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Whole document restricted, see Access Instructions file below for details of how to access the print copy. Note: Thesis now published in various journals, details in the Access Instructions file. / During the past almost three decades, conducting polymers have been the subject of intense scientific and industrial research and development worldwide. A general background of the fundamental principles and concepts of conducting polymers and their applications is presented in Chapter 1. In Chapter 2, the characterization of chemically synthesised emeraldine base polyaniline (EB-PANI), acetone-extracted to remove impurities, is examined. Spectroscopic studies PANI at different levels of oxidation are reported, and the structural changes in as-synthesised EB-PANI upon doping with HCl and iodine vapour are investigated. A maximum in the number of unpaired electron spins was found in 1M HCl doped PANI, corresponding to emeraldine salt PANI (ES-PANI), which indicates that bipolarons form at higher doping levels. Also, a maximum conductivity of 0.478 S cm-1 was observed for 1M HCl doped PANI, and no significant change in the conductivity was observed at higher doping levels. A new mechanism of iodine doping of EB-PANI was proposed, which occurs by the oxidation of the benzenoid diamine units, instead of the quinoid diimine units as previously proposed. In Chapter 3, the incorporation of planar Cu(II) complexes as dopants into ES-PANI was investigated by means of EPR and IR spectroscopy. A decrease in the intensity of the EPR signals from polarons in Cu(II) complex-doped PANI samples was observed, while the Cu(II) anion concentration increases and favors the formation of bipolarons in Cu(II) complex-doped PANI systems. The reactions of EB-PANI following different levels of reduction or HCl doping with CuCl2 aqueous solution are also investigated and new reaction mechanisms are proposed. The conductivities of the resulting samples have also been measured and discussed. The ability of aniline and PANI samples to act as antioxidants using the 1,1-diphenyl-2-picrylhydrazyl (DPPH) free-radical method are investigated by means of UV-VIS, FTIR and EPR spectroscopy in Chapter 4. A study of the kinetics of the reaction between DPPH and aniline showed that the reaction is first order with respect to DPPH and approximately second order with respect to aniline. A further investigation of the mechanism of the aniline/DPPH reaction and products of the reaction (aniline oligomers and DPPHH) by magnetic resonance techniques is discussed in Chapter 5. This study has resulted in the identification for the first time of uncapped dimers and trimers of aniline oligomers in solution by EPR spectroscopy. In Chapter 6, for the first time, the applicability of various 13C and 15N solid-state nuclear magnetic resonance (SSNMR) techniques in the investigation of the changes in the structure of PANI that occur upon reaction with DPPH radicals was investigated and discussed. The results indicate partial oxidation of PANI samples upon reaction with DPPH, which is consistent with previously obtained FTIR and EPR data in Chapter 4. In Chapter 7, some further research directions and projects involving chemically synthesised PANI are briefly described.

