Thesis (Ph. D.)--West Virginia University, 2006. / Title from document title page. Document formatted into pages; contains xx, 149 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 144-149).

The shear force mechanism has been utilized as a distance regulation method in scanning probe microscopes. However, the origin of shear force is still unclear. One of the most important reasons for the shear-force damping is due to the presence of a water contamination layer at the sample surface in ambient conditions. Understanding the behavior of such mesoscopic fluid-like films is of significance for studies of not only scanning probe microscopy but also other complex surface phenomena, such as nanotribology, lubrication, adhesion, wetting, and the microfluidity of biological membranes. This thesis investigates, in particular, the dynamics of mesoscopic fluids confined between two sliding solid boundaries. When fluids are constrained to nanometer-sized regions, their physical properties can greatly differ from those displayed by bulk liquids. To gain an insight into the fundamental characteristics of the confined fluid films, we exploit the versatile capabilities of the novel shear-force/acoustic near-field microscope (SANM), which is able to concurrently and independently monitor the effects of the fluid-mediated interactions acting on both the microscope's probe and the sample to be analyzed. Two signals are monitored simultaneously during each experimental cycle: the tuning fork signal, which is the oscillation amplitude of the probe and gives access to the shear force; and acoustic signal, which is detected by an acoustic sensor placed under the sample. Systematic experiments are carried out to investigate the effects of probe geometry, environmental humidity, and chemical properties of probe and sample surface (water affinity: hydrophobicity or hydrophilicity) on the probe-sample interactions, expressing the influence of the fluid-like contamination films.

One-color resonance two-photo ionization (R2PI) spectra of mixed clusters of styrene molecule (S) with polar molecules [water (W), methanol (M), ethanol (E), and trifuoroethanol (T)] were measured through the S1←S0 transition of the styrene molecule. The spectra reveal a rapid increase in complexity with the number of polar molecules in the cluster, associated with van der Waal modes and isomeric forms. The spectral shifts of the cluster origins from the S1-S0 transition of the bare styrene molecule reflect the nature of the intermolecular interactions within the binary clusters. The obtained R2PI spectra xv were compared with the spectra of the analogous benzene containing clusters. The styrene-water and the styrene-methanol complexes exhibited very different spectral shifts and structures as compared to the benzene-water and benzene-methanol complexes, respectively. The favorable interactions of polar molecules with the olefin group of styrene may explain the strong inhibition effects of exerted by small concentrations of water and alcohols on the cationic polymerization of styrene. Size-specified intracluster proton transfer reactions were observed for mixed clusters of styrene dimer with water, methanol and ethanol molecules. It was proposed that the polar molecules tend to aggregate around the olefin center, which promotes the transfer of the charge from the propagating chain to the hydrogen-bonded polar molecules subcluster. The minimum number of polar molecules required for a proton transfer to take place exothermically depends on the proton affinity of the polar molecules subcluster. The estimated upper limit value for the proton affinity of styrene dimer radical was evaluated based on the energetic of the proton transfer reaction to be ≤ 220.4 kcal/mol. No intracluster reaction was observed for styrene-trifluoroethanol (STn) system. In order to provide a comparison between the styrene and benzene systems, the benzene-ethanol (BEn) and benzene-trifluoroethanol (BTn) clusters were studied by using the R2PI technique via the 6¹0 transition of the benzene molecule. Both dissociative electron transfer and dissociative proton transfer reactions were observed within the BEn clusters, where n = 2 and 3, respectively. Proton transfer reactions were observed following dissociative electron transfer reactions within the (BTn) clusters, where n = 4, to generate the protonated clusters (H+Tn).

