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<p> Poly(N-isopropylacrylamides) and copolymers of N-(isopropylacrylamide) and N(tetrahydrofurfurylacrylamide) bearing cholesterol substituents were prepared and their solution properties in water and in methanol were studied by dynamic light scattering, turbidity measurements and by fluorescence spectroscopy. These polymers were obtained in two steps: 1) preparation of a reactive polymer; and 2) coupling of cholesterol to the reactive polymer. In one case the reactive group (N-hydroxysuccinimide) was introduced at one chain end, in the other case, the same group was introduced randomly along the polymer chain. Reaction of an amino-terminated cholesteryl derivative with the reactive polymers led to modified polymers in which cholesterol was attached either to one chain end or to a small number of monomer units along the polymer chain. In the latter case, copolymers bearing pyrene and cholesterol were prepared as well. The copolymers were characterized by 1H NMR, IR and UV spectroscopy and their molecular weights were determined. </p> <p> Studies of the cholesterol-bearing polymers in aqueous solution by dynamic light scattering and fluorescence spectroscopy provided evidence for the formation of polymeric micelles via association of the cholesterol groups. Fluorescence probe and label experiments, using pyrene as a chromophore, gave strong indication that the micelle formation is controlled primarily by the cholesterol groups and only to a lesser extent by the architecture and composition of the polymer. </p> / Thesis / Master of Science (MSc)

Water-soluble fullerene containing polymers comprising of poly(2-(dimethylamino) ethyl methacrylate)-fullerene (PDMAEMA-C60) with targeting moieties, poly(oligo(ethylene glycol) methyl ether methacrylate)-C60 (POEGMA-C60), nanocrystalline cellulose-fullerene (NCC-C60) and NCC-C60-POEGMA were synthesized and their solution properties were investigated. PDMAEMA-C60 with galactose targeting moiety was prepared by atom transfer radical polymerization (ATRP) and atom transfer radical addition (ATRA) processes. The self-assembly of galactose functionalized PDMAEMA-C60 structure in aqueous solutions was investigated using dynamic light scattering (DLS) at different pHs. A smaller hydrodynamic radius (Rh) was observed at pH 10 than at pH 3 due to electrostatic repulsion at low pH values. In addition, free PDMAEMA chains induced the demicellization of self-assembled nanostructures caused by the formation of charge transfer complex between PDMAEMA and C60. A well-defined poly(di(ethylene glycol) methyl ether methacrylate–stat-oligo(ethylene glycol) methyl ether methacrylate)-block-poly(di(ethylene glycol) methyl ether methacrylate ((PMEO2MA-stat-POEGMA300)-b-PMEO2) was successfully synthesized at room temperature via a two-step ATRP process. The block copolymer exhibited two thermal transitions at ~ 30 and 45 oC, which was believed to be associated with the formation of micelles and larger aggregates. The Rh of the aggregates increased from 47 to 90 nm, the aggregation number increased from 76 to ~9800 and Rg/Rh increased from 0.75 to 1.2 within the temperature range of 34 to 45oC. Well-defined statistical (PMEO2MA-stat-POEGMA300)-C60 was synthesized via ATRP and ATRA. The lower critical solution temperature (LCST) of (PMEO2MA-stat-POEGMA300)-C60 increased with methanol content in water, exhibiting lower LCSTs than PMEO2MA-stat-POEGMA300 for all methanol/water compositions. Higher critical micelle concentration (CMC) and larger spherical micelles were observed for (PMEO2MA-stat-POEGMA300)-C60 with increasing methanol content. The Rh of the micelles remained constant at temperature below the LCST and increased dramatically at temperature greater than the LCST, and (Rg/Rh) increased from ~ 0.75 to ~ 1.0. Nanocrystalline cellulose (NCC) was modified with water-soluble C60-(β-cyclodextrin) and (PMEO2MA-stat-POEGMA300)-C60) through a radical coupling reaction. NCC-C60-(PMEO2MA-stat-POEGMA300) possessed thermal responsive behavior in water and ~3.5 oC hysteresis associated with the heating/cooling cycles. No observable damage to NCC occurred during the radical coupling reaction as determined by TEM. NCC-C60-(β-cyclodextrin) possessed a similar thermal degradation behavior as NCC except it possessed a broader temperature range. Both NCC-fullerene systems demonstrated a radical scavenging activity when screened with the 2,2-diphenyl-1-picrylhydrazyl (DPPH). In addition, the drug loading and delivery using PDMAEMA-C60 with targeting moieties was explored. Two model drugs, namely fluorescein and pyrene were employed to evaluate the location of drug in the self-assembled structure of PDMAEMA-C60. It was found that the hydrophobic drugs were partitioned between the PDMAEMA shells and the hydrophobic fullerene cores. The drug delivery profiles indicated that PDMAEMA-C60 is an efficient drug carrier, however, it was cytotoxic to cells. The gene transfection efficacy of PDMAEMA-C60 to different cell lines was investigated and the results demonstrated that PDMAEMA-C60 exhibited good gene transfection performance. However, the targeting selectivity to liver cells cannot be determined in both cases. This study demonstrates that nanostructures of stimuli-responsive fullerene polymers can be controlled and manipulated by changing the external environments. Several potential applications, such as in drug and gene delivery, and free radical scavenging can be further explored.