Whole document restricted, see Access Instructions file below for details of how to access the print copy. Note: Thesis now published in various journals, details in the Access Instructions file. / During the past almost three decades, conducting polymers have been the subject of intense scientific and industrial research and development worldwide. A general background of the fundamental principles and concepts of conducting polymers and their applications is presented in Chapter 1. In Chapter 2, the characterization of chemically synthesised emeraldine base polyaniline (EB-PANI), acetone-extracted to remove impurities, is examined. Spectroscopic studies PANI at different levels of oxidation are reported, and the structural changes in as-synthesised EB-PANI upon doping with HCl and iodine vapour are investigated. A maximum in the number of unpaired electron spins was found in 1M HCl doped PANI, corresponding to emeraldine salt PANI (ES-PANI), which indicates that bipolarons form at higher doping levels. Also, a maximum conductivity of 0.478 S cm-1 was observed for 1M HCl doped PANI, and no significant change in the conductivity was observed at higher doping levels. A new mechanism of iodine doping of EB-PANI was proposed, which occurs by the oxidation of the benzenoid diamine units, instead of the quinoid diimine units as previously proposed. In Chapter 3, the incorporation of planar Cu(II) complexes as dopants into ES-PANI was investigated by means of EPR and IR spectroscopy. A decrease in the intensity of the EPR signals from polarons in Cu(II) complex-doped PANI samples was observed, while the Cu(II) anion concentration increases and favors the formation of bipolarons in Cu(II) complex-doped PANI systems. The reactions of EB-PANI following different levels of reduction or HCl doping with CuCl2 aqueous solution are also investigated and new reaction mechanisms are proposed. The conductivities of the resulting samples have also been measured and discussed. The ability of aniline and PANI samples to act as antioxidants using the 1,1-diphenyl-2-picrylhydrazyl (DPPH) free-radical method are investigated by means of UV-VIS, FTIR and EPR spectroscopy in Chapter 4. A study of the kinetics of the reaction between DPPH and aniline showed that the reaction is first order with respect to DPPH and approximately second order with respect to aniline. A further investigation of the mechanism of the aniline/DPPH reaction and products of the reaction (aniline oligomers and DPPHH) by magnetic resonance techniques is discussed in Chapter 5. This study has resulted in the identification for the first time of uncapped dimers and trimers of aniline oligomers in solution by EPR spectroscopy. In Chapter 6, for the first time, the applicability of various 13C and 15N solid-state nuclear magnetic resonance (SSNMR) techniques in the investigation of the changes in the structure of PANI that occur upon reaction with DPPH radicals was investigated and discussed. The results indicate partial oxidation of PANI samples upon reaction with DPPH, which is consistent with previously obtained FTIR and EPR data in Chapter 4. In Chapter 7, some further research directions and projects involving chemically synthesised PANI are briefly described.

Whole document restricted, see Access Instructions file below for details of how to access the print copy. Note: Thesis now published in various journals, details in the Access Instructions file. / During the past almost three decades, conducting polymers have been the subject of intense scientific and industrial research and development worldwide. A general background of the fundamental principles and concepts of conducting polymers and their applications is presented in Chapter 1. In Chapter 2, the characterization of chemically synthesised emeraldine base polyaniline (EB-PANI), acetone-extracted to remove impurities, is examined. Spectroscopic studies PANI at different levels of oxidation are reported, and the structural changes in as-synthesised EB-PANI upon doping with HCl and iodine vapour are investigated. A maximum in the number of unpaired electron spins was found in 1M HCl doped PANI, corresponding to emeraldine salt PANI (ES-PANI), which indicates that bipolarons form at higher doping levels. Also, a maximum conductivity of 0.478 S cm-1 was observed for 1M HCl doped PANI, and no significant change in the conductivity was observed at higher doping levels. A new mechanism of iodine doping of EB-PANI was proposed, which occurs by the oxidation of the benzenoid diamine units, instead of the quinoid diimine units as previously proposed. In Chapter 3, the incorporation of planar Cu(II) complexes as dopants into ES-PANI was investigated by means of EPR and IR spectroscopy. A decrease in the intensity of the EPR signals from polarons in Cu(II) complex-doped PANI samples was observed, while the Cu(II) anion concentration increases and favors the formation of bipolarons in Cu(II) complex-doped PANI systems. The reactions of EB-PANI following different levels of reduction or HCl doping with CuCl2 aqueous solution are also investigated and new reaction mechanisms are proposed. The conductivities of the resulting samples have also been measured and discussed. The ability of aniline and PANI samples to act as antioxidants using the 1,1-diphenyl-2-picrylhydrazyl (DPPH) free-radical method are investigated by means of UV-VIS, FTIR and EPR spectroscopy in Chapter 4. A study of the kinetics of the reaction between DPPH and aniline showed that the reaction is first order with respect to DPPH and approximately second order with respect to aniline. A further investigation of the mechanism of the aniline/DPPH reaction and products of the reaction (aniline oligomers and DPPHH) by magnetic resonance techniques is discussed in Chapter 5. This study has resulted in the identification for the first time of uncapped dimers and trimers of aniline oligomers in solution by EPR spectroscopy. In Chapter 6, for the first time, the applicability of various 13C and 15N solid-state nuclear magnetic resonance (SSNMR) techniques in the investigation of the changes in the structure of PANI that occur upon reaction with DPPH radicals was investigated and discussed. The results indicate partial oxidation of PANI samples upon reaction with DPPH, which is consistent with previously obtained FTIR and EPR data in Chapter 4. In Chapter 7, some further research directions and projects involving chemically synthesised PANI are briefly described.

