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京都大学 / 新制・課程博士 / 博士(理学) / 甲第23022号 / 理博第4699号 / 新制||理||1674(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 時任 宣博, 准教授 加納 太一, 教授 依光 英樹 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

京都大学 / 新制・課程博士 / 博士(医学) / 甲第23379号 / 医博第4748号 / 新制||医||1052(附属図書館) / 京都大学大学院医学研究科医学専攻 / (主査)教授 石見 拓, 教授 戸口田 淳也, 教授 中山 健夫 / 学位規則第4条第1項該当 / Doctor of Medical Science / Kyoto University / DFAM

The reaction of [BrRe(CO)₄]₂ with 2-(diphenylphosphino)pyridine (PN) and 6-(diphenylphosphino)-2-formylpyridine (PON) was investigated. The reactions were regiospecific and exclusively produced the phosphorus-coordinated products, BrRe(CO)₄(κᵖ-PN) and BrRe(CO)₄(κᴾ-PON). The kinetics for the chelate ring closure (κᴾ→ κᴾᴺ) in BrRe(CO)₄(κᴾ-PN) were confirmed to occur by dissociative CO loss. The reaction of [BrRe(CO)₄]₂ with 2-(diphenylphosphino)pyridine (PN) was modeled computationally by DFT calculations. The preferred reaction pathway for the substitution reaction was determined to occur by direct attack of the pnictogen donor on the dimer and formation of the κᴺ isomer as the kinetic substitution product occurs. The κᴺ kinetic product then rapidly isomerizes to the κᴾ thermodynamic product by way of a reversible ligand dissociation. Treatment of the tetrahedral cluster H₂Ru₃(CO)₃(μ₃-S) (1) with 2-(diphenylphosphino)thioanisole (PS) furnishes the cluster H₂Ru₃(CO)₇(κ²-PS)(μ₃-S) (2). Cluster 2, which exhibits a chelated thiophosphine ligand (κ²-PS), exists as a pair of diastereomers with Keq = 1.55 at 298 K that differ in their disposition of ligands at the Ru(CO)(κ²-PS) center. The PS ligand occupies the equatorial sites (Peq, Seq) in the kinetic isomer and axial and equatorial sites (Pax, Seq) in the thermodynamically favored species. The reversible first-order kinetics to equilibrium have been measured experimentally by NMR spectroscopy and HPLC over the temperature range 293-323 K. The substitution reaction involving 1 and the isomerization of the PS ligand in 2 were investigated by DFT calculations. The computational results support a phosphine-induced expansion of the cluster polyhedron that is triggered by the associative addition of the PS donor to 1. The observed isomerization of the PS ligand in 2 is best explained by a tripodal rotation of the CO and PS groups at the Ru(CO)(κ²-PS) center that is preceded by a regiospecific migration of one of the edge-bridging hydrides to the non-hydride-bridged Ru-Ru bond in 2. The chiral clusters 1,2-Ru₃(μ-H)₂(μ₃-S)(CO)₇(μ-1p1,2p2-POP) (A) and 1,2-Ru₃(μ-H)₂(μ₃-S)(CO)₇(μ-1p2,2p1-POP) (B) were formed were formed from reaction of Ru₃(μ-H)₂(μ₃-S)(CO)₉ with 1-diphenylphosphino-2-[2-(diphenylphosphino)ethoxy]benzene (POP). Chiral clusters A and B were fully characterized by IR and NMR spectroscopy. Additionally, the molecular structure of A was solved by X-ray crystallography. Chiral cluster A was resolved into its enantiomers by preparative HPLC with a chiral column. The enantiomers were characterized by electronic circular dichroism (ECD) spectroscopy and their absolute stereochemical configuration was determined by X-ray crystallography.

Master’s thesis deals with the use of virtualization and consolidation technologies in order to optimize IT infrastructure in a selected company. The analysis contains current state of IT infrastructure and requirements for future upgrade. The theoretical part contains description of technologies and procedures used in virtualization and consolidation. Subsequently, the proposal of optimization and expansion of IT equipment is created together with management, implementation and economic evaluation of the solution.

This paper explores the possibilities and tools for creating High-Performace Computing cluster. It contains a project for his creation and a detailed description of the setup and configuration in a virtual environment.

