腐乳是中國傳統豆類發酵製品，具有綿軟的口感和特殊的風味。其是豆腐通過真菌固態發酵，并加入鹽，米酒和香料等進行後期熟化而成的產品。本文的研究分為兩部份，第一部份對腐乳發酵過程中的毛胚，鹽胚，熟化第一天，熟化一個月以及熟化六個月的腐乳樣本進行採樣，并採用傳統微生物培養法和克隆文庫法對每個階段真菌和細菌的生態結構和動態變化進行研究。第二部份重點比較了四株腐乳產品中分離的微生物和購自台灣生物資源保存及研究中心的四株細菌的產揮發性含硫化合物能力，并挑選了最高產的一株微生物進行紫外誘變，最後獲得理想的突變株。本研究的結論如下： / 1. 真菌和細菌的總數均是在毛胚階段為最高，在進入熟化階段后開始下降。在傳統微生物培養方法下分別分離出了三株真菌和九株細菌，通過18S rDNA和16 rDNA測序，發現絲孢酵母屬（Trichosporon spp.）是真菌中的優勢菌種，蠟狀芽孢桿菌（Bacillus cereus）和解澱粉芽孢桿菌（Bacillus amyloliquefaciens）為細菌中的優勢菌種； / 2. 本研究建立了五個真菌18S rDNA克隆文庫和五個細菌16 rDNA克隆文庫用于研究真菌和細菌的生態結構和動態變化。通過聚合酶鏈式反應-限制性片段長度多態性（PCR-RFLP）的研究，分別在真菌和細菌克隆文庫中發現23和38種圖譜類型，并計算其相應比例。在進行真菌細菌測序之後，對優勢菌群進行了定性和定量分析； / 3. 在對比傳統微生物培養方法和克隆文庫技術的結果后發現，二者的結果存有差異，有些在克隆文庫中鑒定到的微生物在傳統培養方法中未能分離鑒定，而有些微生物則只能在傳統培養方法中被分離鑒定。因此，本研究中將這兩種方法結合有助於我們更為全面、客觀地研究腐乳發酵過程中真菌和細菌的生態結構和多樣性。 / 4. 對四株腐乳中分離純化的微生物和四株外來購入細菌的產揮發性含硫化合物能力進行比較，結果發現，從腐乳產品中分離純化的B-1菌株擁有最高的產揮發性含硫化合物能力，通過紫外誘變后，突變株#3在產揮發性含硫化合物以及L-蛋氨酸代謝酶活力都比初始菌株有了顯著的提升。B-1菌經測序比對后鑒定為絲孢酵母（Trichosporon sp.）。 / 本研究結果對于傳統腐乳發酵的有效控制和現代腐乳生產工藝的建立有一定指導意義，並且對於腐乳產品中的風味物質，特別是揮發性含硫化合物的產生和優化提供信息。 / Sufu (fermented soybean curd) is a soft creamy cheese-type product with a pronounced flavor and is made by fungal solid state fermentation of tofu (soybean curd) followed by aging in brine containing salt and alcohol. In first part of this research, the eco-structure and the dynamic changes of microbes during sufu production process (Pehtze, Salted pehtze, 0 Month sufu, 1 Month sufu and 6 Month sufu sample) were studied by combined microbiology techniques, including plate culture, 16S rDNA and 18S rDNA clone library and restriction fragment length polymorphism (RFLP) analysis. The second part of this research focus on the comparison of volatile sulfur-containing compounds (VSCs) production ability within isolated strains in sufu product and bacteria purchased commercially, the strain that possessed highest ability was selected and followed by a UV mutation experiment, finally obtained the desired mutant. The results of this research are as followed: / 1. The population of both fungi and bacteria were all at highest number in Pehtze stage and started to decrease in ripening stages. A combined total of three and nine living strains of fungi and bacteria were obtained from the plate culture, respectively. Through 18S rDNA and 16S rDNA sequencing, Trichosporon spp. was the dominant fungi and Bacillus cereus and Bacillus amyloliquefaciens were the dominant bacteria; / 2. Five 18S rDNA clone libraries and five 16S rDNA clone libraries from different stages of sufu production were constructed to analyze the structure and dynamic changes of fungi and bacteria. A total of 23 and 38 RFLP patterns were found, and the ratio of each pattern were calculated. After sequencing, qualitative and quantitative analysis on the dynamic changes of dominant strains was performed; / 3. After comparing the results of plate culture and clone library, it was found that there were some differences between the two. Some strains were only found in clone library while some only found in plate culture approach. Therefore, the combination of the two microbiology methods will help us to objectively and completely analyze the structure and dynamic changes of microbes in the sufu production process; / 4. The ability to produce VSCs within four strains (B-1, B-2, B-3 & B-4) isolated from a commercial sufu manufacturing process and four commercial strains (B. acetylicum, L. Lactics, S. thermophilus and L. Paracasei) were compared. Results showed that B-1 possessed both the highest VSCs production ability and L-methionine metabolism enzymatic activities among the eight strains. After UV light mutagenesis of B-1 strain, its mutant #3 significantly increased in DMDS and DMTS production and all four L-methionine-related enzymatic activities in reference to that of the starting strain (B-1). B-1 was identified as Trichosporon sp. by sequencing. / These results would make a profound significance on the control of traditional sufu production and the development of new technology for modern sufu manufacturing. They will also help to provide some important information of optimal production of VSCs in sufu ripening and the overall flavor in sufu product. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Huang, Ruolan. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2012. / Includes bibliographical references (leaves 106-117). / Abstracts also in Chinese. / Abstract --- p.i / 摘要 --- p.iii / Acknowledgement --- p.v / Table of contents --- p.vi / List of Figures --- p.x / List of Tables --- p.xiii / Chapter Chapter 1 --- : Introduction --- p.1 / Chapter 1.1 --- Sufu --- p.1 / Chapter 1.1.1 --- Classification --- p.1 / Chapter 1.1.1.1 --- Classified by processing technology --- p.1 / Chapter 1.1.1.2 --- Classified by color and flavor --- p.1 / Chapter 1.1.1.3 --- Other classifications --- p.2 / Chapter 1.1.2 --- Typical commercial manufacturing process --- p.2 / Chapter 1.1.2.1 --- Production process of naturally fermented sufu --- p.2 / Chapter 1.2.2.2 --- Production process of traditional mold-based sufu --- p.5 / Chapter 1.2.2.3 --- Production process of traditional bacteria-based sufu --- p.5 / Chapter 1.2.2.4 --- Acceleration of sufu ripening process --- p.6 / Chapter 1.1.3 --- Important ingredients in sufu production --- p.6 / Chapter 1.1.4 --- Flavor components in sufu --- p.7 / Chapter 1.1.4.1 --- Volatile flavor components --- p.7 / Chapter 1.1.4.2 --- Essential odor in sufu product --- p.8 / Chapter 1.1.4.3 --- Volatile sulfur compounds in sufu --- p.9 / Chapter 1.1.4.4 --- Using Head Space-Solid phase Microextraction (HS-SPME) to analyze the volatile sulfur components --- p.9 / Chapter 1.1.5 --- Relationship between microbes and sufu --- p.12 / Chapter 1.1.5.1 --- Microbes involved in fermentation process --- p.13 / Chapter 1.1.5.2 --- Microbial changes during the production of sufu --- p.14 / Chapter 1.1.6 --- Study on microbial ecology in food product --- p.15 / Chapter 1.1.6.1 --- PCR-based molecular techniques --- p.16 / Chapter 1.1.6.2 --- Non-PCR based molecular techniques --- p.16 / Chapter 1.1.6.3 --- The common techniques used in microbial ecology research --- p.17 / Chapter 1.1.6.4 --- Microbial ecology study by molecular biological techniques --- p.18 / Chapter 1.2 --- Objectives --- p.19 / Chapter Chapter 2 --- : Analysis of fungi diversity during sufu fermentation process --- p.21 / Chapter 2.1 --- Introduction --- p.21 / Chapter 2.2 --- Materials and methods --- p.21 / Chapter 2.2.1 --- Sample collection and preparation --- p.22 / Chapter 2.2.2 --- Plate count of fungi during sufu fermentation process --- p.22 / Chapter 2.2.3 --- Change of pH values and moisture content --- p.22 / Chapter 2.2.4 --- Total DNA extraction from fungi --- p.23 / Chapter 2.2.5 --- Preparation of competent cell --- p.23 / Chapter 2.2.6 --- 18S rDNA PCR amplification and construction of 18S rDNA clone library --- p.24 / Chapter 2.2.7 --- RFLP analysis of 18S rDNA clone library --- p.25 / Chapter 2.2.8 --- DNA sequencing for fungi identification --- p.26 / Chapter 2.2.9 --- Analysis of the diversity of 18S clone library --- p.26 / Chapter 2.2.10 --- Frequency percentage analysis --- p.27 / Chapter 2.2.11 --- Enzyme Solutions --- p.27 / Chapter 2.2.12 --- Determination of protease activity --- p.28 / Chapter 2.2.13 --- Determination of lipase activity --- p.29 / Chapter 2.2.11 --- Microtox test --- p.30 / Chapter 2.2.12 --- Statistical analysis --- p.30 / Chapter 2.3 --- Results and discussion --- p.30 / Chapter 2.3.1 --- Fungi growth on plate counting result --- p.30 / Chapter 2.3.2 --- Changes in pH and moisture content of sufu during production --- p.33 / Chapter 2.3.3 --- Construction and selection of 18S rDNA clone library --- p.35 / Chapter 2.3.4 --- Fungal diversity based on 18S rDNA clone library analysis --- p.38 / Chapter 2.3.5 --- Protease and lipase activities in Actinomucor elegans and Trichosporon japonicum --- p.45 / Chapter 2.3.5.1 --- Protease activity --- p.46 / Chapter 2.3.5.2 --- Lipase activity --- p.47 / Chapter 2.3.6 --- Toxicity of Actinomucor elegans and Trichosporon japonicum --- p.49 / Chapter 2.3.7 --- Analysis of fungi eco-structure and function during sufu fermentation process --- p.50 / Chapter 2.3.8 --- The influence of PCR bias and artifact --- p.53 / Chapter 2.2 --- Summary --- p.55 / Chapter Chapter 3 --- : Analysis of bacteria diversity during sufu fermentation process --- p.57 / Chapter 3.1 --- Introduction --- p.57 / Chapter 3.2 --- Materials and methods --- p.57 / Chapter 3.2.1 --- Sample collection and preparation --- p.57 / Chapter 3.2.2 --- Plate count of bacteria during sufu fermentation process --- p.57 / Chapter 3.2.3 --- Total DNA extraction from bacteria --- p.58 / Chapter 3.2.4 --- Preparation of competent cell --- p.58 / Chapter 3.2.5 --- 16S rDNA PCR amplification and construction of 16S rDNA clone library --- p.58 / Chapter 3.2.6 --- RFLP analysis of 16S rDNA clone library --- p.59 / Chapter 3.2.7 --- DNA sequencing for bacteria identification --- p.60 / Chapter 3.2.8 --- Analysis of the diversity of 16S rDNA clone library --- p.60 / Chapter 3.3 --- Results and discussion --- p.60 / Chapter 