<p> Propylene oxide (PO), is a key intermediate in the production of value-added products, such as polyurethanes and propylene glycol. Current industrially practiced methods of propylene epoxidation, including hydrochlorination, epoxidation by organic peroxides, and the Hydrogen Peroxide to Propylene Oxide (HPPO) process either produce PO unselectively, necessitating energy intensive separation processes, produce environmentally damaging byproducts, or require several sequential reaction vessels. A potential solution for these issues exists in the form of a single-step, highly selective gas phase reaction to produce PO. Industrial adoption of a process utilizing this technology has not occurred due to the failure of state-of-the-art Au/TS-1 catalysts, consisting of gold supported on titanium MFI, to meet economic targets for hydrogen use efficiency, selectivity to PO, and PO rate-permass, improvement on all of which has been hindered by a lack of understanding of how Au-TS-1 catalysts fundamentally operate. Therefore, the goal of this work has been to understand the active site requirements and reaction kinetics with the aim of lowering barriers to commercialization of this more environmentally benign process. Once we had developed a general understanding of product inhibition, we applied this knowledge to the kinetics of propylene epoxidation over Au/TS-1 catalysts. We measured gas phase kinetics in a continuous stirred tank reactor (CSTR) free from temperature and concentration gradients. Apparent reaction orders measured at 473 K for H2, O2, and propylene for a series of Au-DP/TS-1 with varied Au and Ti contents were consistent with those reported previously. Co-feeding propylene oxide enabled measurement of the apparent reaction order in propylene oxide and the determination that relevant pressures of propylene oxide reversibly inhibit propylene epoxidation over Au-DP/TS-1, while co-feeding carbon dioxide and water had no effect on the propylene epoxidation rate. The measured reaction orders for propylene epoxidation, after corrected to account for propylene oxide inhibition, are consistent with a ‘simultaneous’ mechanism requiring two distinct, but adjacent, types of sites. H2 oxidation rates are not inhibited by propylene oxide, implying that the sites required for hydrogen oxidation are distinct from those required for propylene epoxidation. 26 We then shifted focus to elucidate structural details of gold active sites and their interaction with Ti active sites. To determine whether the roles of extracrystalline and intracrystalline gold nanoparticles supported on titanosilicate-1 on direct propylene epoxidation are intrinsically different, the kinetics of direct propylene epoxidation were measured in a gas-phase continuous stirred tank reactor (CSTR) over PVP-coated gold nanoparticles (Au-PVP/TS-1) deposited on TS-1 supports. The PVP-coated gold nanoparticles were too large to fit into the micropores of TS-1, even after ligands were removed in situ by a series of pretreatments, as confirmed by both TEM and TGA-DSC. The activation energy and reaction orders for H2, O2, propylene, propylene oxide, carbon dioxide, and water for propylene epoxidation measured on Au-PVP/TS-1 catalysts were consistent with those reported for Au/TS-1 prepared via deposition-precipitation (Au-DP/TS-1). However, while the reaction orders for hydrogen oxidation on Au-PVP/TS-1 were similar to those measured on AuDP/TS-1, a decrease in activation energy from approximately 30 kJ mol−1 for Au-DP/TS-1 to 4-5 kJ mol−1 for Au-PVP/TS-1 suggests there is a change in mechanism, rate-limiting step, and/or active site for hydrogen oxidation. Additionally, an active site model was developed which determines the number of Ti within an interaction range of the perimeter of extracrystalline Au nanoparticles (i.e., the number of Au-Ti active site pairs). Turnover frequencies estimated for this active site model for a dataset containing both Au-DP/TS-1 and Au-PVP/TS-1 were ∼20x higher than any previous report ( 80 s−1 vs. 1-5 s−1 at 473 K) for catalytic oxidation on noble metals, suggesting that the simultaneous mechanism occurring over proximal Au-Ti sites alone is incapable of explaining the observed rate of propylene epoxidation and that short-range migration of hydrogen peroxide is necessary to account for the catalytic rate. The agreement of reaction orders, activation energy, and active site model for propylene epoxidation on both Au-DP/TS-1 and Au-PVP/TS-1 suggests a common mechanism for propylene epoxidation on both catalysts containing small intraporous gold clusters and catalysts with exclusively larger extracrystalline nanoparticles. Rates of hydrogen oxidation were found to vary proportionally to the amount of surface gold atoms. This is also consistent with the hypothesis that the observed decrease in hydrogen efficiency and PO site-time-yield per gold mass with increasing gold loading are driven primarily by the gold dispersion in Au/TS-1 catalysts. </p>