Magíster en Gestión para la Globalización / Polymeros SA ingeniería creativa, especialistas en soluciones innovadoras en base a plásticos, finalizó exitosamente el desarrollo de un producto denominado bordes plásticos para la obtención de cátodos de cobre. Este proyecto fue financiado y apoyado por el programa de proveedores de clase mundial Codelco, que busca desarrollar competencias en los proveedores locales de la industria minera, y de esta manera apoyar la innovación en el país. La empresa tiene una cantidad importante de reconocimientos por su capacidad innovadora que le han servido de apalancamiento para poder insertarse en distintas industrias. La buena calidad de sus productos, que destacan por ser confiables y duraderos, gatillan la necesidad de una búsqueda de nuevos mercados para explotar, y de esta forma seguir mejorando, o al menos manteniendo, su volumen de ventas. El objetivo que persigue este trabajo es estudiar, desarrollar y entregar una recomendación a la empresa sobre un plan de internacionalización. En una primera instancia se desarrolla una evaluación de mercados atractivos para este plan, en donde la elección se sustenta en base al crecimiento del PIB del país, los volúmenes de cobre producidos por éste y teniendo en cuenta además, índices que favorecerían el desarrollo del negocio. Como resultado de este análisis se obtiene que el país más ad-hoc para este desarrollar este estudio es Perú. Luego el trabajo proporciona un análisis del mercado minero del cobre de este país, estimando el volumen de ventas que se podría alcanzar, analizando precios, visualizando riesgos y también definiendo la mejor estrategia de comercialización para el ingreso al mercado. El contexto es estudiado mediante un análisis de la situación coyuntural del Perú en aspectos demográficos, sociales, políticos, culturales y económicos. También se revisó el movimiento minero actual, en donde se corrige la proyección del crecimiento de la industria, que será relevante para dimensionar el atractivo del negocio para los productos a pedido. Además se segmentó la industria para facilitar la identificación de los potenciales clientes de la industria para los bordes plásticos. Basados en factores críticos de la compañía, tales como, costo, posicionamiento y riesgo, se proyectó una estrategia de entrada para la comercialización denominada exportación concertada, que disminuye el riesgo, entrega conocimientos del mercado y posiciona a la empresa en el medio local. Esta estrategia evoluciona en el sexto año hacia una que considera la fabricación en el mercado de destino. Junto a esta propuesta se detalla un plan operacional, plan de ventas y la estimación de los recursos necesarios para su ejecución. Para finalizar el estudio se realiza una evaluación económica de los flujos probables de este plan que considera la evolución de la estrategia comercial, complementado por un análisis de sensibilidad sobre las principales variables que pueden influir en el negocio. De los resultados obtenidos de la evaluación, NPV de MMUS$ 2,8 y con una recuperación de la inversión en el año 4, se desprende el alto potencial económico que representa este plan para la empresa.

A comprehensive and reliable assessment of work stress, burnout, affective, and physical symptomatology was conducted with 260 hospital nurses. As previous attempts to categorize nursing stress and burnout by ward type have yielded inconsistent results, an alternative method for grouping nursing stress effects was sought. Cluster analysis was chosen as it offers a statistically sound means of delineating natural groupings within data. Sets of questionnaires measuring burnout, work stressors, and physical and emotional symptomatology were sent to all staff nurses at a large university hospital. Of 709 nurses employed there, a total of 260 nurses returned completed questionnaire packets. These nurses were separated into two equal groups using random sampling procedures. Cluster analysis of this data revealed groupings which were based on nursing stressors (particularly workload and conflict with physicians), social support, and patient loads. These cluster-analytic findings were replicated on both samples, and validated using data not used in the original cluster analysis. Results suggest that the effects of stress have more to do with the characteristics of the work environment and overall workload than with the degree of specialization on the unit. Results also suggest that intraprofessional conflict (i.e. with other nurses) is less psychologically damaging than is interprofessional conflict (i.e. conflict with physicians). Findings are discussed with respect to the burnout process and possible interventions.

