The penostatins are a family of polycyclic natural products isolated from marine bacteria. They exhibit unique biological activity and have garnered interest from synthetic organic chemists due to their complex structure. In particular, the complex oxidation pattern combined with either a fused tricyclic or bridged bicyclic core presents significant challenges to synthesis. The lack of a completed total synthesis of the bridged bicyclic congener penostatin F has motivated the pursuit of a strategy for its synthesis based on a Diels-Alder reaction /Claisen rearrangement sequence. In this work, progress and limitations of this approach are presented. A hydroxy-directed Diels-Alder/Claisen Rearrangement cascade was envisioned and explored however a series of roadblocks prevented the elaboration of bridged bicycle intermediates. Through this process, a novel degradation of hydroxy-dienes was uncovered as well as the isolation of a bridged bicycle containing a cyclic anti-Bredt alkene. The challenges uncovered led to a pivot away from this strategy and ultimately to a new approach for the synthesis of penostatin natural products. In this strategy, a hydroxyl group is used as a tether for an intramolecular Michael addition. Following the optimization of this reaction, an unexpected retro-Dieckman rearrangement of the product forced the development of an alternative route to an initially envisioned decarboxylation. This approach was employed to yield 5-deoxypenostatin B. Finally, progress towards integrating the cyclopentanol ring of penostatin B as part of this strategy via a Tamao-Fleming reaction is described.

Thesis advisor: James P. Morken / This dissertation will present three main projects focusing on the transition metal-catalyzed enantioselective synthesis of secondary organoboronic esters and progress towards the total synthesis of sarcodictyins. In the first project, a palladium-catalyzed enantioselective conjunctive cross-coupling reaction with propargylic electrophiles will be described. The tetra-substituted allenes are isolated with good yield and enantioselectivity and the beneficial effects of alcohol additives are investigated. The second project describes the enantioselective synthesis of ɑ-boryl zinc reagents by a nickel-catalyzed carbozincation reaction. The in situ generated ɑ-boryl zinc intermediate can be trapped by copper-mediated allylations, palladium-catalyzed Negishi cross-couplings, and cerium-mediated halogenation reactions to construct various chiral organoboranes. The synthetic utility of this methodology is showcased by the synthesis of natural products, including bruguierol A, (-)-aphanorphine, and (-)-enterolactone. The mechanism is studied with the assistance of EPR and deuterium-labeling experiments and a catalytic cycle through a Ni(I) intermediate is proposed. The third project depicts a synthetic route to essential precursors in the progress of the total synthesis of sarcodictyins. Various attempts to construct the ten-membered ring core of sarcodictyin have been made, including Sonogashira reaction, Dieckmann condensation, and lithium—halogen exchange process. / Thesis (PhD) — Boston College, 2022. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

M.Ing. / The management of quality in companies has become more and more strategically important over recent years. The emphasis on quality is vital to managing projects and achieving excellence in today’s global economy. Modern petrochemical construction project management has incorporated quality management principles and initiatives in their activities. The Quality Management System is used to ensure that the project will satisfy the requirements for which it was undertaken. Improving project quality in construction requires consideration of culture within the project environment that is often associated with miscommunication and fragmentation. The focus of the thesis is to examine how quality culture can improve the quality in organisation and influence the implementation of Quality Management System in construction industry. The dissertation will comprise of extensive survey of the local academic literature and South African press reports concerning state of construction industry. A questionnaire conducted amongst professionals working in petrochemical industry is aimed to determine the impact of organisational culture on the successful implementation of quality management systems. The objective of this dissertation is to identify inefficiencies and possible improvements that can be achieved in current quality management systems. The dissertation concluded that an improvement in the quality management and quality of construction can only be achieved if quality is embedded in the entire operational and managerial processes of its organizations. The thesis recommends that the South African construction industry would benefit from the development of quality culture that fosters deeper human relationships to improve quality management.