3.3.1 --- Bacteria growth on plate counting result --- p.60 / Chapter 3.3.2 --- Construction and selection of 16S rDNA clone library --- p.63 / Chapter 3.3.3 --- 16S rDNA clone library analysis of bacteria diversity --- p.65 / Chapter 3.3.4 --- Analysis of bacteria eco-structure and function during sufu fermentation process --- p.74 / Chapter 3.4 --- Summary --- p.77 / Chapter Chapter 4 --- : Screening the mutant possess higher capacity of forming volatile sulfur compounds (VSCs) from non-starter microbes of sufu product --- p.80 / Chapter 4.1 --- Introduction --- p.80 / Chapter 4.2 --- Materials and methods --- p.82 / Chapter 4.2.1 --- Strains and culture conditions --- p.82 / Chapter 4.2.2 --- Head space-solid phase microextraction (HS-SPME) analysis --- p.83 / Chapter 4.2.3 --- Gas Chromatography-Mass Spectrometry (GC-MS) analysis --- p.84 / Chapter 4.2.4 --- UV mutation --- p.85 / Chapter 4.2.5 --- Ellman’s method --- p.86 / Chapter 4.2.6 --- Preparation of cell-free extracts (CFE) for enzymatic assays --- p.86 / Chapter 4.2.7 --- Enzymatic assay --- p.86 / Chapter 4.2.7.1 --- L-methionine aminotransferase activity assay --- p.86 / Chapter 4.2.7.2 --- L-methionine demethiolase activity assay --- p.87 / Chapter 4.2.7.3 --- α-keto acid decarboxylase activity assay --- p.87 / Chapter 4.2.7.4 --- C-S lyase activity --- p.88 / Chapter 4.2.8 --- Statistical analysis --- p.88 / Chapter 4.3 --- Results and discussion --- p.89 / Chapter 4.3.1 --- Optimization of SPME extraction condition --- p.89 / Chapter 4.3.2 --- Selecting the start strain --- p.90 / Chapter 4.3.4.1 --- Comparison of VSCs production ability --- p.90 / Chapter 4.3.4.2 --- Comparison of enzymatic activity in L-methionine metabolism --- p.92 / Chapter 4.3.3 --- Optimization of UV exposure time --- p.95 / Chapter 4.3.4 --- Screening the mutants --- p.96 / Chapter 4.3.4.1 --- Comparison of VSCs production ability among the mutants --- p.96 / Chapter 4.3.4.2 --- Comparison of the L-methionine related enzymatic activities among the mutants --- p.99 / Chapter 4.3.4.3 --- Identified of strian B-1 --- p.101 / Chapter 4.4 --- Summary --- p.102 / Chapter Chapter 5 --- : General conclusions and future work --- p.103 / References --- p.106

by S.W. Wong. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1996. / Includes bibliographical references (leaves 76-77). / by S.W. Wong. / Title Page --- p.i / Dedication --- p.ii / Acknowledgments --- p.iii / Abstract --- p.iv / Table of Contents --- p.v / Chapter Chapter 1 --- Introduction --- p.1 / Chapter Chapter 2 --- A Brief Introduction to Nonlinear Optics --- p.7 / Chapter Chapter 3 --- Experimental Measurement of the First Hyperpolarizability β for pNA by Hyper-Rayleigh Scattering in Solution --- p.24 / Chapter 3.1 --- Introduction --- p.24 / Chapter 3.2 --- Theory of Measurement of β by HRS --- p.26 / Chapter 3.3 --- Experimental Setup --- p.31 / Chapter 3.4 --- Preparation of Sample --- p.34 / Chapter 3.5 --- Results --- p.35 / Chapter Chapter 4 --- Studies of Depolarization Ratio in HRS --- p.44 / Chapter 4.1 --- Background --- p.44 / Chapter 4.2 --- Theory --- p.45 / Chapter 4.3 --- Results --- p.55 / Chapter 4.4 --- Discussion and Conclusion --- p.57 / Chapter Chapter 5 --- Measurement on other Nonlinear Optical Compounds --- p.63 / Chapter Chapter 6 --- Conclusion --- p.73 / References --- p.76

by Tam Tin Lok Timothy. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2001. / Includes bibliographical references (leaves 75-81). / Abstracts in English and Chinese. / Table of Contents --- p.i / Acknowledgments --- p.iv / Abbreviations --- p.vi / Structural Abbreviations for Porphyrin Complexes --- p.vii / Abstract --- p.viii / Chapter Chapter 1 --- GENERAL INTRODUCTION --- p.1 / Chapter 1.1 --- Carbon-Carbon Bonds Activation by Transition Metal Complexes --- p.1 / Chapter 1.1.1 --- Kinetic and Thermodynamic Considerations in CCA --- p.2 / Chapter 1.1.2 --- C-C Bond Activation in Strained System --- p.3 / Chapter 1.1.3 --- C-C Bond Activation Driven by Aromatization --- p.4 / Chapter 1.1.4 --- C-C Bond Activation of Carbonyl Compounds --- p.5 / Chapter 1.1.5 --- Intramolecular sp2-sp3 C-C Bond Activation in PCP system --- p.8 / Chapter 1.1.6 --- C-C Bond Activation in Homoallylic Alcohol by β-Allyl Elimination --- p.10 / Chapter 1.1.7 --- C-C Bond Activation by Metathesis of Alkanes --- p.11 / Chapter 1.1.8 --- C-C Bond Activation by Nucleophilic Attack of Rhodium Porphyrin Anion --- p.14 / Chapter 1.2 --- Objective of the work --- p.14 / Chapter CHAPTER 2 --- CARBON-CARBON BONDS ACTIVATION (CCA) BY RHODIUM PORPHYRIN RADICAL --- p.16 / Chapter 2.1 --- Serendipitous Discovery of CCA --- p.16 / Chapter 2.1.1 --- Proposed Mechanism of CCA --- p.16 / Chapter 2.2 --- CCA of Rhodium Porphyrin Radical witn Nitroxides --- p.17 / Chapter 2.2.1 --- Synthesis of Rhodium Porphyrins --- p.18 / Chapter 2.2.2 --- Synthesis of Rhodium(II) Porphyrin Radical --- p.19 / Chapter 2.2.3 --- "Synthesis of 1,1,3,3-Tetraalkylisoindolin-2-oxyls" --- p.19 / Chapter 2.2.4 --- Reactions between Rhodium(II) Porphyrin Radical and Nitroxides --- p.21 / Chapter 2.2.5 --- Independent Synthesis of Alkyl Rhodium(III) Porphyrins --- p.24 / Chapter 2.3 --- CCA of Rhodium Porphyrin Radical with Other Substrates --- p.26 / Chapter 2.3.1 --- Reactions between Rhodium(II) Porphyrin Radical and Non-enolizable Ketones --- p.26 / Chapter 2.3.2 --- Reactions between Rhodium(II) Porphyrin Radical and Diketones --- p.27 / Chapter 2.4 --- Ligand Effects on Carbon-Carbon Bonds Activation --- p.28 / Chapter 2.4.1 --- Ligand Coordination between Rhodium(II) Porphyrin Radical --- p.29 / Chapter 2.4.2 --- Phosphine Effects on CCA between Rhodium(II) Porphyrin Radical and Nitroxides --- p.31 / Chapter 2.5 --- Summary --- p.32 / Chapter CHAPTER 3 --- PRELIMINARY MECHANISTIC STUDIES OF CARBON- CARBON BONDS ACTIVATION (CCA) --- p.33 / Chapter 3.1 --- Attempted Mechanistic Studies of CCA --- p.33 / Chapter 3.1.1 --- Proposed Mechanism of CCA via SH2 Pathway --- p.33 / Chapter 3.1.2 --- Homolytic Bimolecular Substitution (Sr2) --- p.33 / Chapter 3.1.3 --- Literature Review on Sh2 Reaction --- p.34 / Chapter 3.1.4 --- Prerequisities on SH2 reactions at Carbon Center --- p.36 / Chapter 3.1.5 --- Kinetic Studies of CCA between Rh(tmp) and TEMPO…… --- p.37 / Chapter 3.2 --- Stereochemical Test for CCA --- p.39 / Chapter 3.2.1 --- Objective of the Stereochemical Test --- p.39 / Chapter 3.2.2 --- Synthesis of Alkyl Rhodium(III) Porphyrins --- p.42 / Chapter 3.2.3 --- Alkyl Exchange Reactions with Rh(por)R --- p.42 / Chapter 3.3 --- Summary --- p.43 / Chapter CHAPTER 4 --- EXPERIMENTAL SECTION --- p.45 / CONCLUSION --- p.74 / REFRENCES --- p.75 / LIST OF SPECTRA --- p.82 / SPECTRA --- p.83

by Kui Chi Fai. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2001. / Includes bibliographical references. / Abstracts in English and Chinese. / Acknowledgements --- p.i / Abstracts --- p.ii / Table of Contents --- p.v / Abbreviations --- p.viii / Chapter CHAPTER 1. --- METALLATION OF AMINOPYRIDINE AND AMINOQUINOLINE / Chapter 1.1 --- INTRODUCTION --- p.1 / Chapter 1.1.1 --- General Background --- p.1 / Chapter 1.1.2 --- A Brief Review on Sodium and Potassium Amides --- p.3 / Chapter 1.1.3 --- Preparation of Sodium and Potassium Amides --- p.8 / Chapter 1.2 --- RESULTS AND DISCUSSION --- p.10 / Chapter 1.2.1 --- "Synthesis of [NH(SiButMe2)(R)] [ R = 2-C5H3N-6-Me, 8-C9H6N ] as Ligand Precursors" --- p.10 / Chapter 1.2.2 --- Synthesis of Sodium and Potassium Amido Complexes Containing the Pyridine-Functionalized Amido Ligand [N(SiButMe2)(2-C5H3N-6-Me)]- --- p.11 / Chapter 1.2.2.1 --- Sodium Pyridyl Amido Complexes --- p.11 / Chapter 1.2.2.2 --- Potassium Pyridyl Amido Complexes --- p.12 / Chapter 1.2.3 --- Synthesis of Sodium and Potassium Amido Complexes Containing the Quinoline-Functionalized Amido Ligand [N(SiButMe2)(8-C9H6N)]- --- p.15 / Chapter 1.2.3.1 --- Sodium Quinolyl Amido Complexes --- p.15 / Chapter 1.2.3.2 --- Potassium Quinolyl Amido Complexes --- p.16 / Chapter 1.2.4 --- Physical Characterization of Compounds 3-9 --- p.17 / Chapter 1.2.5 --- "Molecular Structures of Compounds 3, 5 and 7" --- p.20 / Chapter 1.3 --- EXPERIMENTALS FOR CHAPTER 1 --- p.30 / Chapter 1.3 --- REFERENCES FOR CHAPTER 1 --- p.36 / Chapter CHAPTER 2. --- "Synthesis,Structures, and Catalytic Properties of Lanthanide Metal Amides Containing the Pyridine - Functionalized Amido Ligand [N(SiButMe2)(2-C5H3N-6-Me)]-" / Chapter 2.1 --- INTRODUCTION --- p.39 / Chapter 2.1.1 --- General Background --- p.39 / Chapter 2.1.2 --- A Brief Review on Rare Earth Amido Complexes --- p.40 / Chapter 2.1.3 --- General Preparation Methods to Lanthanide Metal Amides --- p.44 / Chapter 2.1.4 --- Ring-Opening Polymerization of Lactones --- p.45 / Chapter 2.1.5 --- Objectives of This Work --- p.48 / Chapter 2.2 --- RESULTS AND DISCUSSION --- p.49 / Chapter 2.2.1 --- Synthesis and Physical Properties --- p.49 / Chapter 2.2.1.1 --- Homoleptic Lanthanide Metal Amides 10-18 --- p.49 / Chapter 2.2.1.2 --- Heteroleptic Lanthanide Metal Amides 19-22 --- p.53 / Chapter 2.2.2 --- Molecular Structures --- p.56 / Chapter 2.2.2.1 --- Molecular Structures of Homoleptic Lanthanide Metal Amides 10-18 --- p.56 / Chapter 2.2.2.2 --- Molecular Structures of Heteroleptic Lanthanide Metal Amides 19-22..