Low energy electron (LEE) driven chemistry underpins a wide range of interdisciplinary fields, including radiation biology, redox chemistry, astrochemistry and biomaterial design. A growing interest in the chemistry of LEEs concerns the radiative damage to DNA. Studies have found that LEEs can induce single and double-strand breaks in DNA by forming a negative ion resonance (NIR). These processes are remarkably site-specific and have been utilized to synthesize radiosensitizers, which aid in identifying target cells in hypoxic tumors in radiation therapy. Despite the prevalence of LEE-induced reactions, computational studies of such processes are limited compared to thermal and photochemical reactions. The relative scarcity in computational studies of LEE-induced reactions stems from the difficulties in the theoretical treatment of NIRs. In our work, we report new developments on the application of quantum chemical methods to NIRs. We demonstrate that the combination of approaches developed for resonances with multi reference electronic structure methods enables the computation of various types of NIRs in a single calculation. Additionally, we show that multi-reference methods can also quantify the mixing between NIRs. It is observed that the mixing between resonances can have significant consequences on their lifetimes. We also report the development of a new technique, the continuum remover Feshbach projection operator approach, which uses the conventional methods developed for bound states to characterize resonances. We show that this new approach is straightforward to implement with standard electronic structure packages, it is efficient, and provides promising results. / Chemistry

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京都大学 / 新制・課程博士 / 博士(工学) / 甲第23196号 / 工博第4840号 / 新制||工||1756(附属図書館) / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 辻 伸泰, 教授 田中 功, 教授 乾 晴行 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Yes / The design of a melt synthesis of the first air-stable formulation of the metastable form III of paracetamol is derived from thermo-spectroscopic and thermo-diffraction experiments. Melt crystallisation in the presence of β-1,4-saccharides produces form III selectively and the excipients appear to act as stabilising ‘active’ templates of the metastable polymorph. / This article is part of themed collection: Pharmaceutical Solids.

This thesis pertains to two R&D objectives associated with deploying TMFD sensor technology for meeting AARST-NRPP metrics for Radon (Rn) in-air detection, as well as for monitoring of ultra-trace actinides in air, amidst other Rn-progeny alpha emitting radionuclides. A challenge has persisted over the past 40+ years for detecting trace actinides in air amidst a 100-1000x higher Rn-progeny background. This thesis had a primary aim for addressing this challenge, and developing and assessing for a novel technology solution. Both objectives were successfully met. Methods, designs, and experimental effects of apparatus are discussed for successful Rn and progeny detection for 1-100 pCi/L concentration levels, as well as for Rn-progeny “blind” spectroscopic detection of 10-12 μCi/cc concentrations of actinides (Pu/U/Am) in air. The resulting CTMFD based technology was compared with the state-of-art “Alpha Sentry” CAM system and found to offer superior performance in multiple categories, and ~18x improvement in time to detect (e.g. at 0.02 DAC in 3 hrs vs ~70 hrs for state-of-art) for actinides while also remaining ~100% blind to ~102x higher Rn-progeny background; and, with 1 keV energy resolution vs ~300-400 keV for Alpha Sentry.

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O fenômeno da nucleação é um processo intrinsecamente irreversível. A Teoria Entrópica da Nucleação (TEN) aborda-o analisando um processo reversível equivalente no qual há liberação de calor latente (variação da entalpia), concomitante a um rearranjo estrutural descrito pela variação da entropia antes e depois de certa quantidade de material ter nucleado. Para visualizar a dinâmica e facilitar a análise foi escolhido um processo isobárico. O diagrama de Mollier modificado para evidenciar a região metaestável ajudou a desenvolver uma expressão para o cálculo do tamanho do núcleo crítico, mediante a teoria da flutuação de Landau. Para analisar o sistema na região metaestável, obteve-se a função entropia, S(H,P0), em que aspectos físicos e geométricos (como o princípio de estabilidade termodinâmica) foram determinantes. Cálculos do núcleo crítico em relação à temperatura mostraram concordância qualitativa com o trabalho de Dillmann-Meier. Porém, entende-se que a função do núcleo crítico está incompleta. Para lidar com aglomerados e núcleos em uma abordagem termodinâmica, um ensemble a pressão constante é o mais apropriado, cuja variável conjugada é o volume. Com base em uma teoria das flutuações isotérmicas em um fluido ideal (Koper-Reiss), desenvolveu-se a teoria das flutuações não-isotérmicas (Mokross), aplicável a um fluido não-ideal metaestável mantido a pressão e temperatura constantes. Os parâmetros termodinâmicos do elemento de volume que flutua mudam e diferem daqueles do banho, e evolvem acordando com a equação de estado S=S(H,P). / The phenomenon of nucleation is an intrinsically irreversible process. The nucleation is explored by the Entropic Nucleation Theory (ENT), in which, the irreversible process is replaced by an equivalent one, although now, the process is reversible in which there is a change in the enthalpy, and also an structural rearrangement coded in the change of de entropy. To study the dynamics and perform the analysis an isobaric process was chosen. The metastable region was used to develop an expression for the calculation of size of the critical nucleus, having in mind the Landau´s fluctuation theory. This region was obtained with the help of the modified Mollier diagram. The physical and geometric features of the system were crucial to obtain the entropy function, S(H,P0), used to analyze the metastable region. Calculations of the critical nucleus, with respect to the temperature, were in qualitative agreement with Dillmann-Meier work. Although, the function for the critical nucleus is incomplete. To handle with clusters and nucleus in a thermodynamic framework, a constant pressure assemble is preferable having the volume as the conjugated variable. With the help of the isothermal fluctuation theory, in an ideal fluid (Koper-Reiss), the non-isothermal fluctuation theory (Mokross) was developed, and used to study a non-ideal metastable fluid kept at constant pressure and temperature. The thermodynamics parameters of the fluctuating volume element change, differing from those of the bath, and the state equation, S=S(H,P) gives its evolution.