High-power diode lasers (HPDL) are being increasingly used in industrial applications. Deposition of nickel from nickel carbonyl (Ni(CO)4) precursor by laser-induced chemical vapor deposition (CVD) was studied with emphasis on achieving high deposition rates. An HPDL system was used to provide a novel energy source facilitating a simple and compact design of the energy delivery system. Nickel deposits on complex, 3-dimensional polyurethane foam substrates were prepared and characterized. The resulting “nickel foam” represents a novel material of high porosity (>95% by volume) finding uses, among others, in the production of rechargeable battery and fuel cell electrodes and as a specialty high-temperature filtration medium. Deposition rates up to ~19 µm/min were achieved by optimizing the gas precursor flow pattern and energy delivery to the substrate surface using a 480W diode laser. Factors affecting the transition from purely heterogeneous decomposition to a combined hetero- and homogeneous decomposition of nickel carbonyl were studied. High quality, uniform 3-D deposits produced at a rate more than ten times higher than in commercial processes were obtained by careful balance of mass transport (gas flow) and energy delivery (laser power). Cross-flow of the gases through the porous substrate was found to be essential in facilitating mass transport and for obtaining uniform deposits at high rates. When controlling the process in a transient regime (near the onset of homogenous decomposition), unique morphology features formed as part of the deposits, including textured surface with pyramid-shape crystallites, spherical and non-spherical particles and filaments. Operating the laser in a pulsed mode produced smooth, nano-crystalline deposits with sub-100 nm grains. The effect of H2S, a commonly used additive in nickel carbonyl CVD, was studied using both polyurethane and nickel foam substrates. H2S was shown to improve the substrate coverage and deposit uniformity in tests with polyurethane substrate, however, it was found to have no effect in improving the overall deposition rate compared to H2S-free deposition process. Deposition on other selected substrates, such as ultra-fine polymer foam, carbon nanofoam and multi-wall carbon nanotubes, was demonstrated. The HPDL system shows good promise for large-scale industrial application as the cost of HPDL energy continues to decrease.

Various α,β-unsaturated carbonyl compounds and derivatives were explored in order to expand the range of substrates for the 1,4-addition of alkenylboronates using 3,3′-disubstituted binaphthols. Enones 2.60 were examined and found to be suitable for conjugate addition under our proposed reaction conditions. The asymmetric 1,4-additions of alkenylboronates to enones 2.60 using catalytic amounts of 3,3′-disubstituted binaphthols was shown to occur with moderate to good yields and high enantioselectivities. The chiral products could serve as enantioenriched substrates for further transformation such as asymmetric reduction, which was performed with good yield and selectivity. The absolute configuration for the alkenylation of enones was also confirmed to be the (R) enantiomer using (S)-3,3′-disubstituted binaphthols via X-ray crystallographic analysis. Investigations into selective Baeyer-Villiger oxidation of 1,4-addition products of enones was also examined. Although the desire ester products were not obtained, intriguing informative findings were still obtained from the investigation.