… --- p.76 / Chapter 2.2.3 --- Reactivity Studies --- p.89 / Chapter 2.2.3.1 --- "Reaction with 3,5-di-tert-butylcatechol (dbcH2)" --- p.89 / Chapter 2.2.3.2 --- Ring-Opening Polymerization of s-Caprolactone --- p.95 / Chapter 2.3 --- EXPERIMENTALS FOR CHAPTER 2 --- p.100 / Chapter 2.4 --- REFERENCES FOR CHAPTER 2 --- p.108 / Chapter CHAPTER 3. --- Preparation of Pyridine Adducts of Zinc(II) Chloride and Low-coordinate Zinc(II) Dithiolate and Bis(aryloxide) Compounds / Chapter 3.1 --- INTRODUCTION --- p.111 / Chapter 3.1.1 --- General Background --- p.111 / Chapter 3.2 --- RESULTS AND DISCUSSION --- p.115 / Chapter 3.2.1 --- Synthesis of Pyridine Adducts of Zinc(II) Chloride --- p.115 / Chapter 3.2.2 --- Synthesis of Novel Three-Coordinate Zinc(II) Dithiolate and Bis(aryloxide) --- p.116 / Chapter 3.2.3 --- Physical Characterization of Compounds 23-26 --- p.118 / Chapter 3.2.4 --- Molecular Structures of Compounds 23-25 --- p.122 / Chapter 3.3 --- EXPERIMENTALS FOR CHAPTER 3 --- p.129 / Chapter 3.4 --- REFERENCES FOR CHAPTER 3 --- p.133 / Chapter CHAPTER 4. --- Summary of this Research Work --- p.135 / Appendix 1 General Procedures and Physical Measurements --- p.137 / "Appendix 2 Table A-l. Selected Crystallographic Data for Compounds 3, 5，7，10 and 11" --- p.139 / Table A-2. Selected Crystallographic Data for Compounds12-16 --- p.140 / Table A-3. Selected Crystallographic Data for Compounds17-21 --- p.141 / Table A-4. Selected Crystallographic Data for Compounds22-25 --- p.142

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 1982. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE / Vita. / Includes bibliographical references. / by Scott M. Rocklage. / Ph.D.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O presente estudo teve como objetivo quantificar as emissões de Compostos Orgânicos Voláteis do Aterro Controlado Morro do Céu localizado na cidade de Niterói, Rio de Janeiro, Brasil. Para tanto, vinte amostras foram coletadas, usando uma bomba de ar operada a bateria durante dois dias de dezembro de 2009. Uma câmara de fluxo cilíndrica de PVC de 30L foi inserida 5 cm no solo do aterro, e as amostras foram coletadas através de uma válvula na parte superior da câmera. Os resultados indicaram um valor de 1.980 Kg Km-2 h-1. O modelo Gaussiano de dispersão atmosférica ISCST3 foi utilizado para calcular a difusão e transporte dos poluentes a fim de estimar as concentrações de COV no bairro, usando dados topográficos, meteorológicos e de emissões. Valores de 525 μg m-3 de COV foram encontrados a 500 metros do aterro. As emissões do aterro foram usadas em conjunto com dados meteorológicos, utilizando o modelo de trajetória OZIPR e o mecanismo químico SAPRC para demonstrar o impacto na formação do ozônio troposférico na região. É conhecido que o ozônio é formado pela reação entre COV, NOx e luz solar. A contribuição de valores elevados de COV provenientes das emissões do aterro conduzirá a uma nova situação com valores mais elevados de ozônio na região. Os resultados da modelagem indicaram um aumento maior que 1000% nos níveis de ozônio na região do aterro, se comparado com a modelagem do ozônio para a região metropolitana do Rio de Janeiro. Os resultados mostram ser necessário que maior atenção seja dada à política de gerenciamento de RSU no Brasil, incluindo a escolha adequada para o local de instalação, o monitoramento da área durante e após o período de operação e técnicas mais adequadas de disposição dos resíduos sólidos urbanos / The purpose of this work was to quantify the Volatile Organic Compounds emissions by a landfill (Morro do Céu), located in Niterói, Rio de Janeiro State, Brazil. Twenty 10-minute samples were collected using a battery-operated air pump operated at 500 mL min-1, over a period of four days in May and December, 2009. A cylindrical 30 L PVC flux chamber was used, the open, bottom side of which was inserted into the landfill soil to a depth of 5 cm. The samples were collected using a valve at the upper, closed side of the chamber. The results indicated an elevated value of 1,980 kg km-2 h-1. A Gaussian plume dispersion model, implemented by Aermod software, was used to calculate the diffusion and transport of pollutants, and the pollutant concentrations in the surroundings were estimated using the emission, meteorological, and topographical data. Maximum values of 525 μg m-3 