In this study, oligo-porphyrans, obtained by acid hydrolysis of porphyran, were investigated for their H2O2-inducing abilities in the defense responses of P. yezoensis. Oligo-porphyrans with average molecular weights (MWs) lower than 1.43 kDa had H2O2-inducing abilities. In contrast, oligo-porphyrans with average MWs of 6.12 kDa triggered no response. The active oligo-porphyrans were fractioned by anion-exchange chromatography. We found that two distinct mechanisms might be involved in the oligo-porphyran-induced H2O2 release in P. yezoensis. Mixtures of mono-sulfated oligo-galactans with degrees of polymerization (DPs) ranging from 1 to 3 might induce the response through the oxidation of cellular oligosaccharides, which enable P. yezoensis to resist rotting caused by dense incubation. Mixtures of oligo-porphyrans, consisting of 4 ~ 7 monosaccharide residues and 2 ~ 3 sulfate groups, might induce the generation of H2O2 by activation of NADPH oxidase, leading to an oxidative burst in P. yezoensis. The elicitor activity of oligo-porphyrans thus depends on their molecular size.

Screen printed electrodes (SPEs), which are prepared by patterning conductive inks or pastes onto an insulating support (e.g., plastic film), are widely employed as sensing and biosensing platforms due to their ease of fabrication and relatively low cost. This is especially applicable to electrodes of this nature prepared with carbon-based inks (SPCEs). To date, the most successful and significant commercial application of SPEs has been as test strips for glucose meters. Despite the maturity of this technology, SPE research remains very active as improvements in sensitivity and selectivity, which often involve modifying the electrode surface, hold the key to advancing their utility in routine applications and extending their benefits to other target analytes. Recent studies in the Bishop research group have demonstrated that nitrogen-doped SPCEs (N-SPCEs) exhibit enhanced electrochemical response towards hydrogen peroxide (H2O2), a product of oxidase enzyme (e.g., glucose oxidase, lactate oxidase, etc.) reactions and a common target in biosensing strategies. The presence of nitrogen heteroatoms on the carbon surface facilitates breakage of oxygen-oxygen bonds, a key step in reduction of H2O2. Since previous studies showed only modest incorporation of nitrogen species on SPCEs prepared from commercial ink, these studies aim to investigate the possibility of enhancing N-doping by performing a simple pre-treatment strategy that reportedly increases surface oxygen content of SPCEs prior to N-doping. Since surface oxygen sites have been previously reported to be preferentially modified with nitrogen during N-doping strategies, this seems like a promising technique for improving sensitivity of N-SPCEs for H2O2 reduction. To quantify the actuality of these claims, experimental groups were fabricated having undergone no enhancement, pretreatment enhancement only, nitrogen-doping enhancement only, and a combination of the pretreatment and nitrogen-doping enhancements. Here the electrochemical behaviors of pretreated SPCEs, N-SPCEs, and pretreated N-SPCEs for the detection of H2O2 by completing comparative cyclic voltammetry (CV) experiments with and with out the presence of H2O2 and with it present in varying concentrations is compared. It is projected that, if successful, the fabricated electrodes that have undergone both the pretreatment protocol and the nitrogen-doping process will have an increased sensitivity and detection limit towards H2O2.

