCryogels”tobeconsistentwithpreviousstudiesinthis field. The last two contributions in this volume provide an overview of the biotech- nologicalandbiomedicalapplicationsofcryogels.Cryogelswiththeirlargepores open up a range of applications, e.g., isolation of microbial cells, capturing of cancer cells, use as matrices for immobilized cell reactors, and environmental separation. These applications of cryogels are reviewed in chapter “Cryogels for Biotechnological Applications.” The unique mechanical properties of PVA cryogelsmakethemanattractivecandidateforbiomedical,andespeciallymedical device applications. In chapter “Poly(Vinyl Alcohol) Cryogels for Biomedical Applications,” the formation process and processing parameters of PVA cryogels and their application in orthopedic and cardiovascular devices are reviewed and discussed. Theeditorbelievesthatthepresentvolumecoveringabroadrangeoftopicsin thefieldofcryogelswillcontributetoabetterunderstandingofthedevelopments achievedduringthepasttwodecadesinthesynthesisandapplicationsofcryogels. I also hope that this work will promote research in this rapidly developing area. Iwouldliketothankalltheauthorswhohavecontributedtothisexcitingvolumeon polymericcryogels. Istanbul,Turkey OguzOkay Contents ABriefHistoryofPolymericCryogels. . . . . . . . . . . . . . . . . . . . . . . . . . 1 VladimirI.Lozinsky BasicPrinciplesofCryotropicGelation. . . . . . . . . . . . . . . . . . . . . . . . . 49 VladimirI.LozinskyandOguzOkay SynthesisandStructure–PropertyRelationshipsofCryogels. . . . . . . . . 103 OguzOkayandVladimirI.Lozinsky KineticAnalysisofCryotropicGelationofPoly(VinylAlcohol)/Water SolutionsbySmall-AngleNeutronScattering. .. . . .. . . . .. . . .. . . . .. 159 ClaudioDeRosa,FiniziaAuriemma,andRoccoDiGirolamo CryogelsviaUVIrradiation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199 PetarD.PetrovandChristoB.Tsvetanov InorganicCryogels. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223 OlegA.Shlyakhtin CryogelsforBiotechnologicalApplications. . . . . . . . . . . . . . . . . . . . . . 245 BoMattiasson Poly(VinylAlcohol)CryogelsforBiomedicalApplications. . . . . . . . . . . 283 WankeiWan,A.DawnBannerman,LifangYang,andHeliumMak Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323 vii A Brief History of Polymeric Cryogels VladimirI.Lozinsky Contents 1 IntroductoryRemarks........................................................................ 2 2 TypesofInitialSystemsCapableofBeingPrecursors forthePreparationofCryogels.............................................................. 4 2.1 Polymeric/BiopolymericCryogelsFormedby Freeze–ThawAgingofColloidSols.................................................. 6 2.2 CryogelsPreparedfromMonomericPrecursors...................................... 7 2.3 PreparationofCryogelsbyCovalentCrosslinkingofHighMolecularWeight Precursors............................................................................... 8 2.4 Physical(Noncovalent)PolymericCryogels.......................................... 22 2.5 Ionic(Ionotropic)Cryogels............................................................ 36 3 ConcludingRemarks......................................................................... 37 References........................................................................................ 38 Abstract Polymeric cryogels, the gels formed in moderately frozen gelling sys- tems, have been empirically known for many decades, but systematic scientific researchonvariouscryogelsandthepeculiaritiesofcryotropicgelformationonly commencedatthebeginningofthe1980s.Thishistoricalreviewbrieflydescribes the principal stages of the studies on these very interesting gel materials. It also discusses some mechanisms of their formation, as well as summarizes published data on the main representatives of chemically crosslinked (covalent), ionically linked,andnoncovalent(physical)cryogels. Keywords Polymeric cryogels (cid:129) Cryogel history (cid:129) Moderately frozen gelling systems(cid:129)Cryotropicgelationprocesses V.I.Lozinsky(*) LaboratoryforCryochemistryof(Bio)Polymers,A.N.NesmeyanovInstituteof OrganoelementCompounds,RussianAcademyofSciences,VavilovStreet28,119991 Moscow,RussianFederation e-mail:[email protected] O.Okay(ed.),PolymericCryogels,AdvancesinPolymerScience263, 1 DOI10.1007/978-3-319-05846-7_1,©SpringerInternationalPublishingSwitzerland2014 2 V.I.Lozinsky 1 Introductory Remarks Polymeric cryogelsare the gel systems formed via the cryogenic treatment(mod- erate freezing—frozen storage—thawing) of solutions or colloidal dispersions of the appropriate precursors [1]. On a microscopic level, moderately frozen molec- ular or colloid solutions are heterophase systems containing both solids (i.e., the polycrystalsoffrozensolvent)andsomeunfrozenfractioncalled“unfrozenliquid microphase”[2],wherethesolutesareconcentrated.Thus,gelationcanonlyoccur withinthelatterunfrozenregionsofthesystemwhilethecrystalsoffrozensolvent act as porogens. Such specific conditions of gel formation are the key factors in determining the rather unusual heterophase macroporous morphology of the resultingpolymermaterials,thewholesetoftheirphysicochemicalcharacteristics and,asaconsequence,theiroperationalcapabilities.Thepresentvolumedealswith thediverseaspectsofpreparation,properties,structure,andpracticalimplementa- tionofvariouscryogelsbasedonsyntheticorganicorinorganicpolymers,aswell as on natural biopolymers. Taking into account the fact that the number of the works published in this field has grown almost exponentially during recent years (Fig. 1a), it is reasonable to first give a brief historical overview of these gel systems, which are very interesting both from the fundamental and applied view- points. Moreover, the authors of some recent publications devoted mainly to the applied aspects often seem to be unaware of the pioneering studies and main scientific sources. It is hoped that this chapter will also contribute to a better understanding of the developments achieved in cryotropic gel formation over the pastthreedecades. In many cases, it is difficult to indicate which exactly was the very first communication on some experimentally observed phenomenon, especially if it was discovered many years ago in the pre-electronic era, and the report appeared in an issue hardly available now, or if it was patented locally in a language not commonlyused.Thepresentbriefhistoricalinformationcertainlyhasnoclaimto be an exhaustive review of all the early pioneering publications on cryogenically produced gel matrices. Nevertheless, we can assert that the term “cryogel” was most probably applied for the first time in a paper published in 1984 to designate polymeric materials prepared via chemical crosslinking of macromolecular pre- cursorsinmoderatelyfrozenorganicmedia[4].Thetermwascreatedbycombining “cryo”(fromtheGreekkryos,meaningfrostorice)and“gel,”thushighlightingthe specific formation conditions for the gels of this family. Besides the mentioned article, different terms were used for gels formed in frozen systems (mainly, aqueous ones): cryocoacervates [5], cryocoagulates [6], cryo-concentrated gels [7, 8], anomalous gels [9], freeze–thaw gels [10], etc. However, since the end of the1980stheterm“cryogel”hasbecomemoreandmorepopular(Fig.1b). It should also be noted that several other materials are currently called “cryogels.”Specificexamplesareasfollows:
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