Neste trabalho obtivemos o coeficiente de normalização da parte não ressonante da reação de captura 3H(alpha,gama)7Li (ou alternativamente, o fator S astrofísico) aplicando o método indireto ANC (Coeficientes de Normalização Assintótica) para a reação de transferência elástica do sistema 7Li + 4He. Essa reação de captura é de suma relevância na nucleosíntese de elementos leves no Universo primordial. Nesse método, o fator espectroscópico (ou alternativamente, o ANC) é obtido pela investigação de uma reação de transferência periférica que contenha como vértice a correspondente reação de captura. Reações de transferência têm normalmente dois vértices e um deles deve ser conhecido para que possamos obter o outro. No caso de uma transferência elástica, cuja característica é que o canal de saída elástico e de transferência são os mesmos, existe a vantagem da necessidade de consideração de apenas um vértice. Assim, uma análise combinada da distribuição angular para o espalhamento elástico 4He(7Li,7Li)4He, e para a reação de transferência 4He(7Li,4He)7Li, permitiu a extração do fator espectroscópico e consequentemente do ANC para o estado ligado <3He|4He>=7Li de uma forma única. As distribuições angulares para esses processos foram medidas no Laboratório Pelletron de São Paulo em duas energias de centro de massa 9.67 MeV e 10.62 MeV. Utilizamos nessas medidas feixes de 7Li obtidos no acelerador Pelletron com as energias de laboratório de 26.6 e 29.2 MeV. Empregamos um alvo gasoso de 4He e um sistema de colimadores de dupla-fenda na detecção. As partículas de 7Li espalhadas elasticamente e as partículas alfa da reação de transferência foram ambas detectadas em ângulos de laboratório diânteiros por um sistema de telescópios delta E - E com detectores de silício. Um código de simulação de Monte Carlo foi desenvolvido para calcular o ângulo sólido para esse sistema de fendas em ângulos próximos de zero grau. Um conjunto de parâmetros globais do Modelo Óptico foi obtido da análise das distribuições angulares do espalhamento elástico do sistema 7Li + 4He, juntamente com outras distribuições angulares obtidas da literatura em diferentes energias (~ 7-32 MeV). Os parâmetros do potencial óptico encontrados foram usados em uma análise de DWBA (Aproximação de Born de Ondas Distorcidas) para descrever a contribuição da reação de transferência de um tritio nas distribuições angulares. O fator espectroscópico obtido para o sistema ligado <3He|4He>=7Li foi S = 0.55+-0.03 e o coeficiente ANC C2 = 17.5 +- 1.0 fm-1. Com estes resultados, a seção de choque de captura para a reação 3H(alpha,gama)7Li e o respectivo fator S astrofísico foram calculados. / The normalization coefficient for the non-resonant part of the 3H(alpha,gama)7Li capture reaction (or alternately, the astrophysical S-factor) was obtained with the indirect method ANC (Asymptotic Normalization Coefficients). In this method the spectroscopic factor (or alternately, the ANC) is extracted from the investigation of a peripheral transfer reaction, which involves the same vertex as the corresponding capture reaction. Usually transfer reactions have two vertexes and the spectroscopic factor for one of them has to be known to obtain the other. In this work we investigate the 4He(7Li,4He)7Li elastic transfer reaction to obtain the spectroscopic factor and ANC for the 4He + t = 7Li bound system. The elastic transfer process, where the elastic and transfer exit channels are the same, has the advantage of having only one unknown vertex. Thus, the combined analysisof the angular distribution for elastic 4He(7Li,7Li)4He, and transfer process 4He(7Li,4He)7Li, allowed the extraction of the spectroscopic factor (and ANC) for the <3H|4He>=7Li bound system in an unique way. Angular distributions for these processes were measured at the Pelletron Laboratory at the center of mass energies of 9.67 MeV and 10.62 MeV. In these measurements, the 7Li beams with 26.6 MeV and 29.2 MeV were obtained from the Sao Paulo Pelletron accelerator. A 4He gas target and a double-slit collimator system were used. The 7Li scattered particles and alpha particles from transfer reaction were both detected at forward angles by a set of delta E - E silicon detectors telescopes. A Monte Carlo simulation code was developed to calculate the solid angle for the collimator system near the zero degree. A global optical potential parameters set for the 7Li + 4He system were defined using the measured elastic scattering angular distribution and other angular distributions obtained from the literature at different energies (from ~ 7-32 MeV). These optical potential parameters were used in the DWBA (Distorted Wave Born Approximation) analysis to describe the tritium transfer reaction contribution in the angular distributions. The obtained spectroscopic factor for the <3H,4He>=7Li bound system is S = 0.55+-0.03 and the ANC coefficient C2 = 17.5+-1.0 fm-1. With these results, the 3H(alpha,gama)7Li direct capture cross sections and astrophysical S-factor were calculated.