Nitrogen-doped carbon materials have garnered much interest due to their abilities to behave as electrocatalysts for reactions important in energy production (oxygen reduction) and biosensing (hydrogen peroxide reduction). Here, we demonstrate fabrication methods and determine electrocatalytic properties of nitrogen-doped screen-printed carbon (N-SPCE) electrodes. Nitrogen doping of graphite was achieved through a simple soft-nitriding technique which was then used in lab-formulated screen-printing inks to prepare N-SPCEs. N-SPCEs displayed good electrocatalytic activity, reproducibility and long term stability towards the electrochemical reduction of hydrogen peroxide. N-SPCEs exhibited a wide linear range (20 µM to 5.3 mM), reasonable limit of detection of 2.5 µM, with an applied potential of -0.4 V (vs. Ag/AgCl). We also demonstrate that nitrided-graphite can similarly be used as a platform for the deposition of electrocatalytic platinum nanoparticles, resulting in Pt-N-SPCEs with a lower limit of detection (0.4 µM) and better sensitivity (0.52 µA cm-2 µM-1) towards H2O2 reduction.

No description available.

<p>  </p> <p>Monolithic catalyst beds have been used extensively in other industries and are gaining interest for space propulsion applications. Additive manufacturing of monolithic supports allows for catalyst beds with a wider range of geometries than could be produced using conventional methods, potentially allowing for higher performance monoliths that can compete with conventional packed beds in performance. Achieving these gains requires a consistent, even, and well-adhering washcoating procedure for the additively manufactured supports, one which works well on varied geometry and on support materials that can be readily printed. I conducted an extensive development process on improving methods of surface preparation and coating for high temperature ceramic monoliths that resulted in improvements in the state of the art. The materials and methods used are appropriate for rocket grade hydrogen peroxide, hydrazine, or other monopropellants with similar operating temperatures. Using existing published coating methods resulted in uneven coating distribution and poor adhesion. I demonstrate that this was due to the substrate surface morphology producing a hydrophobic effect. Surface morphology plays a significant role in coating coverage and adhesion and differences in initial support surfaces likely account for much of the variation in results seen across the literature. I present a method of controlled thermochemical surface etching using pure sodium hydroxide at 420°C that can reliably produce a roughened hydrophilic surface from a variety of starting morphologies. I also present several modifications to the primer formulation that improve evenness of coverage, the most significant of which is the inclusion of a surfactant at a concentration of 1 g per 36 g water. The surface treatment and coating formulation improvements combine well and produce an even coating with strong adhesion to the substrate. I also conducted preliminary work on the investigation of novel geometric designs for monolithic catalyst beds, and on the reactivity of different transition metal oxide catalysts for rocket grade hydrogen peroxide decomposition. </p>

Previous studies involving copper (II) complexed with a dissymmetric Schiff base and imidazole derivatives had identified catalase activity of these complexes towards H2O2. Reactions such as this are of great interest due to the important role of copper-based complexes in biological systems. Our research has been conducted to add to the base of knowledge regarding the efforts of other researchers to investigate copper complexes that exhibit similar reactivity as copper-based proteins towards dioxygen. The copper complex chosen for this study contained a tri-dentate Schiff base adduct which, when complexed with an imidazole derivative, limited the manner in which peroxo adducts could bind while providing distinct spectral peaks which were used to conduct kinetic studies. Our results indicate a reaction mechanism by which the role of the complexed copper (II) ion is to activate the peroxo adduct for decomposition through reactions with other peroxide molecules, dioxygen, and water.

No description available.

