As mankind attempts to halt climate change and global warming, large-scale carbon dioxide (CO2) capture, utilization and storage (CCUS) technologies are viewed as an indispensable approach to curb CO2 emission. This thesis focused on better understanding CO2-amine interactions during adsorption, while developing in parallel covalently immobilized polyethylenimine (PEI) adsorbents for CO2 adsorption. In addition, catalyst reusability issues reported in the synthesis of cyclic carbonates (CCs) from CO2 and epoxides using metal-free supported immobilized quaternary ammonium salts are addressed, while developing new organosilicas for the synthesis of CCs. The reaction between CO2 and amine was investigated at the gas-solid interface in an attempt to provide a unified CO2-amine interaction both in adsorption and absorption. A combination of density functional theory calculations and experimental data (FTIR and 13C NMR) showed that the formation of the zwitterion intermediate often reported in the literature is highly unlikely, instead a six-atom centered zwitterion mechanism involving the “assisting” effect of water, amine or other functional groups was found to be more feasible due to its lower activation energy. Moreover, evidence was provided to suggest that under humid conditions, bicarbonate and carbonate are formed from the reaction between water and CO2, and not the widely reported carbamate hydrolysis. With a goal of minimizing the leaching of amines on PEI-impregnated adsorbents, PEI was covalently immobilized on mesoporous aluminosilica using 3-glycidoxypropyltrimethoxysilane or 3-triethoxysilylpropyl isocyanate as linkers. The resultant materials were found to be more resistant to leaching (in ethanol) and degradation (air at 100 oC) compared to their impregnated counterparts. Further enhancement in oxidation stability was achieved by covalently grafting epoxide-functionalized PEI onto mesoporous aluminosilica. CO2 uptake over amine-containing adsorbents is widely reported to be enhanced in the presence of moisture. However, the same cannot be said for other adsorbents, such as, carbonaceous and zeolite-based materials, and most MOFs. In a soon to be submitted review manuscript, a comprehensive analysis on the role of water on CO2 uptake (equilibrium and kinetics), material structure and regeneration over a wide range of adsorbents is presented. As for CO2-epoxides fixation to cyclic carbonates, a quaternary ammonium salt supported on SBA-15 was used to investigate the observed literature trend between product yield and substrate type with catalyst reuse. Under mild reaction conditions (1.0 MPa CO2, 100 oC and 4 h), 1,2-butylene carbonate was obtained in high yields (> 95%) over 5 cycles as the substrate is easy to activate and the product can be completely removed from the catalyst surface due to its low boiling point. Nonetheless, using styrene oxide led to decrease in yield over reuse cycles, mainly because styrene carbonate crystals were trapped on the catalysts surface (13C MAS NMR and TGA data), thereby blocking access to active sites. By extensively washing all spent catalysts in acetone and using chromatographic grade SiO2 as support material, styrene carbonate was obtained in very good yield (> 93%) over five cycles. Finally, novel quaternary ammonium iodide-based organosilicas, grouped into disordered, ordered and periodic mesoporous organosilicas, were prepared and tested for the cycloaddition of CO2 to epoxide to yield cyclic carbonates. Under mild reaction conditions (0.5 MPa CO2, 50 oC and 10 – 15 h) catalysts with the ordered mesoporous organosilicas structure were found to be more active owing to their larger surface area and pore volume, enhancing the accessibility of active sites by epoxides.

<p>Thin film photovoltaic materials have garnered much interest recently due to their processability in addition to good properties for conversion of solar photons to usable energy. Amine-thiol chemistry has shown the ability to produce solution processed materials such as Cu₂ZnSn(S,Se)₄ (CZTSSe), a thin film absorber composed of earth abundant metals. Using similar solution processing methods as those used to produce CZTS, we wish to synthesize a phase pure solution processed material from molecular precursors of metals and metal chalcogenides into an Ag₂ZnSnSe₄ absorber which lacks the electronic defects that plague CZTSSe. Additionally, we will utilize the reactive dissolution of metal in amine-thiol solution chemistry for a more detailed understanding of how metal-sulfur complexes form and then decompose into films, to gain insight about the conditions that produce stable solutions and high quality films for a better ability to optimize processing conditions. </p><p><br></p><p>We find we are able to individually dissolve zinc metal, tin metal, and silver sulfide precursors to produce solutions of metal thiolate complexes. Based on results from electrospray ionization mass spectrometry (ESI-MS), proton nuclear magnetic resonance (¹H-NMR), and extended X-ray absorption fine structure (EXAFS)/ X-ray absorption near edge spectra (XANES) we propose that these structures contain thiolate molecules coordinated with Ag, Zn, and Sn in the +1, +2, and +2 oxidation states respectively. However, mixing these produces an AZTS solution which is only stable for 3 hours, due to a redox reaction between Ag⁺ and Sn²⁺ which forms Sn⁴⁺ and insoluble Ag metal. To solve this, we synthesize SnS₂ and show this produces a different Sn-thiolate complex with fully oxidized Sn⁴⁺. This is then used to produce the first stable AZTS solution, an essential step to fabricating reproducible films. We use this AZTS solution to fabricate films containing AZTS, and selenize these films in a tube furnace to produce films which contain AZTSe as well as secondary phases. We then use rapid thermal processing furnace to remove some of these secondary phases, and discuss ways to further improve our material quality.<br></p><p></p>

No description available.