High-power diode lasers (HPDL) are being increasingly used in industrial applications. Deposition of nickel from nickel carbonyl (Ni(CO)4) precursor by laser-induced chemical vapor deposition (CVD) was studied with emphasis on achieving high deposition rates. An HPDL system was used to provide a novel energy source facilitating a simple and compact design of the energy delivery system. Nickel deposits on complex, 3-dimensional polyurethane foam substrates were prepared and characterized. The resulting “nickel foam” represents a novel material of high porosity (>95% by volume) finding uses, among others, in the production of rechargeable battery and fuel cell electrodes and as a specialty high-temperature filtration medium. Deposition rates up to ~19 µm/min were achieved by optimizing the gas precursor flow pattern and energy delivery to the substrate surface using a 480W diode laser. Factors affecting the transition from purely heterogeneous decomposition to a combined hetero- and homogeneous decomposition of nickel carbonyl were studied. High quality, uniform 3-D deposits produced at a rate more than ten times higher than in commercial processes were obtained by careful balance of mass transport (gas flow) and energy delivery (laser power). Cross-flow of the gases through the porous substrate was found to be essential in facilitating mass transport and for obtaining uniform deposits at high rates. When controlling the process in a transient regime (near the onset of homogenous decomposition), unique morphology features formed as part of the deposits, including textured surface with pyramid-shape crystallites, spherical and non-spherical particles and filaments. Operating the laser in a pulsed mode produced smooth, nano-crystalline deposits with sub-100 nm grains. The effect of H2S, a commonly used additive in nickel carbonyl CVD, was studied using both polyurethane and nickel foam substrates. H2S was shown to improve the substrate coverage and deposit uniformity in tests with polyurethane substrate, however, it was found to have no effect in improving the overall deposition rate compared to H2S-free deposition process. Deposition on other selected substrates, such as ultra-fine polymer foam, carbon nanofoam and multi-wall carbon nanotubes, was demonstrated. The HPDL system shows good promise for large-scale industrial application as the cost of HPDL energy continues to decrease.

Various α,β-unsaturated carbonyl compounds and derivatives were explored in order to expand the range of substrates for the 1,4-addition of alkenylboronates using 3,3′-disubstituted binaphthols. Enones 2.60 were examined and found to be suitable for conjugate addition under our proposed reaction conditions. The asymmetric 1,4-additions of alkenylboronates to enones 2.60 using catalytic amounts of 3,3′-disubstituted binaphthols was shown to occur with moderate to good yields and high enantioselectivities. The chiral products could serve as enantioenriched substrates for further transformation such as asymmetric reduction, which was performed with good yield and selectivity. The absolute configuration for the alkenylation of enones was also confirmed to be the (R) enantiomer using (S)-3,3′-disubstituted binaphthols via X-ray crystallographic analysis. Investigations into selective Baeyer-Villiger oxidation of 1,4-addition products of enones was also examined. Although the desire ester products were not obtained, intriguing informative findings were still obtained from the investigation.

The seasonal and diurnal concentrations of atmospheric carbonyls were measured by the LpDNPH-Cartridge and the microcomputer air sampling device at Nan-Chie and Hsiung-Kong sites in Kaohsiung area. Then, factor analysis and absolute principal component analysis were also used to determine the source apportionment in Kaohsiung area. Total concentrations of carbonyls were higher in Summer than in winter at Nan-Chie and Hsiung-Kong sites. Measurements showed that the highest carbonyls were formaldehyde and acetaldehyde, due to the fact that photochemical activities are stronger in summer than in winter. The concentrations of total carbonyls, formaldehyde, acetaldehyde were showed similar diurnal variations, that highest concentrations were found in the morning and noon, then drop down at afternoon and increased at night. Due to the fact that photochemical activities and vehicle exhausts. C1-C3 ratio indicated the local participation of anthropogenic hydrocarbons was important in the production of carbonyls in the Kaohsiung area. C1/C2 was highest in the summer than in the winter, that photochemical activities cause highest concentrations of formaldehyde, especially in the summer noon. The results of factor analysis and absolute principal component analysis showed that the primary pollution sources at Nan-Chie were traffic exhausts (diesel and gasoline vehicle) and stationary sources (petrochemical and food industry) and restaurant emissions, and the primary pollution sources at Hsiung-Kong were traffic exhausts (diesel and gasoline vehicle), stationary emissions (metal assembly and petrochemical industry) and restaurant emissions.

