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High-Precision Particle Arrangement in Gold‒Polymer-Nanocomposites Using RAFT Polymerization

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High-Precision Particle Arrangement in Gold‒Polymer-Nanocomposites Using RAFT Polymerization High-Precision Particle Arrangement in Gold‒Polymer-Nanocomposites using RAFT Polymerization Dissertation zur Erlangung des mathematisch-naturwissenschaftlichen Doktorgrades “Doctor rerum naturalium” der Georg-August-Universität Göttingen im Promotionsprogramm Gauss der Georg-August University School of Science (GAUSS) vorgelegt von Christian Roßner Göttingen, 2016 Betreuungsausschuss Prof. Dr. Philipp Vana, MBA Institut für Physikalische Chemie Georg-August-Universität Göttingen Prof. Dr. Alec Wodtke Institut für Physikalische Chemie Georg-August-Universität Göttingen Mitglieder der Prüfungskommission Referent Prof. Dr. Philipp Vana, MBA Institut für Physikalische Chemie Georg-August-Universität Göttingen Korreferent Prof. Dr. Alec Wodtke Institut für Physikalische Chemie Georg-August-Universität Göttingen Weitere Mitglieder der Prüfungskommission Prof. Dr. Michael Buback Institut für Physikalische Chemie Georg-August-Universität Göttingen Prof. Dr. Martin Suhm Institut für Physikalische Chemie Georg-August-Universität Göttingen Prof. Dr. Dietmar Stalke Institut für Anorganische Chemie Georg-August-Universität Göttingen Prof. Dr. Claudia Höbartner Institut für Organische Chemie Georg-August-Universität Göttingen Tag der mündlichen Prüfung: 27.09.2016 Abbreviations and Symbols 4-ClMeBnA 4-(chloromethyl)benzyl acrylate ACCN azobis(cyclohexanecarbonitrile) AF(M) atomic force (microscopy) AgNP silver nanoparticle AIBN azobis(isobutyronitrile) approx approximately ATRP atom-transfer radical polymerization AuNP gold nanoparticle br broad signal calcd calculated CCD charge-coupled device CPB concentrated polymer brush d doublet DC DaoudCotton DEGEMA diethyleneglycol ethylmethacrylate DEGMMA diethyleneglycol methylmethacrylate DFT density functional theory DLS dynamic light scattering DMAAM N,N-dimethylacrylamide DMAc N,N-dimethyacetamide DMAEMA N,N-Dimethylaminoethyl methacrylate DMF N,N-diemthylformamide DMSO dimethylsulfoxide DMT Derjaguin-Muller-Toporov DNA deoxyribonucleic acid EELS electron energy loss spectroscopy EDTA ethylenediaminetetraacetic acid EFTEM energy-filtered transmission electron microscopy equiv equivalents ESI electrospray ionization et al. et alii etc et cetera GIF Gatan imaging filter GMA glycidyl methacrylate HBP hyperbranched polymer IFT indirect Fourier Transformation IONP iron oxide nanoparticle IR infrared IUPAC International Union of Pure an Applied Chemistry LAMP lipoic acid 2-hydroxy-3-(methacryloyloxy)-propyl ester LCST lower critical solution temperature LSPR localized surface plasmon resonance m multiplet i MPC 2-(methacryloyloxy)ethyl phosphorylcholine MS mass spectrometry NiPAAM N-isopropylacrylamide NMR nuclear magnetic resonance NMRP nitroxide-mediated radical polymerization NP nanoparticle P(4-ClMeBnA) poly(4-(chloromethyl)benzyl acrylate) PDDF pair-distance distribution function PDMAAM poly(N,N-diemthylacrylamide) PDMAEMA poly(N,N-diemthylaminoethyl methacrylate) PEG poly(ethylene glycol) PEO poly(ethylene oxide) PdNP palladium nanoparticle PGMA poly(glycidyl methacrylate) pH pondus hydrogenii PMAA poly(methacrylic acid) PMMA poly(methyl methacrylate) PMPC poly(2-(methacryloyloxy)ethyl phosphorylcholine) PNiPAAM poly(N-isopropylacrylamide) POEGMA poly(oligo(ethylene glycol) methacrylate) ppm parts per million PS polystyrene PSS polymeric support system PTFE polytetrafluoroethylene PVBC poly(vinylbenzylchloride) PVP poly(vinylpyridine) q quartet RAFT reversible addition−fragmentation chain transfer ref. reference RDRP reversible-deactivation radical polymerization R group RAFT leaving group s singlet SAXS small-angle X-ray scattering SDPB semi-dilute polymer brush SDV styrene-divinylbenzene copolymer SEC size-exclusion chromatography SEM scanning electron microscopy SI surface-initiated SiNP silica nanoparticle stat statistical STEM scanning transmission electron microscopy STEM-SI scanning transmission electron microscopy and spectrum imaging t triplet TE(M) transmission electron (microscopy) TGA thermogravimetric analysis THF tetrahydrofuran ii TOAB tetraoctylammonium bromide TTC trithiocarbonate UV ultraviolet VBC vinylbenzylchloride vis visible VP vinylpyridine XPS X-ray photoelectron spectroscopy Z group RAFT stabilizing group iii Abstract This thesis provides a comprehensive analysis of the scientific background on nanocomposites generated via reversible-deactivation radical polymerization (RDRP) techniques. Starting from this basis, nanocomposites with the special combination of a polymeric part from reversible additionfragmentation chain transfer (RAFT) polymerization and gold nanoparticles were investigated in greater detail. It was shown by means of