Proton exchange membrane (PEM) fuel cells are at the forefront among different types of fuel cells and are likely to be important power sources in the near future. PEM is a key component of the PEM fuel cells. The objective of this research is to investigate the fundamental aspects of PEM in terms of thermodynamics and proton transport in the membrane, so that the new proton conducting materials may be developed based on the detailed understanding. Since the proton conductivity increases dramatically with the amount of water in PEM, it is important to maintain a high humidification during the fuel cell operation. Therefore, the water uptake characteristics of the membrane are very important in developing fuel cell systems. Thermodynamic models are developed to describe sorption in proton-exchange membranes (PEMs), which can predict the complete isotherm as well as provide a plausible explanation for the long unresolved phenomenon termed Schroeder¡¯s paradox, namely the difference between the amounts sorbed from a liquid solvent versus from its saturated vapor. The sorption isotherm is a result of equilibrium established in the polymer-solvent system when the swelling pressure due to the uptake of solvent is balanced by the surface and elastic deformation pressures that restrain further stretching of the polymer network. The transport of protons in PEMs is intriguing. It requires knowledge of the PEM structure, water sorption thermodynamics in PEM, proton distribution in PEM, interactions between the protons and PEM, and proton transport in aqueous solution. Even proton conduction in water is anomalous that has received considerable attention for over a century because of its paramount importance in chemical, biological, and electrochemical systems. A pore transport model is proposed to describe proton diffusion at various hydration levels within Nafion¢ÃƒÂ§ by incorporating structural effect upon water uptake and various proton transport mechanisms, namely proton hopping on pore surface, Grotthuss diffusion in pore bulk, and ordinary mass diffusion of hydronium ions. A comprehensive random walk basis that relates the molecular details of proton transfer to the continuum diffusion coefficients has been applied to provide the transport details in the molecular scale within the pores of PEM. The proton conductivity in contact with water vapor is accurately predicted as a function of relative humidity without any fitted parameters. This theoretical model is quite insightful and provides design variables for developing high proton conducting PEMs. The proton transport model has been extended to the nanocomposite membranes being designed for higher temperature operation which are prepared via modification of polymer (host membrane) by the incorporation of inorganics such as SiO2 and ZrO2. The operation of fuel cells at high temperature provides many advantages, especially for CO poisoning. A proton transport model is proposed to describe proton diffusion in nanocomposite Nafion¢ÃƒÂ§/(ZrO2/SO42-) membranes. This model adequately accounts for the acidity, surface acid density, particle size, and the amount of loading of the inorganics. The higher proton conductivity of the composite membrane compared with that of Nafion is observed experimentally and also predicted by the model. Finally, some applications of PEM fuel cells are considered including direct methanol fuel cells, palladium barrier anode, and water electrolysis in regenerative fuel cells.

Tobacco smoke particulate matter (PM) is a complex mixture of condensed organic compounds, with about 5 to 10% water. Its general properties are similar in some respects to that of atmospheric organic aerosol PM and thus provides a useful surrogate when studying atmospheric PM. Due to its ability to undergo acid-base chemistry, nicotine is of particular interest in the tobacco smoke system. The gas/particle partitioning of nicotine depends on the protonation state of nicotine in the particles, so the distribution of nicotine between these phases provides a means of understanding the acid-base balance in the tobacco smoke system. The goal of this work is to develop an acid-base balance for mainstream tobacco smoke that accounts for the extent of protonation of nicotine. Samples of extracted smoke particulate matter from seven brands of cigarettes were analyzed by ion chromatography (IC) and titration by both acid (HCl) and base (lithium phenoxide) for comparison with nicotine data collected by colleagues. IC analysis was used to quantify tracers of known acidic and basic species in tobacco smoke. Anion tracers for acids included: glycolate, acetate, formate, lactate, chloride, nitrite, sulfate, and nitrate. The cation tracers for base were ammonium, sodium, and potassium. The tobacco smoke extracts were also analyzed after acidification by the HCl titrant for changes in ammonia and organic acid concentrations to determine whether "bound" forms of these compounds were present in the PM. The titration data provided total concentrations of weak acid and bases in the samples. This titration data was compared with the concentrations of the tracers for weak acids and bases (along with the quantification of total nicotine by colleagues) to determine whether the IC analyses were accounting for all of the important species. The results of this comparison show that these analyses missed relevant species in the tobacco smoke system. As tobacco smoke PM is a complex organic mixture, the ability of acid species to protonate nicotine will be different than in aqueous media. The acidic species of interest were assumed to be either strong or weak, with the strong species assumed to be fully ionized after protonation of nicotine. Some portion of the weak acid species could then protonate any available nicotine. An electroneutrality equation (ENE) was developed for the tobacco smoke PM and populated using the IC data and the nicotine data obtained by colleagues. Using this ENE, the extent ionization of the weak acids species (α1A) and the net reaction constant for the protonation of nicotine by these weak acids (K*) was estimated. However, interpretation of the results were complicated by the underrepresentation of the pertinent weak acid species in our IC analyses. This study concluded that further work is needed to identify the missing weak acid and base species to obtain a better representation of the acid-base balance in tobacco smoke PM and to understand the ability of these weak acid species to protonate nicotine.