This study investigated the fuel properties, engine performances, and emissions of two biodiesels and diesel. The fuels examined were D100 (ultra-low sulfur diesel), B20 (20% palm biodiesel +80% ultra-low sulfur diesel) and B100 (palm biodiesel). The fuel properties analysis results showed that the benefits of biodiesel were high cetane value, extremely low sulfur and aromatic contents, and good lubricity. While the defects of biodiesel were high pour point. The particulates emitted from the burning of D100, B100, B20 were mainly fine particulates, also known as young aerosols. Particles smaller than 2.5 µm easily enter the trachea and bronchus via the upper respiratory tract, finally deposit on the alveolus, which could cause severe injury to human health. The emission of soluble organic fraction (SOF) from diesel engine using D100, B100 and B20 were 23.2%, 19.9% and 20.2%, respectively. The SOF of D100 is slightly higher than B100 and B20. It suggested that adding biodiesel into diesel can decrease SOF and thus reduce the potential danger to human health. The original total PAHs concentration of tail gas emitted from engines using D100, B100 and B20 were 241, 50.6 and 98.8 µg/m3, respectively. Adding 20% biodiesel into D100 could reduce 59.0% of PAHs emission. Moreover, the original total BaPeq concentration of tail gas emitted from diesel engines using D100, B100 and B20 were 0.714, 0.509 and 0.570 µg/m3, respectively. Adding 20% biodiesel into D100 could also reduce 20.2% of total BaPeq emission. Hence, adding biodiesel into diesel can effectively reduce the emission of PAHs and the potential danger to human health. The emission factors of carbonyl compounds from diesel engines using D100, B100 and B20 were 395, 1,170 and 326 mg/BHP-hr, respectively. carbonyl compounds of B100 were obviously higher than D100 and B20. The results indicated that using pure palm biodiesel in diesel engine can increased the emission of carbonyl compounds. However, adding 20% biodiesel into D100 can effectively reduce 17.5% of carbonyl compounds emission. Keyword: ultra-low sulfur diesel, palm biodiesel, fuel properties¡BThe emission of soluble organic fraction (SOF)¡BPAHs¡Bcarbonyl compounds¡C

Thesis (Ph. D.)--Oregon State University, 2010. / Printout. Includes bibliographical references (leaves 190-208). Also available on the World Wide Web.

The focus of my graduate research in the Krische group has been the development of catalytic carbon-carbon bond forming reactions with an emphasis on controlling diastereo- and enatio-selectivity in transfer hydrogenative couplings. The broad goal of our research program has been the development and implementation of efficient green methods for carbonyl addition employing [pi]-unsaturates as surrogates to preformed organometallic reagents, thus enabling byproduct free variants of traditional carbanion chemistry. This dissertation shows the new reactions that I have developed toward this goal. These reactions includes new metal catalyzed approaches for carbonyl crotylation, aminoallylation, and vinylogous reformatsky aldol reactions. / text

published_or_final_version / abstract / toc / Chemistry / Master / Master of Philosophy

Protein dynamics play a key role in enzyme-catalyzed reactions. Vibrational spectroscopy provides a method to follow these structural changes and thereby describe the reaction coordinate as a function of space and time. A vibrational spectroscopic technique, reaction-induced FTIR spectroscopy, has been applied to the study of the oxygen-evolving complex (OEC) of photosystem II (PSII). In plant photosynthesis, PSII evolves oxygen from the substrate, water, by the accumulation of photo-oxidizing equivalents at the OEC. Molecular oxygen and protons are the products of this reaction, which is responsible for the maintenance of an aerobic atmosphere on earth. The OEC is a Mn4CaO5 cluster with nearby bound chloride ions. Sequentially oxidized states of the OEC are termed the S states. The dark-stable state is S1, and oxygen is released on the transition from S3 to S0. Using short laser flashes, individual S states are generated, allowing vibrational spectroscopy to be used to study these different oxidation states of the OEC. In current X-ray crystal structures, hydrogen bonds to water molecules are predicted to form an extensive network around the Mn4CaO5 cluster. In the OEC, four peptide carbonyl groups are linked to the water network, which extends to two Mn-bound and two Ca-bound water molecules. This dissertation discusses a vibrational spectroscopic method that uses these peptide carbonyl frequencies as reporters of solvatochromic changes in the OEC. This technique provides a new, high-resolution method with which to study water and protein dynamics in PSII and other enzymes.