Water-soluble fullerene containing polymers comprising of poly(2-(dimethylamino) ethyl methacrylate)-fullerene (PDMAEMA-C60) with targeting moieties, poly(oligo(ethylene glycol) methyl ether methacrylate)-C60 (POEGMA-C60), nanocrystalline cellulose-fullerene (NCC-C60) and NCC-C60-POEGMA were synthesized and their solution properties were investigated. PDMAEMA-C60 with galactose targeting moiety was prepared by atom transfer radical polymerization (ATRP) and atom transfer radical addition (ATRA) processes. The self-assembly of galactose functionalized PDMAEMA-C60 structure in aqueous solutions was investigated using dynamic light scattering (DLS) at different pHs. A smaller hydrodynamic radius (Rh) was observed at pH 10 than at pH 3 due to electrostatic repulsion at low pH values. In addition, free PDMAEMA chains induced the demicellization of self-assembled nanostructures caused by the formation of charge transfer complex between PDMAEMA and C60. A well-defined poly(di(ethylene glycol) methyl ether methacrylate–stat-oligo(ethylene glycol) methyl ether methacrylate)-block-poly(di(ethylene glycol) methyl ether methacrylate ((PMEO2MA-stat-POEGMA300)-b-PMEO2) was successfully synthesized at room temperature via a two-step ATRP process. The block copolymer exhibited two thermal transitions at ~ 30 and 45 oC, which was believed to be associated with the formation of micelles and larger aggregates. The Rh of the aggregates increased from 47 to 90 nm, the aggregation number increased from 76 to ~9800 and Rg/Rh increased from 0.75 to 1.2 within the temperature range of 34 to 45oC. Well-defined statistical (PMEO2MA-stat-POEGMA300)-C60 was synthesized via ATRP and ATRA. The lower critical solution temperature (LCST) of (PMEO2MA-stat-POEGMA300)-C60 increased with methanol content in water, exhibiting lower LCSTs than PMEO2MA-stat-POEGMA300 for all methanol/water compositions. Higher critical micelle concentration (CMC) and larger spherical micelles were observed for (PMEO2MA-stat-POEGMA300)-C60 with increasing methanol content. The Rh of the micelles remained constant at temperature below the LCST and increased dramatically at temperature greater than the LCST, and (Rg/Rh) increased from ~ 0.75 to ~ 1.0. Nanocrystalline cellulose (NCC) was modified with water-soluble C60-(β-cyclodextrin) and (PMEO2MA-stat-POEGMA300)-C60) through a radical coupling reaction. NCC-C60-(PMEO2MA-stat-POEGMA300) possessed thermal responsive behavior in water and ~3.5 oC hysteresis associated with the heating/cooling cycles. No observable damage to NCC occurred during the radical coupling reaction as determined by TEM. NCC-C60-(β-cyclodextrin) possessed a similar thermal degradation behavior as NCC except it possessed a broader temperature range. Both NCC-fullerene systems demonstrated a radical scavenging activity when screened with the 2,2-diphenyl-1-picrylhydrazyl (DPPH). In addition, the drug loading and delivery using PDMAEMA-C60 with targeting moieties was explored. Two model drugs, namely fluorescein and pyrene were employed to evaluate the location of drug in the self-assembled structure of PDMAEMA-C60. It was found that the hydrophobic drugs were partitioned between the PDMAEMA shells and the hydrophobic fullerene cores. The drug delivery profiles indicated that PDMAEMA-C60 is an efficient drug carrier, however, it was cytotoxic to cells. The gene transfection efficacy of PDMAEMA-C60 to different cell lines was investigated and the results demonstrated that PDMAEMA-C60 exhibited good gene transfection performance. However, the targeting selectivity to liver cells cannot be determined in both cases. This study demonstrates that nanostructures of stimuli-responsive fullerene polymers can be controlled and manipulated by changing the external environments. Several potential applications, such as in drug and gene delivery, and free radical scavenging can be further explored.