Thesis (Ph. D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2009. / Committee Chair: Bridgette Barry; Committee Member: El-Sayed, Mostafa; Committee Member: Fahrni, Christoph; Committee Member: Kröger, Nils; Committee Member: McCarty, Nael. Part of the SMARTech Electronic Thesis and Dissertation Collection.

Neste trabalho obtivemos o coeficiente de normalização da parte não ressonante da reação de captura 3H(alpha,gama)7Li (ou alternativamente, o fator S astrofísico) aplicando o método indireto ANC (Coeficientes de Normalização Assintótica) para a reação de transferência elástica do sistema 7Li + 4He. Essa reação de captura é de suma relevância na nucleosíntese de elementos leves no Universo primordial. Nesse método, o fator espectroscópico (ou alternativamente, o ANC) é obtido pela investigação de uma reação de transferência periférica que contenha como vértice a correspondente reação de captura. Reações de transferência têm normalmente dois vértices e um deles deve ser conhecido para que possamos obter o outro. No caso de uma transferência elástica, cuja característica é que o canal de saída elástico e de transferência são os mesmos, existe a vantagem da necessidade de consideração de apenas um vértice. Assim, uma análise combinada da distribuição angular para o espalhamento elástico 4He(7Li,7Li)4He, e para a reação de transferência 4He(7Li,4He)7Li, permitiu a extração do fator espectroscópico e consequentemente do ANC para o estado ligado <3He|4He>=7Li de uma forma única. As distribuições angulares para esses processos foram medidas no Laboratório Pelletron de São Paulo em duas energias de centro de massa 9.67 MeV e 10.62 MeV. Utilizamos nessas medidas feixes de 7Li obtidos no acelerador Pelletron com as energias de laboratório de 26.6 e 29.2 MeV. Empregamos um alvo gasoso de 4He e um sistema de colimadores de dupla-fenda na detecção. As partículas de 7Li espalhadas elasticamente e as partículas alfa da reação de transferência foram ambas detectadas em ângulos de laboratório diânteiros por um sistema de telescópios delta E - E com detectores de silício. Um código de simulação de Monte Carlo foi desenvolvido para calcular o ângulo sólido para esse sistema de fendas em ângulos próximos de zero grau. Um conjunto de parâmetros globais do Modelo Óptico foi obtido da análise das distribuições angulares do espalhamento elástico do sistema 7Li + 4He, juntamente com outras distribuições angulares obtidas da literatura em diferentes energias (~ 7-32 MeV). Os parâmetros do potencial óptico encontrados foram usados em uma análise de DWBA (Aproximação de Born de Ondas Distorcidas) para descrever a contribuição da reação de transferência de um tritio nas distribuições angulares. O fator espectroscópico obtido para o sistema ligado <3He|4He>=7Li foi S = 0.55+-0.03 e o coeficiente ANC C2 = 17.5 +- 1.0 fm-1. Com estes resultados, a seção de choque de captura para a reação 3H(alpha,gama)7Li e o respectivo fator S astrofísico foram calculados. / The normalization coefficient for the non-resonant part of the 3H(alpha,gama)7Li capture reaction (or alternately, the astrophysical S-factor) was obtained with the indirect method ANC (Asymptotic Normalization Coefficients). In this method the spectroscopic factor (or alternately, the ANC) is extracted from the investigation of a peripheral transfer reaction, which involves the same vertex as the corresponding capture reaction. Usually transfer reactions have two vertexes and the spectroscopic factor for one of them has to be known to obtain the other. In this work we investigate the 4He(7Li,4He)7Li elastic transfer reaction to obtain the spectroscopic factor and ANC for the 4He + t = 7Li bound system. The elastic transfer process, where the elastic and transfer exit channels are the same, has the advantage of having only one unknown vertex. Thus, the combined analysisof the angular distribution for elastic 4He(7Li,7Li)4He, and transfer process 4He(7Li,4He)7Li, allowed the extraction of the spectroscopic factor (and ANC) for the <3H|4He>=7Li bound system in an unique way. Angular distributions for these processes were measured at the Pelletron Laboratory at the center of mass energies of 9.67 MeV and 10.62 MeV. In these measurements, the 7Li beams with 26.6 MeV and 29.2 MeV were obtained from the Sao Paulo Pelletron accelerator. A 4He gas target and a double-slit collimator system were used. The 7Li scattered particles and alpha particles from transfer reaction were both detected at forward angles by a set of delta E - E silicon detectors telescopes. A Monte Carlo simulation code was developed to calculate the solid angle for the collimator system near the zero degree. A global optical potential parameters set for the 7Li + 4He system were defined using the measured elastic scattering angular distribution and other angular distributions obtained from the literature at different energies (from ~ 7-32 MeV). These optical potential parameters were used in the DWBA (Distorted Wave Born Approximation) analysis to describe the tritium transfer reaction contribution in the angular distributions. The obtained spectroscopic factor for the <3H,4He>=7Li bound system is S = 0.55+-0.03 and the ANC coefficient C2 = 17.5+-1.0 fm-1. With these results, the 3H(alpha,gama)7Li direct capture cross sections and astrophysical S-factor were calculated.

