Smart Nanohybrids of RAFT Polymers and Inorganic Particles PDF
Preview Smart Nanohybrids of RAFT Polymers and Inorganic Particles
Springer Theses Recognizing Outstanding Ph.D. Research Bastian Ebeling Smart Nanohybrids of RAFT Polymers and Inorganic Particles Springer Theses Recognizing Outstanding Ph.D. Research Aims and Scope The series “Springer Theses” brings together a selection of the very best Ph.D. theses from around the world and across the physical sciences. Nominated and endorsed by two recognized specialists, each published volume has been selected foritsscientificexcellenceandthehighimpactofitscontentsforthepertinentfield of research. For greater accessibility to non-specialists, the published versions includeanextendedintroduction,aswellasaforewordbythestudent’ssupervisor explainingthespecialrelevanceoftheworkforthefield.Asawhole,theserieswill provide a valuable resource both for newcomers to the research fields described, and for other scientists seeking detailed background information on special questions. Finally, it provides an accredited documentation of the valuable contributions made by today’s younger generation of scientists. Theses are accepted into the series by invited nomination only and must fulfill all of the following criteria (cid:129) They must be written in good English. (cid:129) The topic should fall within the confines of Chemistry, Physics, Earth Sciences, Engineering and related interdisciplinary fields such as Materials, Nanoscience, Chemical Engineering, Complex Systems and Biophysics. (cid:129) The work reported in the thesis must represent a significant scientific advance. (cid:129) Ifthethesisincludespreviouslypublishedmaterial,permissiontoreproducethis must be gained from the respective copyright holder. (cid:129) They must have been examined and passed during the 12 months prior to nomination. (cid:129) Each thesis should include a foreword by the supervisor outlining the signifi- cance of its content. (cid:129) The theses should have a clearly defined structure including an introduction accessible to scientists not expert in that particular field. More information about this series at http://www.springer.com/series/8790 Bastian Ebeling Smart Nanohybrids of RAFT Polymers and Inorganic Particles Doctoral Thesis accepted by ö the Georg-August-University G ttingen, Germany 123 Author Supervisor Dr. BastianEbeling Prof. Dr. PhilippVana Instituteof PhysicalChemistry Instituteof PhysicalChemistry Georg-August-University Göttingen Georg-August-University Göttingen Göttingen Göttingen Germany Germany PresentAddress CPE Lyon,Laboratoire de Chimie, Catalyse, PolymèresetProcédés (C2P2),EquipeLCPP Universityof Lyon1 Villeurbanne France Additionalmaterial tothis bookcan bedownloaded from http://extras.springer.com. ISSN 2190-5053 ISSN 2190-5061 (electronic) Springer Theses ISBN 978-3-319-15244-8 ISBN 978-3-319-15245-5 (eBook) DOI 10.1007/978-3-319-15245-5 LibraryofCongressControlNumber:2015932070 SpringerChamHeidelbergNewYorkDordrechtLondon ©SpringerInternationalPublishingSwitzerland2015 Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpart of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilarmethodologynowknownorhereafterdeveloped. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publicationdoesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexempt fromtherelevantprotectivelawsandregulationsandthereforefreeforgeneraluse. Thepublisher,theauthorsandtheeditorsaresafetoassumethattheadviceandinformationinthis book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, express or implied, with respect to the material contained hereinorforanyerrorsoromissionsthatmayhavebeenmade. Printedonacid-freepaper SpringerInternationalPublishingAGSwitzerlandispartofSpringerScience+BusinessMedia (www.springer.com) Previous publications Partsofthisthesishavebeenpublishedinthefollowingjournalarticles: • “IdealMolecularWeightDistributionsofMultiblockCopolymersPrepared