Hylodidae is composed of 46 species distributed in three genera: Crossodactylus (14 spp), Hylodes (25 spp), and Megaelosia (7 spp). These torrent-frogs are diurnal and associated with riverine habitats throughout the Atlantic Rain Forest. The high degree of habitat specificity observed in this group seems to be associated with an extremely conservative external morphology; however, other sources of evidence have been proved useful to distinguish species. My study was designed to review the status of the current hylodid systematics, performing a total evidence analysis that represents as many species (and populations) as possible; confirm the monophyly of currently valid nominal taxa; investigate the evolutionary history of some morphological characters; and reconstruct biogeographical changes in the distribution of hylodids. My total evidence analysis included morphological (293 characters) and molecular data (four mitochondrial and five nuclear genes) for up to 371 hylodid terminals plus 45 outgroups, and resulted in 713 most parsimonious trees. I recovered Hylodidae and its compounding genera as monophyletic, and recognized 58 lineages within this family. Three synapomorphies were identified for Hylodidae based on vocal sac morphology (external double vocal sac, internal double vocal sac, and opening of the m. interhyoideus through which the diverticulum passes). Analysis of the distribution of hylodids revealed the origin of this frog family in the East Atlantic river basin, with subsequent allopatric speciation in adjacent basins / Hylodidae é composta por 46 espécies distribuídas em três gêneros: Crossodactylus (14 spp), Hylodes (25 spp) e Megaelosia (7 spp). Essas rãs-de-corredeiras são diurnas e associadas à ambientes encachoeiradas ao longo da Mata Atlântica. O alto nível de especificacidade à esses habitats observado nesse grupo parece estar relacionado com a morfologia externa extremamente conservada; entretanto, outras fontes de evidências tem provado ser úteis para distinção de espécies. Meu estudo foi designado para revisar o status atual da sistemática dos hilodídeos através de uma análise de evidência total que representa o máximo de espécies (e populações) possíveis; confirmar o monofiletismo dos taxa válidos atualmente; avaliar a história evolutiva de alguns caracteres; e reconstruir mudanças biogeográficas na distribuição de Hylodidae. Minha análise de evidência total incluiu dados morfológicos (293 caracteres) e moleculares (quatro genes mitocondriais e cinco genes nucleares) para 34371 terminais de hilodídeos mais 45 terminais de grupo externo, resultando em 713 árvores mais parcimoniosas com 32.405 passos. Eu recuperei Hylodidae e todos os seus gêneros como monofiléticos e reconheci 59 linhagens dentro da família. Três sinapomorfias putativas foram identificadas para Hylodidae baseadas na morfologia do saco vocal (saco vocal externo duplo, saco vocal interno duplo e abertura no m. interhyoideus por onde o divertículo passa). Análises da distribuição dos hilodídeos revelaram a origem de Hylodidae na bacia Atlântico Leste com subsequentes especiações alopátricas em bacias subjacentes

Esta pesquisa utilizou a revisão sistemática com o objetivo de identificar os principais tratamentos da fístula faringocutânea após a laringectomia total e elaborar recomendações para as intervenções de enfermagem na assistência ao paciente submetido a laringectomia total, com a complicação fístula faringocutânea. Foram previamente localizados 1007 estudos, dos quais foram selecionados 37 estudos publicados em periódicos científicos indexados no Pubmed, Biomednet, Cinahl, Cochrane Library, MEDLINE e LILACS, desses 17 (46%) abordavam o tratamento da fístula faringocutânea, após laringectomia total, 10 (27%) discutiam os fatores de risco e os outros 10 (27%) as complicações após a laringectomia total. A análise desses artigos revelou que o delineamento da pesquisa predominante nos estudos foi o retrospectivo com 88,5%, e 11,5% prospectivos. A média de tempo de acompanhamento foi de 8,8 anos e a incidência de fístula faringocutânea, após a laringectomia total variou entre 8,7% e 27,0%, envolvendo um total de 635 pacientes. Os fatores de risco estudados pelos pesquisadores foram: radioterapia pré-operatória, técnica cirúrgica, traqueostomia pré-operatória, estadiamento do tumor, febre, doenças crônicas, vômito, nível de hemoglobina e reinício da alimentação oral, formando subgrupos com um número menor de pacientes e, conseqüentemente obtiveram percentuais individuais maiores de incidência da fístula faringocutânea, quando comparados com o índice geral de fístula proveniente da amostra inicial do estudo. O tratamento conservador e cirúrgico da fístula tem por finalidade preservar e restaurar a região lesada e envolve um processo complexo, dinâmico e sistêmico. Esta complicação aumentou o período de internação e de cicatrização, com médias de 28 e de 36 dias respectivamente. O tratamento predominante é ainda o conservador que implica cuidados higiênicos intensivos e o tratamento da ferida. O planejamento da assistência de enfermagem alicerçado em conhecimentos e habilidades técnico-científicas acerca do tratamento de feridas aliadas à dimensão psicossocial resultarão em intervenções de maior qualidade.A incorporação de conhecimentos oriundos da prática baseada em evidências na prática clínica, trará maior consistência à atuação do enfermeiro no cuidado do laringectomizado total e portador de fístula faringocutânea. / This research carried out a systematic review aimed at identifying the main treatments of pharyngocutaneous fistula after total laryngectomy and at elaborating recommendations for nursing interventions in care delivered to patients submitted to total laryngectomy, including the pharyngocutaneous fistula complication. In advance, 1007 studies were found, out of which we selected 37 studies published in scientific journals indexed in Pubmed, Biomednet, Cinahl, Cochrane Library, MEDLINE and LILACS. Among these, 17 (46%) dealt with the treatment of pharyngocutaneous fistula after total laryngectomy, 10 (27%) discussed the risk factors and the other 10 (27%) were about complications after total laryngectomy. The analysis of these articles revealed that the predominant research orientation was retrospective (88.5%) and 11.5% corresponded to prospective studies. Average follow-up time was 8.8 years and the occurrence of pharyngocutaneous fistula after total laryngectomy varied from 8.7% to 27.0%, involving 635 patients in total. Analyzed risk factors were: pre-operative radiotherapy, surgical technique, pre-operative tracheostomy, tumor stage, fever, chronic disease, vomiting, hemoglobin level and restarting oral feeding. These constitute subgroups with a lower number of patients which, consequently, obtained higher individual percentage values for the occurrence of pharyngocutaneous fistula in comparison with the general fistula rate from the initial study sample. The conservative and surgical treatment of fistula aims to preserve and restore the injured region and involves a complex, dynamic and systemic process. This complication increased the internment and healing periods, with an average duration of 28 and 36 days respectively. The conservative treatment still predominates and implies intensive hygienic care and wound treatment. The planning of nursing care, based on technical-scientific knowledge and abilities related to wound treatment, in association with the psychosocial dimension, will result in higher-quality interventions. Incorporating evidence-based knowledge into clinical practice will offer greater consistency to nursing actions in caring for patients after total laryngectomy who suffer from pharyngocutaneous fistula.

