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AN ABSTRACT OF THE THESIS OF James Morrow, for the Master of Science degree in Mechanical Engineering, presented on November 3, 2017, at Southern Illinois University Carbondale. TITLE: INVESTIGATION OF THE MATERIAL PROPERTIES OF CERIUM OXIDE WITH DOPANTS FOR AN OXYGEN TRANSPORT MEMBRANE MAJOR PROFESSOR: Dr. Kanchan Mondal Many physical properties of cerium oxide both undoped and doped have been studied herein. These properties include electrical conductivity, hardness, sintered density, and microstructure. These will be used to help determine a cerium oxide compound to use as an oxygen transport membrane in a combustion system. These compounds have been readily studied beforehand with exception to compounds with multiple dopants. Along with single doped cerium oxide, dual doped was investigated as well. The samples to be tested were created using co-precipitation and the subsequent powders were sintered at 1500°C to generate solid pellets. Once the pellets were formed the physical properties were tested. It was found that hardness and sintered density had little to no effect on electrical conductivity and the microstructures of the samples were shown to be favorable. As far as single or dual dopants were concerned, it was found that by including a second dopant along with zirconium that the electrical conductivity was reduced. Except for in the case where iron was doped along with zirconium, where the conductivity was increased. It was suggested to use samarium as the second dopant along with zirconium for the membrane.

Philosophiae Doctor - PhD / Tetrodotoxin (TTX) is a nonpeptidic neurotoxin with a high rate of food poisoning mortality (60%) that has been associated with the consumption of diets from puffer fish and mud snails harbouring TTX-producing bacteria. As this neurotoxin has no known antidote and could not be mitigated by cooking, the only way for safety appears to be the detection of TTX-contaminated fishes at the points of harvest and control. The overall aim of this study was to develop amperometric and impedimetric sensors for TTX based on ionophores and aptamer immobilised on the modified conducting electroactive polyaniline (PANI)/electrode. The undoped polyaniline and poly(4-styrenesulfonic acid) (PSSA) doped electroactive polyanilines were prepared in perchloric acid/acetonitrile and phosphoric acid respectively by electrochemical oxidative polymerisation. Two types of electropolymerisation were applied to prepare the neutral and p-doped PANI−PSSA films composites. The dynamic electroinactivity of TTX was studied which revealed that TTX is not electrochemically active on bare Au, GC, Pt, PG, Ni, Ti and BDD (Boron dopeddiamond) electrodes in acetate buffer pH 4.8. Using ion transfer voltammetry and UV-Vis analysis, the complexation of TTX with two neutral ionophores (sodium ionophore X (NaX) and dibenzo-18-crown6 (B18C6)) was investigated. The cyclic voltammograms (CVs) recorded from ion transfer voltammetry presented no redox peak and no increasing/decreasing current was observed which indicates that no TTX ions transfer from the liquid to the organic phase. In addition, the absorption spectra of the mixture of TTX/NaX and TTX/B18C6 presented the same absorption bands recorded for NaX and B18C6 respectively. Three absorptions bands at 250.4, 278.3, and 370.6 nm for NaX and two at 222.03 and 274.10 nm for B18C6 were observed before and after mixing TTX with NaX and TTX with B18C6 separately. No chemical reaction occurred between the TTX and both ionophores, therefore, sodium ionophore X and dibenzo-18-crown-6 did not form a complex with TTX. Thus, TTX ion sensor cannot be developed based on these two neutral compounds. The electrodynamics of the PANI and PANI−PSSA films electropolymerised on the bare precious metal electrodes were also investigated through various electrochemical techniques. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) studies in sodium phosphate (SPB) and acetate (OAc) buffer revealed that both neutral and p-doped films synthesized were thin (thickness L < 5 nm in acetate buffer and L < 10 nm in sodium phosphate buffer) film polymers.