The research in this dissertation is focused on the synthesis and characterization of sterically crowded, precisely charged polyelectrolytes based on substituted stilbene comonomers. New sterically crowded polyelectrolytes based on functionalized stilbenes with maleic anhydride or functionalized N-phenylmaleimides were prepared via a "protected" precursor polymer strategy. The polyelectrolyte precursors readily dissolved in organic solvents and were characterized by 1H NMR, SEC, TGA, and DSC. The polyelectrolytes were obtained via simple deprotection chemistries. The use of different combinations of the donor-acceptor comonomer pairs and the alternating copolymerization of these comonomers lead to precise control over charge density and placement of charged groups along the polymer backbone. Analogous styrenic copolymers, for direct comparison to the stilbene structures, were also prepared. Broad peaks in 1H NMR spectra were observed. There were no thermal transitions measured by DSC below the degradation temperature. A strong polyelectrolyte effect, for both stilbene and styrene copolymers, occurred in deionized water and was suppressed by adding NaCl to the polymer solution. These results are not consistent with "rigid" rod polyelectrolytes in which chain collapse in the presence of added salt and chain expansion on dilution should not be observed. In response to these observations persistence length measurements were conducted on the stilbene and styrene copolymers to assess directly the steric crowding effect of added phenyl groups in stilbene copolymers. Both SEC and SAXS measurements were used to obtain persistence lengths. The results from three different approaches, Bohdanecký, graphical and Sharp and Bloomfield Global, were in good agreement. The persistence lengths of stilbene containing copolymers range from 3 to 6 nm and the added phenyl groups increase the rigidity of the polymer chain by about 30-50%. This puts these polymers into a broadly defined "semi-rigid" category of polymers and is consistent with the solution polyelectrolyte effect observed. In dilute solution characterization of stilbene containing polyanions, a 2-step dissociation behavior was observed for the two adjacent carboxylic acids in maleic acid containing polyanions. Stilbene polyanion solutions showed high Rh values in deionized water as shown by DLS measurements and a decrease of Rh values followed by aggregation upon gradual addition of salt. Bimodal peaks were observed in SEC measurements with the copolymer of 4-methylstilbene and maleic anhydride. DLS measurements indicated interchain aggregation as the origin of the apparent high molecular weight fraction. The antiviral activity of the polyanion based on sodium 4-styrenesulfonate and N-(4-sodium sulfophenyl)maleimide was found to be ~50 times higher than the microbicide, sodium poly(styrene sulfonate). The early study of antiviral activities of carboxylated stilbene and styrene polyanions also showed promising results. The synthesis of methyl sulfonate ester-functionalized polyanion precursors was attempted because they can be characterized without the complications caused by directly using charged sulfonate groups. / Ph. D.

Two series of aliphatic hyperbranched (HB) polyesters have been synthesized from 2,2-bis(hydroxymethyl)propionic acid and di-trimethylolpropane using pseudo-one-step or one-step procedure. The structure and properties of these HB polyesters, investigated with different characterization techniques in solution, melt and solid state, were compared between each other, with commercial Boltorn HB polyesters and samples obtained by modification of the end -OH groups with ß-alanine or stearic acid. Seven HB polyesters were fractionated in order to obtain three fractions of each sample. The experimental results obtained from NMR spectroscopy, acid and hydroxyl number titration, GPC, vapour pressure osmometry, MALDI TOF and ESI mass spectrometry indicate that during the synthesis reactivity of terminal and linear -OH groups was not the same and that side reactions occurred in significant amount, which led to the lowering of the number average molar mass and broadening of the molar mass distribution. According to the results obtained from viscosimetry of diluted solutions and dynamic light scattering the best solvents for these HB polyesters are 0.7 mass % solution of LiCl in N,N-dimethylacetamide and N-methyl-2-pyrrolidinon (NMP). The limiting viscosity number and the hydrodynamic radius of the samples increase up to the sixth pseudo generation in these two solvents. Investigated HB polyesters behave as Newtonian liquids in concentrated solutions (c < 50 mass % in NMP) at T < 55 °C. The same was observed for the samples from fourth till sixth pseudo generation in melt at T > 70 °C. At all other experimental conditions used in this work these polymers show shear-thinning behaviour due to the high ability for the aggregation. Thermal stability of investigated HB polyesters increases with increasing number of the pseudo generation. The influence of the procedure for the synthesis and type of end groups on the properties of these polymers is discussed.