Quando o paciente com câncer de laringe chega ao tratamento com tumor em estágio avançado, a cirurgia de laringectomia total, retirada cirúrgica da laringe, torna-se a opção de tratamento. Esta cirurgia traz ao indivíduo a possibilidade de sobrevivência, porém com a perda irreversível da voz laríngea. Existem diferentes métodos para reabilitar a voz do laringectomizado total; dentre eles a voz esofágica, a laringe eletrônica e a prótese traqueoesofágica. Podem estes métodos melhorar a qualidade de vida por permitirem ao paciente se comunicar, mesmo possuindo qualidade sonora resultante diferente da produzida pela laringe? O presente estudo se propôs comparar a qualidade de vida de indivíduos submetidos à cirurgia de laringectomia total nas situações de ausência ou presença da reabilitação vocal, bem como nos diferentes métodos utilizados para esta reabilitação, por meio dos questionários de qualidade de vida relacionados ao câncer de cabeça e pescoço (UWQOL e FACT-H&N) e à voz (IDV e QVV). Participaram deste estudo 24 laringectomizados totais, 12 não reabilitados de voz (grupo NR) e 12 reabilitados (grupo R). O grupo R foi subdividido, sendo 7 indivíduos reabilitados por voz esofágica (RVE) e 5 por laringe eletrônica (RLE). Como resultados deste estudo observou-se melhor qualidade de vida para os reabilitados de voz (R) com diferença estatística significativa (p<0,05) em comparação com os laringectomizados totais não reabilitados (NR); isto nos resultados gerais de todos os questionários aplicados. Os domínios específicos dos questionários de qualidade de vida relacionados ao câncer de cabeça e pescoço UWQOL (Fala, Humor, Ansiedade e Paladar) e FACT-H&N (Emocional e Físico) apontaram, também, melhor qualidade de vida para os pacientes com reabilitação vocal. As dificuldades específicas referentes a cada método de reabilitação foram vistas pelos pacientes como inerentes ao processo de cura do câncer. Como conclusão observou-se que a ausência da voz trouxe agravos emocionais e à inserção social dos laringectomizados totais que acabaram por afetar sua qualidade de vida global. A reabilitação vocal tanto por voz esofágica (RVE) quanto por laringe eletrônica (RLE), trouxeram melhoras da qualidade de vida após excisão da laringe. / When the patient with laryngeal cancer begins the treatment with tumor advanced locally, the total laryngectomy becomes the treatment option. This method of cancer\'s remotion brings the chance of survival to the individual, however, with vocal loss. There are different methods to rehabilitate the voice after the total laringectomy. However these methods provide quality of voice distinct from that produced in the larynx. Can these methods improve the quality of life, since allow the oral communication to the individual? The objectives of this study were to compare the quality of life of patients undergoing surgery of total laryngectomy in cases of absence (NR) or presence of rehabilitation vocal (R), as well as in the different methods used for this rehabilitation, through questionnaires of quality of life related to cancer of the head and neck (UWQOL and FACT-H & N) and related to voice (VHI and V-RQOL).The study included 24 TL, 12 non-rehabilitated of voice (NR) and 12 rehabilitated (R). The group of rehabilitated was subdivided, being 7 with esophageal speech (RVE) and 5 electronic larynx users (RLE). As a result there was a better quality of life for the rehabilitated of voice (R) with statistically significant difference (p <0.05) compared with NR, in all questionnaires. Specific areas of questionnaires of the quality of life related to cancer of the head and neck UWQOL (Speech, Mood, Anxiety and Taste) and FACT-H & N (emotional and physical) had better quality of life for individuals with vocal rehabilitation. The specific difficulties relating to each method of rehabilitation were perceived by the patients as inherent to the process of curing cancer. In conclusion it was observed that the absence of voice brought emotional and integration social grievances. These aspects ultimately affected the overall quality of life of the TL. Both the rehabilitation of electronic larynx (RLE) such the esophageal speech (RVE) brought improvements to the quality of life after excision of the larynx.