In the wolf spider Rabidosa punctulata, upon encountering a female, males use one of two distinct strategies: (1) they court the female in an attempt to elicit a mating, or (2) they engage in a direct-mount tactic that involves extensive grappling with the female until a mating is achieved. The latter tactic appears more sexually aggressive, and both tactics come with the risk of being cannibalized. We explored the physiological mechanisms underlying this behavioural variation by assessing the relationship between circulating levels of the biogenic amine octopamine (OA), a neuromodulator suggested to play a role in 'fight or flight' responses of arthropods and male mating tactic expression. We predicted, and found support for, a relationship between OA levels and tactic expression, with males adopting the direct-mount tactic expressing higher OA levels than courting males. Male mating tactic and mass also showed a significant interaction, with a negative trend in direct-mounting males and no relationship in courting males. Males had considerably higher levels of OA circulating in their haemolymph than females and female OA level increased with female mass. Our experimental design cannot disentangle cause from effect, but our results are consistent with the hypothesis that OA plays a role in regulating mating tactic expression in R.punctulata.

京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第18342号 / 農博第2067号 / 新制||農||1024(附属図書館) / 学位論文||H26||N4849(農学部図書室) / 31200 / 京都大学大学院農学研究科応用生命科学専攻 / (主査)教授 栗原 達夫, 教授 三上 文三, 教授 平竹 潤 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DGAM

No description available.

No description available.

Photodynamic Therapy (PDT) of cancer involves radiating photosensitizing drugs with light in tumors, which results in generating active singlet oxygen that kills cancer cells. Photosensitizers currently used in PDT are of low quantum yield and require high energy radiation, normally laser. Therefore there is always need for more effective PDT drugs. In this project we synthesized new derivatives of phenothiazinium for potential applications in PDT. Phenothiazinium was synthesized and derivatized by linking it to side groups containing imidazole rings. These derivatives are also expected to catalyze certain hydrolytic reactions. Such ôhydrolase modelsö use molecular recognition based on ??? stacking between the phenothiazinium ring and aromatic rings of specific substrates, such as anthracene monophosphate, while imidazole groups catalyze the hydrolysis of the phosphate ester by general acid-base mechanism.

The global market for waterborne coatings will continue to grow because alternative solventborne coatings emit environmentally hazardous volatile organic compounds (VOCs). However, most waterborne coatings are softer than solventborne crosslinked thermoset coatings because they feature thermoplastic polymer dispersions. To overcome these challenges, in this thesis we suggest a novel crosslinkable aqueous dispersion system that incorporates epoxy and amine particles into poly(methyl methacrylate) (PMMA); the particles will react when water (the solvent) evaporates, offering a potential one-component (1K) reactive system. Emulsion polymerization was used to synthesize the particles with the help of surfactants. Epoxy and amine particles were successfully incorporated during the synthesis of PMMA and formed a two-component (2K) aqueous dispersion. In this process, a non-ionic surfactant, Triton X405 (TX405), was used to prevent interactions with the amine particles. Nuclear magnetic resonance (NMR) was used to determine the actual incorporation ratios of epoxy and amine and we found an epoxy incorporation plateau. Dynamic light scattering (DLS) was used to determine the particle size distributions and a uniform distribution was observed. The pendulum test and the pencil test were used for coating hardness, which surpassed currently marketed waterborne coatings. The resulting aqueous dispersions could be cured under facile conditions, i.e., in air and at low temperatures. An increase in Tg was observed after crosslinking. Different mechanical properties were observed when the coatings were cured at different temperatures, 25°C, 70°C, and 100°C. These results suggest that we have successfully formed crosslinked coatings that contain our epoxy and amine incorporated particles, with mechanical properties comparable to the traditional solventborne coatings.

Functionalized poly(para-xylylene) (PPX) coatings can be useful for biomaterials applications due to their biocompatibility and useful chemistry for the immobilization of biomolecules. However, their application is not widespread due to the difficulty in synthesizing the corresponding precursors. Here, a two-step method for amine functionalization of [2.2]paracyclophane (PCP) via direct nitration and reduction is developed. Nitration at super acidic conditions and temperatures as low as -78 °C, improved the stability of PCP toward strong acids and successfully minimized side reactions such as oxidation and polymerization. This procedure resulted in quantitative yields of 4-nitro-PCP, which was successively reduced by Raney nickel catalysis with sodium borohydride. Compared to the many other reduction systems, this method is simple, inexpensive and applicable in large scales. Additionally, carboxylation of PCP using the Freidel-Crafts acylation was attempted and so far, we have been able to show the synthesis of intermediate acylated products. Then, through the chemical vapour deposition polymerization of amino-PCP amine-functionalized poly(para-xylylene) (PPX-A) thin films were coated on Si wafer substrates. The substrates coated with PPX-A showed a higher surface energy compared with those of coated with un-substituted or chlorine substituted PPX films. Furthermore, results of the surface characterization demonstrated that the CVD process was able to transfer the functionalities of the precursors to deposited polymer films without alteration. However, the stability of primary amine groups in air and aqueous solutions is a matter of concern. Aging of amino-PCP and corresponding PPX-A films showed a decrease in the amount of primary amines which was accompanied by the appearance and increase of oxygen, indicating that the decrease of available amine groups is associated with oxidation. Nevertheless, both aminated precursor and polymer films remained intact under argon. The method presented here has great potential for widespread application of PPX-A as a convenient biomaterial for microarrays and cell culture. / Thesis / Master of Science (MSc)