As the speed of change is increasing, it’s of great importance that manufacturing companies strive to achieve not only incremental improvements, but also radical improvements within their production systems. Thus, more research has to be focused on how to realize radical improvement. In accordance, the objective of the licentiate thesis is to, through theoretical and empirical work, increase the understanding about radical improvement in production and identify what elements need to be considered when designing support on how to implement radical improvement in industrial production. Throughout the research process these issues has been addressed through theoretical and empirical studies. Three studies have been conducted in total, of which two are mainly of theoretical character and one of empirical character. Besides, a state-of-the-art theoretical review has been carried out as well, further framing the findings. The research results imply that radical improvement in production is a teamwork process that embraces the facilitation of creativity and innovation. The research further implies that there are a number of issues to consider when creating industry-applicable support on how to realize radical improvement in industrial production. For instance, what level of innovation is striven for must be decided, creativity must be facilitated throughout, the opposing cultures of incremental and radical innovation must be managed, and there is a need to apply a holistic perspective, thus embracing not only productivity results but organizational learning as well. As further work, creating industry-applicable support on how to realize radical improvement in industrial production is advocated, focusing not only on meeting the issues addressed above, but also how to make the support industry-applicable. / Kaikakuprojektet / INNOFACTURE - innovative manufacturing development

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Intermolecular complexes between H₂O and atmospheric species HO, HO₂, H₂O₂, O₃, NO and NO₂ have been studied by ab initio molecular orbital methods. The studies have been performed to the MP2 theory level by using 4-31G, 6-31G, D95, 6-31G**, D95**, 6-311G**, 6-311+G**, 6-311++G**, 6-311+G(2d,lp) and 6-311+G(2d,2p) basis sets. The geometries were fully optimized. The vibrational frequencies were calculated. The Basis Set Superposition Error (BSSE) were estimated. Finally, the binding energies of the complexes were predicted with other thermochemical properties. The binding energies of H₂O•HO, H₂O•HO₂, H₂O•H₂O₂, H₂O•O₃, H₂O•NO and H₂O•NO₂ are estimated to be 5.7±0.6, 8.9±1.0, 7.3±1.3, 1.8±0.2, 1.17 (no BSSE correction) and 2.98 (no BSSE correction) Kcal/Mol, respectively. The Kcq for dimerization to yield H₂O•HO, H₂O•HF, H₂O•HO₂, H₂O•H₂O and H₂O•H₂O₂ are estimated to be 0.11, 2.8, 3.3, 0.067 and 0.11 atm¯¹, respectively. The H₂O•HO, H₂O•HF, H₂O•HO₂, H₂O•H₂O and H₂O•H₂O₂ are quite strongly bonded complexes, while H₂O•O₃, H₂O•NO and H₂O•NO₂ are only weakly bonded complexes. The Kcq changes with temperature are discussed, and their importance in atmospheric chemistry are addressed.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18296号 / 工博第3888号 / 新制||工||1596(附属図書館) / 31154 / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 澤本 光男, 教授 中條 善樹, 教授 赤木 和夫 / 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18522号 / 工博第3914号 / 新制||工||1601(附属図書館) / 31408 / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 辻井 敬亘, 教授 金谷 利治, 教授 山子 茂 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19894号 / 工博第4210号 / 新制||工||1651(附属図書館) / 32971 / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 澤本 光男, 教授 秋吉 一成, 教授 杉野目 道紀 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

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京都大学 / 新制・課程博士 / 博士(理学) / 甲第24435号 / 理博第4934号 / 新制||理||1705(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 依光 英樹, 教授 若宮 淳志, 教授 畠山 琢次 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

The present study reports radiation-chemical yields of 2.5-diaminoimidazolone (Iz) derivatives in X-irradiated phosphate-buffered solutions of guanosine and double-stranded DNA. Various gassing conditions (air, N20/O2 (4:1), N2O, vacuum) were employed to elucidate the contribution of several alternative pathways leading to Iz in reactions initiated by hydroxyl radical attack on guanine. In all systems, Iz was identified as the second by abundance guanine degradation product after 8-oxoguanine, formed in 1:5 (guanosine) and 1:3.3 (DNA) ratio to the latter in air-saturated solutions. Experimental data strongly suggest that the addition of molecular oxygen to the neutral guanine radical G(-H)• plays a major in Iz production in oxygenated solutions of double-stranded DNA while in other systems it may compete with recombination of G(-H)• with superoxide and/or alkyl peroxyl radicals. The production of Iz through hydroxyl radical attack on 8-oxoguanine was also shown to take place although the chemical yield of Iz (ca 6%) in this process is too low to compete with the other pathways. The linearity of Iz accumulation with dose also indicates a negligible contribution of this channel to its yield in all systems.

Thesis advisor: X. Peter Zhang / Highly strained three membered heterocycles are a common motif in many biologically relevant molecules and represent a versatile building block for organic synthesis. Of special interest for asymmetric synthesis is the construction of enantioenriched aziridines and epoxides, which are often used as chiral synthons to introduce heteroatoms in a stereoselective fashion. Among different elegant strategies, the direct aziridination and epoxidation of the ubiquitous alkene functionality represents one of the most powerful methods to access these motifs. Given the synthetic importance of the enantioenriched smallest aza- and oxaheterocycles, the focus of this dissertation is centered on the design and use of chiral cobalt porphyrins as catalysts to develop new methodologies for the asymmetric radical aziridination and epoxidation of alkenes.In the first part of this dissertation, we focused on using carbonyl azides as nitrogen source for the enantioselective radical aziridination of alkenes. Despite its high functionality and versatility for further derivatization, carbonyl azides have never been reported as nitrogen source for intermolecular asymmetric alkene aziridination. In the second part of this dissertation, we focused on opening up a new area of research, which involves the generation and characterization of the unprecedented cobalt porphyrin-supported oxygen-centered radical species. Finally, we demonstrated the synthetic utility of these new radical species by developing a new system for the asymmetric epoxidation of alkenes through the design and development of a novel family of catalyst named “JesuPhyrin”. / Thesis (PhD) — Boston College, 2021. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.