viaRAFTPolymerization” B.Ebeling,M.Eggers,P.Vana,Macromolecules2010,43(24),10283–10290. • “MultiblockCopolymersofStyreneandButylAcrylateviaPolytrithiocarbonate- MediatedRAFTPolymerization” B.Ebeling,P.Vana,Polymers2011,3(2),719–739. • “RAFT-PolymerswithSingleandMultipleTrithiocarbonateGroupsasUni- formGold-NanoparticleCoatings” B.Ebeling,P.Vana,Macromolecules2013,46(12),4862–4871. • “Spherical Gold-Nanoparticle Assemblies with Tunable Interparticle Dis- tancesMediatedbyMultifunctionalRAFTPolymers” C.Rossner,B.Ebeling,P.Vana,ACSMacroLetters2013,2,1073–1076. • “OberflächennachMaß” B.Ebeling,F.Ehlers,P.Vana,NachrichtenausderChemie2014,62,24–28. • “FlippingthePressure-andTemperature-DependentCloud-PointBehavior intheCononsolvencySystemofPoly-(N-isopropylacrylamide)inWaterand Ethanol” B.Ebeling,S.Eggers,M.Hendrich,A.Nitschke,P.Vana,Macromolecules 2014,47(4),1462–1469. • “ComparisonofMonomethoxy-,Dimethoxy-,andTrimethoxysilaneAnchor GroupsforSurface-InitiatedRAFTPolymerizationfromSilicaSurfaces” D.Hübner,V.Koch,B.Ebeling,J.Mechau,J.E.Steinhoff,P.Vana,Journalof PolymerScience,PartA:PolymerChemistry2014,53(1),103–113. • “DesignStrategiesfortheFabricationofTailoredNanocompositesviaRAFT Polymerization” C.Rossner,B.Ebeling,P.Vana,ACSSymposiumSeries2015,inpress. v Supervisor’s foreword Reversibledeactivationradicalpolymerization(RDRP),formerlyalsoknownas controlledradicalpolymerizationorlivingradicalpolymerization,hasbecomeone ofthemostprominentmethodsinpolymersciencefortailoringthearchitectureof syntheticpolymers.ReversibleAddition–FragmentationchainTransfer(RAFT) PolymerizationisoneoftheseRDRPprocessesandhasthedistinctadvantageof beingextremelyversatilewithrespecttomonomerchoiceandreactionconditions. Asaconsequence,RAFThasbecomeastandardmethodforsynthesizingpolymers withcomplextopologyanddemandingfunctionalgroups,whichcanbeproduced withthismethodwithrelativeease. RAFTpolymerization,however,alsoshowsgreatpotentialforfunctionalizing surfaceswithwell-definedpolymers,whichcaneitherdirectlybeformedupon the surface via linking the controlling RAFT agents to a specific surface or via graftingpreformedpolymerobtainedbyRAFT.Bothstrategieshavetheirbenefits anddisadvantages,butprovidepathwaystouniquesurfacestructureswhichcannot easilybeobtainedwithalternativemethods.Surface-boundstarpolymers,polymer loops,blockcopolymers,andnetworkstructuresarecurrentlybeingdeveloped, demonstratingtherisingcomplexityofthesematerials.Forobtainingfunctional materials,however,thechoiceofthepartnerthatprovidesthesolidsurfaceisoften ofequalimportance.Nanoparticleshaveattractedmuchattentioninthiscontext, astheyprovidealargesurfaceareaandunfoldspecificfunctionalitiesthatarenot accessiblewithlargerparticles. Thefieldoffunctionalnanocompositesmadeof tailoredpolymerandnanoparticlesofvariousnaturesisthusaveryvividoneand manymaterialswithnewpropertiesarecurrentlyemerging. Goldnanoparticlesareoneofthemostprominentnanoparticlesinthisrespect andtheyareusedas(bio)sensors, inmedicalapplications, forcatalysis, andin manyindustrialapplications(e.g.,cosmetics,foodpackaging,lubricants). Gold and RAFT were long considered to be completely incompatible, as sulfur—the mainactiveelementofanyRAFTagent—isknowntostronglyinteractwithgold surfaces.BastianEbelingdecidedtotacklethisproblemandchosethedevelopment ofnanocompositesmadeofgoldnanoparticlesandfunctionalpolymer—namely thethermoresponsivepoly(NIPAm)—madeviaRAFTpolymerizationastopicfor hisPhDthesis.Thegoaloftheprojectwastoevenlydispersegoldnanoparticles vii viii Supervisor’sforeword inthefunctionalpolymermatrixinordertoarriveatnewsensormaterials, in whichsurfaceplasmonresonancesignalscanbeusedasameasureforinterparticle distancesthatrespondtoexternalstimuli.Theprobabilityofsuccessforthisproject appearedtoberatherlowinthebeginning,butBastianEbelingshowedrealcom- mitmentbyturningmanyobviousdisadvantagesofthesystemintobenefitsand exploitingthespecificcharacteristicsofthesystem,leadingtheprojecttoasuperb completion.Hedesignedthesenanocompositesdirectlyfromscratch,developing andexploringallbuildingblocksindividuallyinanextremelysystematicway.The verywellinvestigatedcomponentswerefinallycombinedtogenerateastonishingly