yes / There are many polymers formed of acrylate monomers in existence. Here we interrogate four commonly-used examples and study how their solution properties are pH dependent, or how their state of ionisation can affect their solution properties. Poly(acrylic acid) and poly(methacrylic acid) are both polyelectrolytes, with ionisable functional groups that make them stimuli responsive, changing their hydrodynamic volume. Poly(acrylamide) is a mass-produced material used in a variety of industrial applications, often with an anionic and cationic co-monomer, which dictates both its efficacy and impact on the environment. Poly(N-isopropyl acrylamide) is a thermally responsive material with applications in smart bioengineering. In solution, these materials can interact with each other due to competing hydrogen bonding interactions. However, this interpolymer complexation is dependent on both the ionisation, and the conformational state, of the polymers involved. This review focuses on the results from fluorescence tagging and turbidimetric techniques.

Efeitos de solventes tem sido um tema de grande interesse científco. Em particular, o estudo dos efeitos de solventes no espectro eletrônico de absorção tem sua própria motivação e complexidade. Neste trabalho, nós estudamos os efeitos da solução aquosa na estabilidade conformacional e no espectro eletrônico de absorção da molécula Óxido Mesitil (OM). Essa molécula pertence a família das cetonas ,-insaturadas e, semelhantemente aos outros membros da família, ela apresenta transições eletrônicas sensíveis ao solvente. Inicialmente, estudamos os isômeros syn e anti do OM isoladamente usando cálculos quânticos para determinar a energia livre relativa, a barreira de rotação, os momentos de dipolo e as transições eletrônicas de absorção. Nosso melhor resultado mostra que o isômero syn do OM é a conformação mais estável, por cerca de 1.3 kcal/- mol calculado com nível MP2/aug-cc-pVDZ. Com o mesmo nível de cálculo, obtivemos os momentos de dipolo de 2.80 e 3.97 D para os isômeros syn e anti respectivamente, que estão em boa concordância com os valores experimentais de 2.8 e 3.7 D. Para o espectro eletrônico de absorção, analisamos a banda mais intensa, -*, com diferentes funcionais de densidade e funções base. Obtivemos o comprimento de transição de 229 nm calculado com nível TD-B3LYP/6-311++G** para o isômero syn em muito boa concordância com o valor experimental de 231 nm medido em solução de iso-octano (solvente de baixa polaridade). Para realizar os estudos em solução, geramos estruturas supermoleculares dos isômeros do OM em solução aquosa usando simulações computacionais com o método Monte Carlo. Usamos os potenciais Lennard-Jones e Coulomb para descrever as interações intermoleculares com os parâmetros do campo de força OPLS. Verifcamos que as cargas atômicas OPLS não descrevem bem o potencial eletrostático do OM. Portanto, realizamos um processo iterativo para incluir a polarização do soluto na presença do solvente para descrever melhor as interações entre o OM e as moléculas de água. Assim, obtivemos um aumento de cerca de 80% nos momentos de dipolo dos isômeros isolados. Adicionalmente, calculamos a energia livre relativa entre os isômeros em solução aquosa usando teoria de perturbação termodinâmica. Obtivemos que o isômero anti do OM é a conformação mais estável, por cerca de 2.8 kcal/mol. Examinando os efeitos de solvente no espectro eletrônico de absorção do OM, identificamos que existem duas contribuições competindo para o deslocamento da banda -*. Uma contribuição vem da mudança conformacional syn anti do OM devido a mudança de polaridade, baixa alta, do solvente. Essa mudança conformacional provoca um deslocamento para o azul de 1210 cm-1 na transição -*. A outra contribuição vem do efeito do solvente na estrutura eletrônica do OM, que provoca um deslocamento para o vermelho de - 4460 cm-1 nessa transição. Adicionando essas duas contribuições, temos o efeito do solvente total no espectro eletrônico de absorção do OM em solução aquosa. Nosso melhor resultado é um valor médio de 248 nm obtido com 75 cálculos TD-B3LYP/6-311++G** de estruturas supermoleculares estatisticamente descorrelacionadas compostas por um anti-OM rodeado por 14 moléculas de água explícitas embebidas no campo eletrostático de 236 moléculas de água tratadas como cargas pontuais simples. Esse resultado está em muito boa concordância com o resultado experimental de 243 nm em solução aquosa. Sendo assim, este trabalho demonstra que a mudança conformacional syn anti é essencial para entender o deslocamento espectral da transição -* do OM em água. / Solvent effects have been the subject of considerable scientifc interest. In particular, the study of solvent effects in electronic absorption spectroscopy has its own motivation and complexities. In this work we study the effects of the aqueous solution in the conformational stability and the electronic absorption spectrum of the Mesityl Oxide (OM) molecule. This molecule belongs to the family of