Parkinson's disease (PD) is a neurodegenerative condition that affects millions of people worldwide. The exact etiology of PD is unknown. However, it is well established that environmental factors contribute to the onset of PD. In particular, chemicals such as the insecticide Rotenone have been shown to increase the death of dopaminergic (DA) neurons by increasing levels of reactive oxygen species (ROS). ROS such as hydrogen peroxide (H2O2) have been shown to be elevated above basal levels in PD patients. Currently, to measure H2O2 concentrations, a commercially available (Amplex® Red) fluorescent assay is used. However, the assay has limitations: it is not completely specific to hydrogen peroxide and can only measure extracellular ROS concentrations. This research focuses on testing an electrochemical sensor that uses cyclic voltammetry to quantitatively determine concentrations of H2O2 released from a cell culture. The sensor was first tested in normal cell culture conditions. Next, chemical interference was reduced and the sensor was optimized for accuracy by altering protein concentrations in the media. Finally, Rotenone was added to a cell culture to induce H2O2 production. Near real-time measurements of H2O2 were taken using the sensor and comparisons made to the fluorescent assay method. Overall, we are trying to determine if the electrochemical sensor can selectively and quantitatively measure H2O2 released from cells. Being able to track the production, migration and concentration of H2O2 in a cell can help researchers better understand its mechanism of action in cell death and oxidative damage, thus getting closer to finding a cure for PD.

Advances in the interconnection technology have played a key role in the continued improvement of the integrated circuit (IC) density, performance and cost. Copper (Cu) metallization, dual damascenes processing and integration of copper with low dielectric constant material are key issues in the IC industries. Chemical mechanical planarization of copper (CuCMP) has emerged as an important process for the manufacturing of ICs. Usually, Cu-CMP process consists of several steps such as the removal of surface layer by mechanical action of the pad and the abrasive particles, the dissolution of the abraded particles in the CMP solution, and the protection of the recess areas. The CMP process occurs at the atomic level at the pad/slurry/wafer interface, and hence, slurries and polishing pads play critical role in its successful implementation. The slurry for the Cu-CMP contains chemical components to facilitate the oxidation and removal of excess Cu as well as passivation of the polished surface. During the process, these slurry chemicals also react with the pad. In the present study, investigations were carried out to understand the effect of hydrogen peroxide (H2O2) as an oxidant and benzotriazole (BTA) as an inhibitor on the CMP of Cu. Interaction of these slurry components on copper has been investigated using electrochemical studies, x-ray photoelectron spectroscopy (XPS) and secondary ion mass spectroscopy (SIMS). In the presence of 0.1M glycine, Cu removal rate was found to be high in the solution containing 5% H2O2 at pH 2 because of the Cu-glycine complexation reaction. The dissolution rate of the Cu was found to increase due to the formation of highly soluble Cu-glycine complex in the presence of H2O2. Addition of 0.01M BTA in the solution containing 0.1M glycine and 5% H2O2 at pH 2 exhibited a reduction in the Cu removal rate due to the formation of Cu-BTA complex on the surface of the Cu further inhibiting the dissolution. XPS and SIMS investigations revealed the formation of such Cu-glycine complex, which help understand the mechanism of the Cu-oxidant-inhibitor interaction during polishing. Along with the slurry, pads used in the Cu-CMP process have direct influence an overall process. To overcome problems associated with the current pads, new application specific pad (ASP) have been developed in collaboration with PsiloQuest Inc. Using plasma enhanced chemical vapor deposition (PECVD) process; surface of such ASP pads were modified. Plasma treatment of a polymer surface results in the formation of various functional groups and radicals. Post plasma treatment such as chemical reduction or oxidation imparts a more uniform distribution of such functional groups on the surface of the polymer resulting in unique surface properties. The mechanical properties of such coated pad have been investigated using nanoindentation technique in collaboration with Dr. Vaidyanathan’s research group. The surface morphology and the chemistry of the ASP are studied using scanning electron microcopy (SEM), x-ray photoelectron spectroscopy (XPS), and fourier transform infrared spectroscopy (FTIR) to understand the formation of different chemical species on the surface. It is observed that the mechanical and the chemical properties of the pad top surface are a function of the PECVD coating time. Such PECVD treated pads are found to be hydrophilic and do not require being stored in aqueous medium during the not-in-use period. The metal removal rate using such surface modified polishing pad is found to increase linearly with the PECVD coating time. Overall, this thesis is an attempt to optimize the two most important parameters of the Cu-CMP process viz. slurry and pads for enhanced performance and ultimately reduce the cost of ownership (CoO).