for VOC were found at approximately 500 m from the landfill. The landfill emissions were also compiled with meteorological data, using the OZIPR trajectory model coupled with SAPRC chemical mechanism, to demonstrate their impact on the formation of tropospheric ozone. It is well known that ozone is formed by the reactions of VOC, NOx and sunlight. The contribution of high VOC levels from the landfill emissions was expected to lead to higher ozone values. The results indicated a 1000% increase in ozone in the region of the landfill, compared to the ozone values for the metropolitan region of Rio de Janeiro. The results show that it is both necessary and desirable that greater attention be given to the political management of municipal solid waste in the Brazil, including the location choice, the monitoring of landfill areas during and after their period of operation and techniques more appropriate of disposition of municipal solid waste

Neste trabalho foi estudado o comportamento de hidróxi-calcogenetos (Se e Te) frente a biotransformações, empregando enzimas isoladas em meio orgânico ou aquoso e empregando microorganismos (fungos). Estudos comparativos sobre a influência de diversas variáveis, como solvente, temperatura, imobilização enzimática e estrutura do hidróxi-calcogeneto, foram realizados. Inicialmente os compostos foram sintetizados utilizando métodos descritos na literatura, em seguida foi estudada a resolução de hidróxiselenetos em meio orgânico empregando lipases isoladas (Esquema 1), (ver arquivo), incluindo um estudo de imobilização da PSL em diversos suportes, além do estudo da influência da variação do solvente, da temperatura, da lipase, etc. Na resolução em meio aquoso empregando enzimas isoladas, primeiramente os hidróxi-selenetos foram acetilados quimicamente e depois realizado uma triagem (com dez enzimas de diferentes fontes) empregando indicador de pH colori métrico. Posteriormente os acetatos dos hidróxi-selenetos (Esquema 2) (ver arquivo) foram submetidos à resolução enzimática em meio aquoso empregando as enzimas que foram selecionadas na triagem enzimática. As biotransformações utilizando fungos foram realizadas empregando células inteiras de algumas linhagens de Aspergillus terreus. Na seqüência foi realizada a resolução de hidróxi-teluretos em meio orgânico utilizando lipases isoladas (Esquema 3)(ver arquivo). Nessas resoluções também foi estudada a influência da variação do solvente, da lipase, do tempo, etc. De forma a demonstrar a importância dos compostos resolvidos, um hidróxi-seleneto quiral e dois hidróxi-teluretos quirais foram usados para preparar compostos pertencentes a classes de unidades estruturais de vasta ocorrência em produtos naturais: um álcool alílico e duas lactonas (Esquema 4)(ver arquivo). / In this work, the behavior of hydroxy chalcogenides (Se and Te) towards the biotransformations using isolated enzymes in organic media or aqueous media and using microorganisms (fungi) was studied. A comparative study of the effect of temperature, solvent, enzyme immobilization and structure of the substrates on the resolution was performed. Initially, the compounds had been synthesized using described methods in the literature, after, the resolution of hydroxy selenides in organic media using isolated lipases was carried out (Scheme 1)(see PDF), including a study on the immobilization of PPL on some supports, as well studies on the influence of the variation of the solvent, the temperature, lipase, etc. In the resolution in aqueous media using isolated lipases, initially the hydroxy selenides were transformed into their acetates by convertional chemical methods, and then, a screening with ten enzymes from different sources was carried out using pH indicator. In the following, the enzymatic resolution of the selanyl acetates in aqueous media using the enzymes selected in the screening step was performed (Scheme 2)(see file). The biotransformations by fungi were performed using whole cells of some Aspergillus terreus strains. In the sequence, the resolution of hydroxy tellurides in organic media using isolated lipases was carried out (Scheme 3) (see file). In these resolutions, the influence of the variation of the solvent, lipase and the reaction time was also studied. In order to demonstrate the potencial of the resolved compounds, one chiral hydroxy selenide and one chiral hydroxy telluride were used to prepare compounds belonging to classes of building blocks of wide occurrence in natural products: an allylic alcohol and a lactone (Scheme 4)(see file).