regularnanocomposites,whichnotonlyconstituteanewclassofmaterials,butalso provideasystemthatcanbeusedforprobingmacromolecularstructuresofthe matrixpolymer.Byinvestigatingtheresponsivenessofthepolymermatrix,healso madesubstantialcontributionstothethermodynamicunderstandingoftheLCST behaviorofpoly(NIPAm). Theexperimentalapproachesforlinkingpolymerto goldnanoparticles,whichhedevelopedduringhisthesis,areinvaluableforfurther progressinthisfieldandhavealreadysparkednewmaterialdesignstrategies,such asplanet–satellitestructures,whichhavenotbeenaccessiblebefore. ThePhDthesisbyBastianEbelingisineveryessenceoutstanding:Itdescribes excellentscience,isenjoyabletoread,andalsolooksgreat.Itwasarealpleasure andprivilegeformetosuperviseBastianduringhisdoctorateandIamdeeply convincedthatwewillseemanymoreexcellentpublicationsbyhim.Iwishhim theverybestforhisfuture. Göttingen,27.11.2014 Prof.Dr.PhilippVana Preface and acknowledgements ThisbookisthefinalrevisedversionofthethesisforwhichIobtainedthe“Doktor- grad(Doctorrerumnaturalium)”fromthe“Georg-August-UniversitätGöttingen”. ItsummarizestheresearchIperformedintheMacromolecularChemistryGroup ofProf.Dr.PhilippVanaatthe“InstitutfürPhysikalischeChemie”from2010to 2014.IamhonoredthatthisthesiswasalsoawardedtheRichard-Zsigmondyprize forGöttingen’sbestchemistrythesisin2014. Theunderlyingworkwouldhavebeenimpossibletocompletewithoutreceiving supportandhelpinanumberofdifferentways. Ratherthanhidingtheacknow- ledgementsattheendofthisbook,Ifeelthattheonlyappropriateplacetorecognize severalspecialpeopleisintheveryfirstpages. Firstofall,IwanttoextendmysincerestthankstomymainsupervisorProf. Dr.PhilippVanaforhisextraordinaryscientificguidance,hisincrediblemotiva- tionalcapabilities,andforshowingperpetualconfidenceinmyskills. Ialsowanttothankmyco-supervisorProf.Dr.Hans-UlrichKrebsforhisfriendly personalsupportandalsoasarepresentativeforhisgroupandthewhole“Institut fürMaterialphysik”.Theinterdisciplinarycooperationwasextremelyvaluablefor me.ItwasespeciallyhelpfulthatIwasgiventheopportunitytoregularlyworkwith theirtransmissionelectronmicroscope.Withinthecourseofthepresentedstudies, Itookalargenumberofmicrographs,severalofwhichcanbeseeninthisthesis andsignificantlycontributetotheinformativevalueofthiswork(mostnotablyin Sections4.1and5.1andinChapter8.2).Dr.Peter-JoachimWilbrandtandMatthias Hahnparticularlyhelpedmebyofferingplentyofassistancewiththeinstrument andthoroughlyrefreshingmyunderstandinginoptics. IwouldliketoexpressmygratitudetoProf. Dr.MichaelBubackforvaluable andinterestingdiscussionsandfortheopportunitytoworkwiththehigh-pressure apparatus (Chapter 6). Concerning these experiments, Dr. Hans-Peter Vögele providedindispensabletechnicaladviceandSandraLotzeandHeikeRohmann offeredgreatpracticalsupport,forwhichIamalsoverygrateful. I thank Martin Eggers for his assistance in the creation of the script for the processingofAFMimages(Section4.2). Thebackgroundofthisthesis’original coverillustration(Figure1)isactuallyarealmicroscopicimageofpolymer-coated goldnanocrystalsonaglasssurface(Section8.3.2.1)thatwasconvertedintoa3- ix x Prefaceandacknowledgements Fig.1:Originalcoverofthisthesis. dimensionalmeshusingthisscript.Theoriginalsceneisapproximately200times smallerinwidththanahumanhair. Iconsidermyselfveryluckytohavesupervisedacoupleofhighlytalentedstu- dents,thatcontributedpracticallytosomeoftheexperimentspresentedhere:Stefan Ringe(double-anchorRAFTagent,Sections5.2.1and7.1),JannikMechau(mono- functionalsilylanchor,Sections5.2.2and7.2),andAnnikaNitschke(high-pressure cloudpoints,Chapter6)workedinourlabintheframeworkoftheirbachelortheses. SteffenEggersandMichaelHendrich(alsohigh-pressurecloudpoints)didtheir practicallabcourseundermysupervision.Myspecialthanksgotoallofthem. Itwasverypleasanttobeabletoworkinthefriendly,supportive,andproductive atmosphereoftheVana/Bubackgroup.Iwarmlythankallofmyformercolleagues and representativelylistthe people with whom Ispentmore timein the office: CathrinConrad,NadjaFörster,HendrikKattner,VanessaKoch,JoachimMorick, WibkeMeiser,andKatharinaTietz.
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