In part 1 of this thesis, the antidiabetic activity of a series of novel oxovanadium(IV) complexes was investigated. A range of bidentate N,O-donor ligands, which partially mimic naturally occurring bioligands, were prepared and reacted with the vanadyl ion to form the corresponding bis-coordinated complexes. Initially, 2-(2ˊ-hydroxyphenyl)-1R-imidazoline (where R = H, ethyl and ethanol) ligands were prepared. The aqueous pH-metric chemical speciation was investigated using glass electrode potentiometry which allowed for the determination of protonation and stability constants of the ligands and complexes, respectively. The species distribution diagrams generated from this information gave an indication of how the complexes might behave across the broad pH range experienced in the digestive and circulatory systems. This information was used to create an improved 2nd generation of ligands that were constructed by combining the imidazole and carboxylic acid functionalities. These corresponding bis[(imidazolyl)carboxylato]-oxovanadium(IV) complexes displayed a broader pH-metric stability. Both sets of complexes improved glucose uptake and reduced coagulation in vitro. In part 2 of this thesis, a range of homogeneous and heterogeneous oxovanadium(IV) catalysts were prepared. Firstly, Merrifield beads were functionalized with ligands from Part 1 and then reacted with vanadyl sulfate to afford the corresponding heterogeneous catalysts. These displayed promising catalytic activity for the peroxide facilitated oxidation of thioanisole, styrene and ethylbenzene as well as the oxidative bromination of phenol red. Smaller imidazole-containing beads with higher surface areas than the Merrifield beads were prepared by suspension polymerization. These beads similarly demonstrated excellent catalytic activity for the oxidation of thioanisole and were highly recyclable. In attempt to increase the exposed catalytic surface area, while retaining the ease of separation achieved in the before mentioned systems, micron to nano sized electrospun fibers containing coordinating ligands were fabricated. The corresponding oxovanadium(IV) functionalized fibers were applied to the oxidation of thioanisole using a continuous flow system. The flexible and porous nature of the fiber mats was well suited to this approach. After optimization of the reactant flow rate and catalyst amount, near quantitative (> 99%) oxidation was achieved for an extended period. In addition, leaching of vanadium was mitigated by modification of the attached ligand or polymer material.

No description available.