Whole document restricted, see Access Instructions file below for details of how to access the print copy. Note: Thesis now published in various journals, details in the Access Instructions file. / During the past almost three decades, conducting polymers have been the subject of intense scientific and industrial research and development worldwide. A general background of the fundamental principles and concepts of conducting polymers and their applications is presented in Chapter 1. In Chapter 2, the characterization of chemically synthesised emeraldine base polyaniline (EB-PANI), acetone-extracted to remove impurities, is examined. Spectroscopic studies PANI at different levels of oxidation are reported, and the structural changes in as-synthesised EB-PANI upon doping with HCl and iodine vapour are investigated. A maximum in the number of unpaired electron spins was found in 1M HCl doped PANI, corresponding to emeraldine salt PANI (ES-PANI), which indicates that bipolarons form at higher doping levels. Also, a maximum conductivity of 0.478 S cm-1 was observed for 1M HCl doped PANI, and no significant change in the conductivity was observed at higher doping levels. A new mechanism of iodine doping of EB-PANI was proposed, which occurs by the oxidation of the benzenoid diamine units, instead of the quinoid diimine units as previously proposed. In Chapter 3, the incorporation of planar Cu(II) complexes as dopants into ES-PANI was investigated by means of EPR and IR spectroscopy. A decrease in the intensity of the EPR signals from polarons in Cu(II) complex-doped PANI samples was observed, while the Cu(II) anion concentration increases and favors the formation of bipolarons in Cu(II) complex-doped PANI systems. The reactions of EB-PANI following different levels of reduction or HCl doping with CuCl2 aqueous solution are also investigated and new reaction mechanisms are proposed. The conductivities of the resulting samples have also been measured and discussed. The ability of aniline and PANI samples to act as antioxidants using the 1,1-diphenyl-2-picrylhydrazyl (DPPH) free-radical method are investigated by means of UV-VIS, FTIR and EPR spectroscopy in Chapter 4. A study of the kinetics of the reaction between DPPH and aniline showed that the reaction is first order with respect to DPPH and approximately second order with respect to aniline. A further investigation of the mechanism of the aniline/DPPH reaction and products of the reaction (aniline oligomers and DPPHH) by magnetic resonance techniques is discussed in Chapter 5. This study has resulted in the identification for the first time of uncapped dimers and trimers of aniline oligomers in solution by EPR spectroscopy. In Chapter 6, for the first time, the applicability of various 13C and 15N solid-state nuclear magnetic resonance (SSNMR) techniques in the investigation of the changes in the structure of PANI that occur upon reaction with DPPH radicals was investigated and discussed. The results indicate partial oxidation of PANI samples upon reaction with DPPH, which is consistent with previously obtained FTIR and EPR data in Chapter 4. In Chapter 7, some further research directions and projects involving chemically synthesised PANI are briefly described.

Molecular brushes of poly(2-oxazoline)s (POx) are an intriguing class of polymers as they combine a unique architecture with the properties of POx as a biomaterial. Here, the synthesis of several POx macromonomers with methacrylate end groups and consecutive grafting through polymerization by aqueous atom transfer radical polymerization (ATRP) at room temperature is reported. 1H-NMR spectroscopy and size exclusion chromatography (SEC) confirmed the synthesis of POx molecular brushes with maximum side chain grafting densities, narrow molar mass distributions (Đ ≤ 1.16) and final molar masses corresponding to the initial macromonomer : initiator ratio. Chain extension experiments show high end group fidelity and formation of block copolymer molecular brushes, and kinetic studies revealed a polymerization behavior of oligo(2-methyl-2-oxazoline) methacrylate very similar to the frequently used oligo(ethylene glycol) methacrylate (OEGMA475). Aqueous solutions of POx molecular brushes with poly(2-ethyl- and 2-isopropyl-2-oxazoline) side chains exhibit the typically defined thermoresponsive behavior with a tunable, very narrow and reversible phase transition