O ozônio (O3) é um dos poluentes que representa grande preocupação em termos de qualidade do ar na Região Metropolitana de São Paulo (RMSP). No ano de 2012 foram observados 98 dias de ultrapassagens do padrão horário da qualidade do ar para este poluente na RMSP. A exposição aos poluentes atmosféricos como O3 e outros está associada ao prejuízo da saúde respiratória. O enfoque deste estudo é determinar os principais Compostos Orgânicos Voláteis (COV) precursores de O3 para auxiliar no controle deste poluente. Neste trabalho foram realizadas 78 amostragens durante a semana de hidrocarbonetos no ano de 2006 e 66 amostragens de hidrocarbonetos, 62 de aldeídos e 42 de etanol durante o ano de 2011/2012, 7:00 h às 9:00 h, na estação CETESB IPEN/USP. Medidas de COV também foram realizadas no ano de 2006 e 2008, na Estação CETESB Cerqueira César. Adicionalmente, foram efetuados testes de emissões veiculares durante o ano de 2009 de 5 veículos a diesel, 3 a etanol, 2 a gasolina C e 1 motocicleta. O modelo de trajetórias OZIPR foi utilizado para determinar os principais precursores de O3. Durante o ano de 2011/2012, na Estação CETESB IPEN/USP, a classe de aldeídos representou 35,3% dos COV analisados em concentração na atmosfera, seguido pelo etanol 22,6%, compostos aromáticos 15,7%, alcanos 13,5%, cetonas 6,8%, alcenos 6,0% e alcadienos < 0,1%. Considerando a concentração dos compostos e sua reatividade, as simulações executadas com o modelo OZIPR mostraram que o acetaldeído contribuiu com 61,2% da formação do O3 na atmosfera da RMSP no ano de 2011/2012. Dos COV analisados, a classe dos aldeídos contribui com 74% da produção de O3, aromáticos 14,5%, alcenos 10,2%, alcanos 1,3% e alcadienos (isopreno) 0,03%. O estudo de emissão veicular mostrou que 39% dos aldeídos foram provenientes de veículos a etanol, 28% a diesel, 26% a gasolina C e 7% de motocicletas. As emissões dos COV por veículos a gasolina contribuíram com 44% da formação de O3, a diesel 22%, a etanol 19% e motocicletas 15%. / Ozone (O3) is a pollutant that represents great concern in terms of air quality in the metropolitan area of São Paulo (MASP). In 2012 were observed 98 days of exceedances of the standard time air quality for this pollutant in the MASP. Exposure to air pollutants such as O3 and others is associated with the injury of respiratory health. The focus of this study is to determine the main Volatile Organic Compounds (VOCs) precursors of O3 to auxiliary in control this pollutant. In this work were made 78 samples during the week of hydrocarbons in 2006 and 66 samples of hydrocarbons, 62 of aldehydes and 42 of ethanol during the year 2011/2012, 7:00 am to 9:00 am, at the CETESB IPEN/USP station. Measurements of VOCs also were realized in 2006 and 2008, in the CETESB Cerqueira Cesar station. Additionally, were performed tests vehicle emissions during the year 2009 of 5 diesel vehicles, 3 ethanol, 2 gasool and 1 motorcycle. The OZIPR trajectory model was used to determine the main O3 precursors. During the year 2011/2012, in the CETESB IPEN/USP station the class of aldehydes represented 35.3% of VOCs analyzed in concentration in the atmosphere, followed by ethanol 22.6%, aromatics 15.7%, alkanes 13.5%, ketones 6.8%, alkenes 6.0% and alkadienes <0.1%. Considering the concentration of the compounds and their reactivity, the simulations executed with the model showed that acetaldehyde OZIPR contributed with 61.2% to the formation of O3 in the atmosphere of MASP in the year 2011/2012. VOCs analyzed, the class of aldehydes contributed with 74% of the production of O3, aromatics 14.5%, alkenes 10.2%, alkanes 1.3% and alkadienes (isoprene) 0.03%. The study of vehicular emission showed that 39% of aldehydes were obtained from ethanol vehicles, 28% diesel, 26% gasoline and 7% of motorcycles. Emissions of VOCs by gasoline vehicles contributed with 44% of the formation of O3, diesel 22%, ethanol 19% and motorcycles gasoline 15%.