Esta investigación se enfoca en evaluar los cambios que se dan en una innovación de modelo de negocio, a fin de conocer cómo se generan los tipos y niveles de innovaciones requeridas en el proceso de cambio. También, se analizan los cambios generados en el sistema de gestión de calidad (SGC) a partir de la innovación en modelo de negocio y de qué manera el SGC puede aportar a la generación de innovaciones. La investigación es de tipo cualitativa y se basa en un estudio de caso; por tanto, el análisis se hace bajo la metodología de un caso simple con un diseño holístico (Yin, 2009). Para el marco teórico, la investigación se centra en explicar los principios, componentes, elementos y modelos de la calidad total. También, se definen los niveles, tipos y modos de innovación; y se hace una contextualización sobre modelos de negocio y su innovación. La información para el estudio de caso fue recolectada mediante la revisión de documentos internos del sistema integrado de gestión de la empresa (procedimientos y manuales); entrevistas a personas claves de la organización; y observación directa. / Tesis

Orientador: Ademir Jose Petenate / Dissertação (mestrado profissional) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-11-06T15:27:02Z (GMT). No. of bitstreams: 1 Silva_FlorinezPugliesida_M.pdf: 8762463 bytes, checksum: 2b81b3ba9fd5ff73026d3ef9cfb65e6e (MD5) Previous issue date: 2004 / Resumo: O Programa de Produtividade foi desenvolvido na área de usinagem da ¿Schrader Bridgeport Brasil¿ acompanhando o processo de produção do Grupo de Máquinas de Usinagem ¿Simplex¿. É um programa de ¿Gestão à Vista¿, uma vez que existem planilhas que registram, diariamente, o cálculo de produtividade das máquinas e as causas de suas paradas. Este programa surgiu com o objetivo de aperfeiçoar a operação da planta brasileira; melhorar a ¿produtividade¿ do Setor de Usinagem, por meio do aumento da eficiência dos equipamentos; reduzir as horas paradas de máquinas; os custos de produção e as horas não absorvidas por elas. O programa tem base teórica em um dos pilares do ¿TPM ¿ Manutenção Produtiva Total¿ que é a maximização da eficiência dos equipamentos (OEE ¿ Overall Equipment Efectiveness) / Abstract: The Productivity Program was developed in the Schrader Bridigeport Brasil Machine Department, following the production process of ¿Simplex¿ Machine Group. It is an ¿on View Management¿, once there are worksheets that register, daily, the machine roductivity calculations and stop causes. This program was created with the objetive of improve the brazilian site operations, increase productivity in machine department, through efficiency increase of equipament, reduce the time of stopped machines, the production costs and hours and other lost hours not include in previus itens. This program has a theorethical base in one of the foundations of ¿TPM - Total Productive Maintence¿ that is the optimization of equipment efficiency (OEE - Overall Equipament Effectiveness) / Mestrado / Gestão da Qualidade Total / Mestre Profissional em Engenharia Mecanica