Background: Cluster randomized control trials (cRCTs) are useful for asking about system-level interventions compared to other types of clinical research design, however they present unique challenges with conduct and delivery. Numerous cRCTs in hospitals have encountered challenges and time delays in enrolling hospitals and launching the trials which contributes to research waste. While each cRCT has unique barriers and enablers to their conduct, it is important to understand and explore these factors at the general level of the cRCT itself. Previous literature has documented factors associated with successful cRCTs, however, these studies focused primarily on the statistical aspect, while neglecting to evaluate the delivery of the trial. Objectives: The goal of this dissertation was to explore barriers and enablers to conducting cRCTs in hospitals, and to identify potential strategies that facilitate their delivery. This research was conducted to identify evidence and generate guidance for researchers aiming to conduct these trials. Specifically, the objectives were: 1) To explore the current knowledge and evidence surrounding the implementation of cRCTs in hospitals; 2) To explore from the perspective of the coordinating site, what influenced the delivery and hospital engagement of an ongoing cRCT, and what challenges were encountered; 3) To identify strategies to facilitate delivery of cRCTs in hospitals; 4) To systematically review reported recruitment strategies of healthcare facilities in cRCTs. Methods: The dissertation employed multiple research methods. To address the first objective, a scoping review was performed of current literature related to hospitals in cRCTs. The second objective was addressed with a qualitative case study. Semi-structured interviews were carried out with six key members of the team to understand their perceptions of the delivery of the trial. For the third objective, a tool matching two implementation concepts (the Consolidated Framework for Implementation Research (CFIR)- Expert Recommendations for Implementing Change (ERIC) matching tool) was used to identify strategies targeted to address barriers and enablers to cRCT conduct identified in the first two studies. Lastly, a systematic review was performed to address the fourth objective, to identify reported strategies used for hospital engagement in cRCTs. The thesis was guided and analyzed using an over-arching implementation framework, CFIR, and an implementation strategies list, the ERIC compilation. This was done to allow comparability and synthesis of results between methodologies from the dissertation, and between the results from the studies and previous literature. Results: Several key CFIR domains were identified in the literature in the scoping review that were determined to being influential for conducting the cRCTs in hospitals: the adaptability to tailor the trial to each site; the engagement of opinion leaders, champions and formally appointed implementation leaders in the cRCT process as facilitators to conducting the trial; the lack of a site perceiving a relative priority for the trial or tension for change for the clinical field presenting barriers to conducting the cRCT; and limited available resources can present barriers to conducting the cRCT. The qualitative case study identified similar CFIR domains and constructs as potentially influential for cRCT conduct, including the emphasis on adaptability of trial, the importance of tension for change in the sites for accepting inclusion in the trial, the availability of resources, and the engagement of leaders. The CFIR-ERIC matching study identified strategies that may be used to overcome barriers and target enablers for cRCT delivery from CFIR domains and constructs identified in the first two studies. A list of strategies was generated, ranked by the number of many determinants for which the strategy was listed as a Level 1 strategy, then by how many determinants for which the strategy was listed as a Level 2 strategy. The top ERIC strategies that were endorsed as a Level 1 strategy for any or multiple CFIR domains were: 1) Identify and prepare champions, 2) Conduct local needs assessment, 3) Conduct educational meetings, 4) Inform local opinion leaders, 5) Build a coalition, 6) Promote adaptability, 7) Develop a formal implementation blueprint, 8) Involve patients/consumers and family members, 9) Obtain and use patients/consumers and family feedback, 10) Develop educational materials, 11) Promote network weaving, 12) Distribute educational materials, 13) Access new funding, and 14) Develop academic partnerships. The systematic review identified literature reporting on the recruitment of healthcare facility sites into cRCTs. Numerous strategies for cRCT site recruitment were identified, and these were coded to the ERIC compilation. Strategies that were commonly cited were: involve executive boards, promote network weaving, conduct educational meetings, inform local opinion leaders, and centralize technical assistance. Conclusions: The results from the dissertation can contribute to the knowledge for facilitating cRCT delivery in hospitals while recognizing the critical limitations in the studies. Key concepts and strategies to facilitate the conduct and delivery of cRCTs in hospitals were identified. Future research should aim to empirically evaluate the identified strategies. Researchers should aim to address the reporting gap for cRCT delivery identified by this dissertation.

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