elemental mapping via scanning transmission electron microscopy and spectrum imaging (STEM-SI) in hybrid gold/RAFT polymer coreshell particles that the RAFT polymers’ sulfur-containing end group is always co- localized with the lateral position of gold cores. This provides, for the first time, microscopic evidence for the claim that the RAFT moiety can be used as an anchoring group for the grafting of polymers to gold nanoparticles. The interaction strength of the trithiocarbonate-type RAFT group used in this work was also investigated employing a specially developed model system and following a literature-known UV/vis-based method for analyzing the Langmuir isotherm of adsorption. For the trithiocarbonate model system studied here, a similar free enthalpy of adsorption (36 kJ mol1) as compared with phenyl dithioesters studied earlier had been obtained. The characteristic features of RAFT polymerization had been exploited for the fabrication of defined particle arrangements. The discovery was made that RAFT polymers with specific macromolecular design can be used to assemble gold nanoparticles into unique nanohybrid architectures. It was demonstrated the possibility to precisely arrange gold nanoparticles in a controllable fashion by rationally tailoring the polymers used. Specifically, two different systems were realized to illustrate this point: (i) Gold nanoparticles from the two-phase BrustSchiffrin synthesis were found by means of transmission electron microscopy (TEM) and dynamic light scattering (DLS) to assemble into globular particle network structures, when they are treated ex situ after their synthesis and work-up with linear RAFT oligomers of styrene featuring trithiocarbonate groups at both their termini (telechelic oligomers) or evenly distributed along the backbone (multifunctional oligomers). Here, the density of the primary gold nanoparticles within the network structures can be controlled by adjusting the degree of polymerization of the oligomeric particle linker, as evidenced by TEM. (ii) Higher-order particle assemblies featuring a hierarchical arrangement of two types of gold nanoparticles can be obtained from gold- coreRAFT-star-polymer-shell scaffold architectures. Such nanohybrid particles are shown to provide free star polymer termini (featuring v trithiocarbonate groups) in the polymeric shell, which are accessible for further functionalization reactions. Addition of a second type of gold nanoparticles to such scaffold architecture leads to the attachment of these particles on the exterior of the polymer shell, resulting in planetsatellite nanostructures. These unique nanoarchitectures had been thoroughly analyzed by a combination of several analytical techniques, including electron microscopy in the dried state and small-angle X-ray scattering for characterization in the colloidally dispersed state. When the planetsatellite structures are cast on surfaces for TEM characterization, it is found that the planetsatellite distance can be tightly controlled by adjusting the degree of polymerization of the star polymer linker. These nanostructures can also be equipped with functional polymer, illustrating the possibility of combining several distinct building units into one highly functionalized and well- defined nanostructure. vi Foreword Humans have always been intrigued by the formation of ordered structures from chaos; this may find its best expression in the fact that already at the very beginning of the developing rational thinking (LÓGOS), the cosmos and its decorative order were central and recurring subjects of debate of the presocratics.1 This fascination for order formation persists, as is exemplified today for example by the study of the assembly of distinct building units into defined architectures performed within the intellectual framework of chemistry:2 It is justified to claim that the formation of structures and their control on different length scales is one of the major driving forces within contemporary chemical sciences. On the length scale of small molecules, chemists had been remarkably successful in synthesizing chemical compounds with intriguing complexity. Also on the larger micrometer-length scale, specific structuring can be successful by using masking techniques3 or lithography.4 The powerful and widely applied lithographic methods, however, currently reach their inherent limitations (dictated by the laser wavelength, numerical aperture of the lens used, and diffusion of the photo-resist) regarding the smallest possible size resolution (< 20 nm). Yet, there is a tremendous demand in further miniaturization of devices for technological applications.5 Consequently, there is vibrant research activity in the precision design of smaller structures and their assembly on substrates (for specific applications).6 Novel strategies are currently under exploration. For example, the precise synthesis
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