Surface engineering with polymer brushes has become one of the most versatile techniques to tailor surface properties of substrates for a broad variety of (bio-) technological applications. We report on a new facile approach to prepare defined and dense polymer brushes on planar substrates by surface-initiated Cu(0) mediated controlled radical polymerization (SI-CuCRP) of numerous vinyl monomers using a copper plate at room temperature. The fabrication of a variety of homo-, block, gradient and patterned polymer brushes as well as polymer brush arrays is demonstrated. The SI-CuCRP was found to be strictly surface-confined, of highly living character, proceeds remarkably fast and results in polymer brushes of very high grafting densities. The brush layer thickness can be modulated by the polymerization time or by the distance of the copper plate to the modified substrate. As the copper plate can be reused multiple times, no additional copper salts are added and only minimal amount of chemicals is needed, the simple and low-cost experimental conditions allows researchers from various fields to prepare tailored polymer brush surfaces for their needs.

This dissertation investigates non-covalent macromolecular chemistry using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) based techniques. The included studies reveal the impact of molecular structure on conformation and binding energetics. Supramolecules that might be too heavy to be dissociated in single collision-induced dissociation (CID) were dissociated using sustained off-resonance collision induced dissociation (SORI-CID) techniques. Relative binding energies and thresholds were evaluated for various macromolecular host-guest systems. Besides the non-covalent binding energies, conformation characterization was undertaken by a novel method to determine collision cross sectional areas using FTICR (CRAFTI, and multi-CRAFTI), initially developed by the Dearden lab. The systems chosen for further understanding of macromolecular interactions include calixarene-alkali metal complexes, cucurbit[5]uril-alkali halide complexes and cryptand-alkali metal complexes. The results were found to be consistent with expected behavior, and strongly correlated with predictions from computations. Size- and shape selectivity, as well as host-guest polarizability, are the main factors that govern the non-covalent macromolecular interactions that control complex conformation and dissociation. The results demonstrate the ability of FTICR to simultaneously determine binding energy, structure and conformation, which are the most important aspects for determination of comprehensive molecular characterization.

På senare tid har forskning syftat till att främja miljövänligare teknik inom alla fält. Det visar sig inom materialframställningen som en önskan att använda material som inte är beroende av olja, inte tillverkade med tungmetaller samt nedbrytbara med en minimal miljöpåverkan. Detta har bland annat gett organiska katalysatorer en större plats inom forskningen. En av dessa är cyclodextrin, en cyklisk oligosackarid som har påvisats bilda makromolekylara komplex med andra molekyler. En aspekt av detta är att den kan hydrolysera polymerer då den bildar komplex med hydrofila molekyler och kan aktivera dessa genom vätebindning. Vilket Harada et. al. visade kunde utnyttjas for att polymerisera cycliska estrar. Detta examensarbete utforskar en del av det arbetet genom att dels verifiera polymerisationstekniken som ar en lösningsmedelsfri polymerisation dels försök till att framstalla en ny dimer av cyclodextrin som ska effektivt kunna polymerisera cycliska estrar mer effektivt an tidigare. Den nya dimern bygger på en thiourea-länk. Aven om polymerisation med vanlig cyclodextrin har visats fungera sa kan den föreslagna  dimern inte polymerisera lika effektivt. Syntesen ar problematisk och annars åtråvarda egenskaper hos cyclodextrin, som makromolekylär komplexbildning, kan inhibera polymerisationen och tidigare uppreningssteg.

Surface engineering with polymer brushes has become one of the most versatile techniques to tailor surface properties of substrates for a broad variety of (bio-) technological applications. We report on a new facile approach to prepare defined and dense polymer brushes on planar substrates by surface-initiated Cu(0) mediated controlled radical polymerization (SI-CuCRP) of numerous vinyl monomers using a copper plate at room temperature. The fabrication of a variety of homo-, block, gradient and patterned polymer brushes as well as polymer brush arrays is demonstrated. The SI-CuCRP was found to be strictly surface-confined, of highly living character, proceeds remarkably fast and results in polymer brushes of very high grafting densities. The brush layer thickness can be modulated by the polymerization time or by the distance of the copper plate to the modified substrate. As the copper plate can be reused multiple times, no additional copper salts are added and only minimal amount of chemicals is needed, the simple and low-cost experimental conditions allows researchers from various fields to prepare tailored polymer brush surfaces for their needs.