the ,-unsaturated ketones and, like other members of the family, presents sensitivity to solvent in the absorption transitions. Initially we studied the isolated syn and anti isomers of OM by performing quantum mechanical calculations to obtain the relative free energy, the rotational barrier, the dipole moments and the electronic absorption transitions. Our best result showed that the OM syn isomer is the most stable conformer, by approximately 1.3 kcal/mol calculated with the MP2/aug-cc-pVDZ level. With the same level of calculation, we obtained the dipole moments of 2.80 and 3.97 D for the syn and anti isomers respectively, which are in good agreement with the experimental values of 2.8 and 3.7 D. For the electronic absorption spectrum, we analyzed the most intense band, -*, with different density functional and basis sets. We obtained a transition wavelength of 229 nm calculated with TD-B3LYP/6-311++G** level for the syn isomer in good agreement with the experimental value of 231 nm measured in iso-octane (solvent of low polarity). For performing the in-solution studies, we generated supermolecular structures of the OM isomers in aqueous solution using computer simulations with the Monte Carlo method. We used the Lennard-Jones and Coulomb potentials to describe the intermolecular interactions with the OPLS force field parameters. We found that the OPLS atomic charges do not describe well the electrostatic potential of OM. Therefore we performed an iterative process for including the solute polarization in the presence of the solvent to better describe the interactions between the OM and the water molecules. We obtained an increase of about 80% in the dipole moments of the isolated isomers. Additionally, we calculated the relative free energy between the isomers in aqueous solution using thermodynamic perturbation theory. We found that the anti isomer is the most stable conformer in aqueous solution, by about 2.8 kcal/mol. Examining the solvent effects in the electronic absorption spectrum of OM, we found that there are two competing contributions to the -* band shift. One contribution is due to the syn anti conformational change of OM caused by the low high polarity change of the solvent. This conformational change led to a blue shift of 1210 cm-1 in the * band. The remaining contribution is due to the solvent effect in the electronic structure of OM, which led to a red shift of -4460 cm-1. Adding these two contributions, we obtained the total solvent effect in the electronic absorption spectrum of OM in aqueous solution. Our best result was an average wavelength transition of 248 nm obtained using 75 TD-B3LYP/6-311++G** quantum calculations on statistically uncorrelated supermolecular structures composed by one anti-OM surrounded by 14 explicit water molecules in the electrostatic embedding composed of 236 water molecules described as simple point charges. This result is in very good agreement with the experimental result of 243 nm in aqueous solution. Thus, this work demonstrates that the syn anti conformational change is the essential ingredient to understand the spectral shift of the - * absorption transition of OM in water.

Polyaniline was chemically synthesized at three different temperatures of 25, 0, and -25oC, by oxidative polymerization with ammonium peroxidisulfate at equimolar of aniline to oxidant ratio and 1M HCl. The resulted polyaniline was in a powder form which was characterized by several techniques such as: electrical conductivity, elemental analysis, thermal analysis, wide-angle X-Ray diffraction, and scanning electron microscope. The solution properties of the reduced polymer were studied by viscometry, static and dynamic light scattering. It was found that as the polymerization temperature decreased, the molecular weight, crystallinity, and thermal stability of polyaniline increased, while the electrical conductivity was independent of the polymerization temperature. Moreover, the morphology of the polymer was changed from granular to tubular with reducing polymerization temperature. Viscometry and static light scattering showed that polyaniline has a flexible random coil conformation when dissolved in N-methyl-2-pyrrolidinone which proved to be a good solvent for this polymer. Dynamic light scattering indicated that the polymer solution is a polyelectrolyte with high hydrodynamic radius at low polymer concentrations. All mechanical features except Young&#039 / s modulus of polyaniline-filled low density polyethylene composites became poorer as polyaniline content increased. Moreover, a sudden increase in the electrical conductivity with increasing polyaniline contents was also observed. The conductivity of the tubular composites of multi wall nanotubes (MWNTs)-filled polyaniline increased with increasing MWNTs loading, and became weakly temperature dependent. The morphological analysis indicated that the MWNTs were well dispersed and isolated, and the tubes became crowded proportionally to MWNTs weight percent used in the composites.