by Chan Chun Wai. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1996. / Includes bibliographical references (leaves 128-137). / ABSTRACT --- p.ii / TABLE OF CONTENTS --- p.iii / LIST OF TABLES --- p.vi / LIST OF FIGURES --- p.ix / PREFACE --- p.x / Chapter / Chapter I. --- INTRODUCTION --- p.1 / Chapter II. --- LITERATURE REVIEW --- p.6 / Definition of Terms --- p.6 / Definition of Quality --- p.6 / Definition of Total Quality Management --- p.7 / "Comparison of Quality Management Approaches of Deming, Juran and Crosby" --- p.9 / Deming's Approach to Quality Management --- p.9 / Juran's Approach to Quality Management --- p.10 / "Crosby,s Approach to Quality Management" --- p.11 / Evaluation of Quality Management Frameworks --- p.12 / International Quality Standards --- p.12 / The Deming Prize --- p.14 / The Malcolm Baldrige National Quality Award --- p.15 / Selection of Quality Management Framework --- p.17 / Past Research on the Malcolm Baldrige National Quality Award Criteria --- p.20 / Chapter III. --- THE CONCEPTUAL RESEARCH MODEL AND RESEARCH HYPOTHESIS --- p.23 / The Conceptual Research Model --- p.23 / Research Hypothesis --- p.25 / Chapter IV. --- RESEARCH METHODOLOGY --- p.34 / Research Design --- p.34 / Questionnaire Design --- p.34 / Identification and Selection of Measurement Items in the Questionnaire --- p.34 / Measurement Method --- p.37 / Pretest and Refinement of the Questionnaire --- p.38 / Data Collection --- p.39 / Respondent Characteristics --- p.41 / Adjustment of Industry Effect --- p.44 / Chapter V. --- STATISTICAL ANALYSIS --- p.48 / Analysis of Construct Reliability --- p.48 / Analysis of Validity --- p.49 / Content Validity --- p.50 / Construct Validity --- p.51 / Analysis of Structural Equation Model --- p.51 / Analysis of Overall Model Fitness --- p.53 / Analysis of Measurement Model --- p.54 / Analysis of Structural Model --- p.55 / Path Analysis --- p.56 / Hypothesis Testing --- p.58 / Chapter VI. --- REFORMULATION OF THE MODEL --- p.67 / Chapter VII. --- DISCUSSION --- p.72 / The Measurement Model --- p.72 / The Structural Model --- p.78 / Chapter VIII . --- CONCLUSION --- p.89 / TABLE 1-25 --- p.92 / FIGURE 1-6 --- p.122 / BIBLIOGRAPHY --- p.128 / APPENDIX --- p.138

by Chew Chun-Ho Albert. / Includes questionnaire. / Thesis (M.B.A.)--Chinese University of Hong Kong, 1998. / Includes bibliographical references (leaves 65-66). / ABSTRACT --- p.ii / TALBE OF CONTENTS --- p.iii / LIST OF FIGURES --- p.v / LIST OF TALBES --- p.vi / ACKNOWLEDGEMENTS --- p.vii / Chapter / Chapter I. --- INTRODUCTION --- p.1 / Hong Kong's Investment in the Southern China --- p.2 / The Quality Issue --- p.3 / Research Objectives --- p.5 / Chapter II. --- LITERATURE REVIEW --- p.6 / Background of Total Quality Management --- p.7 / Definition of TQM --- p.7 / Words from the 'Quality Gurus' --- p.8 / Key Success Factors of TQM Adoption --- p.11 / Quality Movement in Hong Kong --- p.16 / Quality Movement In China --- p.18 / Chapter III. --- RESEARCH METHODOLOGY --- p.19 / Literature Review --- p.19 / Questionnaire Survey --- p.19 / Questionnaire Construction --- p.19 / Data Collection --- p.20 / Chapter IV. --- RESEARCH FINDINGS --- p.22 / Questionnaire Survey --- p.22 / Company Description and Background Information --- p.22 / Status of TQM Program --- p.27 / Implementation and Maintenance of TQM Program --- p.29 / Limitation of Questionnaire Survey --- p.35 / Chapter V. --- DISCUSSION --- p.36 / Chapter VI. --- RECOMMENDATIONS AND CONCLUSION --- p.41 / APPENDIX 1 QUSTIONNAIRE --- p.45 / APPENDIX 2 LIST OF PARTICIPANTS --- p.49 / APPENDIX 3 SUMMARY OF QUESTIONNAIRE RESPONDENTS --- p.52 / APPENDIX 4 PROFIT-SHARING PROGRAM -JOHNSONVILLE EXAMPLE --- p.61 / BIBLIOGRAPHY --- p.65