Choline oxidase catalyzes the two-step oxidation of choline to glycine betaine, one of limited osmoprotectants, with the formation of betaine aldehyde as an enzyme bound intermediate. Glycine betaine accumulates in the cytoplasm of plants and bacteria as a defensive mechanism to withstand hyperosmolarity and elevated temperatures. This makes the genetic engineering of relevant plants which lack the property of salt accumulation of economic interest, and the biosynthetic pathway of the osmolyte a potential drug target in microbial infections. The reaction of alcohol oxidation occurs via a hydride ion tunneling transfer from the substrate donor to a flavin acceptor within a highly preorganized active site environment in which choline and FAD are in a rigidly close proximity. In this dissertation, factors contributing to the enzyme-substrate preorganization which is required for the hydride ion tunneling reaction mechanism in choline oxidase have been investigated. Crystallographic studies of wild-type choline oxidase revealed a covalent linkage between C8M atom of the FAD isoalloxazine ring and the N(3) atom of the side chain of a histidine at position 99, and a solvent excluded cavity in the substrate binding domain containing glutamic acid at position 312 as the only negatively charged amino acid residue in the active site of the enzyme. The role of the histidine residue and the contribution of the 8á-N(3)-histidyl covalent linkage of the flavin cofactor to the reaction of alcohol oxidation was investigated in a variant form of choline oxidase in which the histidine residue was replaced with an asparagine. The role of the glutamate residue and the importance of the spatial location of the negative charge at position 312 was investigated in variant forms of choline oxidase in which the negatively charged residue was replaced with glutamine and aspartate. Mechanistic data obtained for the variant enzymes and their comparison to previous data obtained for wild-type choline oxidase are consistent with the residues at positions 99 and 312 being important for relative positioning of the hydride ion donor and acceptor. The residues are important for the enzyme-substrate preorganization that is required for the hydride tunneling reaction in choline oxidase.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22459号 / 工博第4720号 / 新制||工||1737(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 作花 哲夫, 教授 安部 武志, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21783号 / 工博第4600号 / 新制||工||1717(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 安部 武志, 教授 作花 哲夫, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

京都大学 / 新制・課程博士 / 博士(工学) / 甲第24108号 / 工博第5030号 / 新制||工||1785(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 安部 武志, 教授 作花 哲夫, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

>Magister Scientiae - MSc / Amperometric sensors for Tenofovir, a model nucleotide/ nucleoside reverse transcriptase inhibitor ARV drug, were studied based on the principle of ion-transfer electrochemistry at the membrane-stabilized oil/ water interface (O||W) in a four-electrode cell set-up. Solutions of the hydrophobic salts tetradodecylammonium tetrakis(4-chlorophenyl) borate (ETH500), ethyl violet tetraphenylborate (EthVTPB), tetrabutylammonium tetraphenylborate (TBATPB), tetraphenylphosphnium tetraphenylborate (TPphTPB) and three ionic liquids (Methyltrioctylammonium bis(trifluoromethyl sulfonyl)imide (IL1), 1-butyl-3- methylimdazolium bis(trifluoromethyl sulfonyl)imide (IL3) and 1-propyl-3- methylimdazolium bis(trifluoromethylsulfonyl)imide (IL4)) in nitrobenzene (NB), 1,2- dichloroethane (DCE), and 2-nitrophenyloctyl ether (NPOE) were each tested as O-phases. The cyclic voltammograms of the resulting O||W interfaces in aq. Li2SO4 or aq. MgSO4 were compared with respect to noise, potential window, and other parameters. The three ILs were also tested as self-sufficient salts without a solvent medium. In the end, the ETH500/ DCE salt/ solvent pair was found to yield the best behaved polarizable O||W interface in aq. MgSO4. The analytical characteristics of the resulting sensors to tenofovir without (Ag|ETH500/DCE||) and with the dibenzo-18-crown-6 (Ag|ETH5000/DB18C6/DCE|| in the O-phase were studied with respect to the two pairs of peaks in the CV, namely the WO ion transfer peak and the reverse OW peak. Both sensors exhibited operational stability of 90 min. After consideration of reasonable S/N ratio and sample throughput rates, the scan rate of 25 mV/ s was used in subsequent signal interrogation with CV. The final potential windows were 0.95 V wide for Ag|ETH500 (10 mM)/ DCE|| in aq. MgSO4 (50 mM) and 0.70 V wide for Ag|ETH500 (10 mM)/ DB18C6 (50 mM)/ DCE|| in aq. MgSO4 (50 mM). From plots of peak currents versus square of scan rate, tenofovir diffusion coefficients of about 2.48 × 10-11 cm2/ s were estimated, which indicated diffusion through the supporting membrane as the rate limiting process. Based on WO ion transfer peaks, the first one exhibited a detection limit of about 5 M, a linear range of 15 – 100 M, and sensitivity of 7.09 nA M-1 towards tenofovir, whereas for the second one these were respectively 3 M, 6.32 nA M-1, and 9 – 100 M. In this way, a four-electrode amperometric detection of ion transfer process at liquid | liquid interface, both under simple and ionophore-facilitated mode, has been demonstrated as promising for analysis of tenofovir as a representative of the nucleotide/ nucleoside reverse transcriptase inhibitor ARV drugs

Electrochemical methods have been used to study electron transfer reactions at the interface between an aqueous phase of less than 1 femto liters in volume and a bulk organic phase. The small aqueous phase is formed at the end of a slightly recessed platinum electrode. When a negative potential is applied between the Pt electrode and the aqueous phase, Ru(NH3)63+ in the aqueous phase could be reduced to Ru(NH3)62+. Because the volume of the aqueous phase is very small, the electrochemically formed Ru(NH3)62+ could instantly reach the interface between the aqueous phase and the organic phase which contains 7,7,8,8-Teteracyanoquinodimethane (TCNQ), and be oxidized to form Ru(NH3)63+ by giving electrons to TCNQ at the interface. Our results showed a positive shift in the E1/2 comparing the reaction undertaken in the recessed cavity and the bulk solution.

<p dir="ltr">Nanoparticles have seen immense development in the past several decades due to their intriguing physicochemical properties. The modern chemist is interested not only in methods of synthesizing nanoparticles with tunable properties but also in the chemistry that nanoparticles can drive. While several methods exist to synthesize nanoparticles, it is often advantageous to put nanoparticles on a variety of conductive substrates for multiple applications (such as energy storage and conversion). Despite enjoying over 200 years of development, the electrodeposition of nanoparticles suffers from a lack of control over nanoparticle size and morphology. Understanding that structure-function studies are imperative to understand the chemistry of nanoparticles, new methods are necessary to electrodeposit a variety of nanoparticles with control over macro-morphology but also microstructure. When a nanodroplet full of a metal salt precursor is incident on the electrode biased sufficiently negative to drive electroplating, nanoparticles form at a shocking rate (on the order of microseconds to milliseconds). We start with the general nuts-and-bolts of the experiment (nanodroplet formation and methods for electrodeposition). The deposition of new nanomaterials often requires one to develop new methods of measurement, and we detail new measurement tools for quantifying nanoparticle porosity and nanopore tortuosity within single nanodroplets. Owing to the small size of the nanodroplets and fast mass transfer, the use of nanodroplets also allows the electrodeposition of high entropy alloy nanoparticles at room temperature. Electrodeposition in aqueous nanodroplets can also be combined with stochastic electrochemistry for a variety of interesting studies. We detail the quantification of the growth kinetics of single nanoparticles in single aqueous nanodroplets. Nanodroplets can also be used as tiny reactors to trap only a few molecules, and the reactivity of those molecules can be electrochemically probed and evaluated with time. Overall, this burgeoning synthetic tool is providing unexpected avenues of tunability of metal nanoparticles on conductive substrates. Moreover, there is little understanding of how ion transfer can affect the fundamental of nanoparticle synthesis with nanodroplet-mediated electrodeposition. This thesis details different experiments performed to study the role of ion transfer during the nucleation and growth of nanoparticles.</p>