Made available in DSpace on 2017-07-10T19:25:14Z (GMT). No. of bitstreams: 1 Francielly.pdf: 1180381 bytes, checksum: 95d877ecc0c1c4369c711f30dadfbf6c (MD5) Previous issue date: 2012-03-02 / The commercial production of flowers and ornamental plants in Brazil has increased worldwide. Gerbera has been highlighted among the most commercialized flowers; however, studies concerning its management are still needed, especially in Brazil. Thus, this study aimed at evaluating fertilization with agribusiness waste, applied as liquid organic fertilizer (fertirrigation) to produce gerbera (Gerbera jamesonii) in pots as well as monitoring the development and quality of Florist Red Black cultivar. The statistical design was in randomized blocks with four replications and five treatments. The potted seedlings were carried out in a commercial substrate. The treatments were: mineral fertilizer and four treatments with different organic compositions using fertirrigation. The liquid organic fertilizers were chemically characterized according to pH, electrical conductivity, macro and micronutrients. The irrigation of mineral treatment was carried out with water and the organic treatments were irrigated with liquid organic fertilizers, both were carried out according to the crop evaporation. During this study, the number of leaves, plant diameter, dry mass of aerial part, analyses of development and concerning nutrient content in leaves, pH and electric conductivity of substrate solution were recorded. At the sale moment, some characteristics were evaluated, as: plant height, plant diameter, head diameter, diameter of flower stalks, inflorescence height and number of inflorescences. A sensorial analysis was used at the sale point to evaluate the visual quality of plants according to the discriminative and affective method, as for ornamental plants, the best obtained results by the metrics analysis mostly do not reflect plants with the best aesthetic characteristics. Considering the obtained data in this study, it was concluded that the liquid organic fertilizer, when applied at a suitable pH to produce gerbera, improved development and visual quality of plants with suitable features for trading. The liquid organic fertilizer in the composite number 4 provided the highest averages of phytometric parameters at the sale moment and sensory analysis. / A produção comercial de flores e plantas ornamentais no Brasil vem aumentando, bem como no mundo. Dentre as flores mais comercializadas no mundo, a gérbera se destaca, porém, estudos referentes ao manejo desta cultura ainda são necessários, principalmente no Brasil. Nesse sentindo, o objetivo deste trabalho foi avaliar a adubação com composto de resíduos da agroindústria, aplicados na forma de adubo orgânico líquido (fertirrigação), no cultivo de gérberas (Gerbera jamesonii) em vasos, bem como monitorar o desenvolvimento e a qualidade da cultivar Florist Red Black. O delineamento estatístico foi em blocos casualizados, com quatro repetições e cinco tratamentos. As mudas foram conduzidas em vaso com substrato comercial. Os tratamentos foram: adubação mineral e quatro tratamentos com diferentes composições orgânicas utilizando a fertirrigação. Os adubos orgânicos líquidos foram caracterizados quimicamente quanto ao pH, à condutividade elétrica, aos macro e micronutrientes. A irrigação do tratamento mineral foi realizada com água e os tratamentos orgânicos foram irrigados com adubos orgânicos líquidos, ambas realizadas de acordo com a evapotranspiração da cultura. No decorrer da pesquisa foram avaliados o número de folhas, diâmetro da planta, massa de matéria seca da parte aérea, análise de crescimento, análise do teor de nutrientes nas folhas, pH e condutividade elétrica da solução do substrato. No ponto de comercialização, foram avaliados: altura de planta, diâmetro da planta, diâmetro do capítulo, diâmetro de hastes florais, altura de hastes florais e número de inflorescências. Utilizou-se análise sensorial no ponto de comercialização para avaliação da qualidade visual das plantas, segundo o método discriminativo e afetivo, visto que, para plantas ornamentais, os melhores resultados obtidos por análises métricas nem sempre refletem plantas com melhores características estéticas. Considerando os dados obtidos nesta pesquisa, conclui-se que os adubos orgânicos líquidos, quando aplicados com pH adequado para a cultura de gérbera, promovem desenvolvimento e qualidade visual às plantas, com aspectos satisfatórios para comercialização. O adubo orgânico líquido na composição quatro proporcionou as maiores médias dos parâmetros fitométricos no ponto de comercialização bem como na análise sensorial.

Submitted by admin tede (tede@pucgoias.edu.br) on 2018-05-10T14:00:43Z No. of bitstreams: 1 ROSEMARY GUADELUP SILVA.pdf: 1636727 bytes, checksum: ac69c6018239051d1c31d6c17286cfce (MD5) / Made available in DSpace on 2018-05-10T14:00:43Z (GMT). No. of bitstreams: 1 ROSEMARY GUADELUP SILVA.pdf: 1636727 bytes, checksum: ac69c6018239051d1c31d6c17286cfce (MD5) Previous issue date: 2018-03-27 / The process of organic food production should be linked to environmental sustainability. It should avoid pesticides and soluble mineral fertilizers and feature a balanced use of natural resources and the provision of high quality food, free of toxic waste. Therefore, the use of organic and bio fertilizers derived from composting is presented as a key practice, integrated in the production process. Not only in rural areas but also in urban and peri-urban agriculture - involving urban gardens in public spaces or not, with the practice of "clean" plantation, combining a vision of a common world and the desire for a healthier diet. In this context of expansion of organic farming, with the involvement of society in programs anchored on the theme of sustainability and quality of life, some concerns emerge, for example, it is possible that home-based composting that uses as raw material food wastes can produce compost that still carries chemical contaminants that were present in the food leftovers that were used for composting; the residues of these contaminants might not be completely absorbed by vermicomposting and that traces of chemicals remain in the final product, so that traces of these contaminants remain in the organic compounds that will be used in the production of organic food, counter to regulations. Can social-economic conditions of the population interfere in the quality of the final results of domestic composting? What were the motives that led 100 families to take part in the pilot project RisíduoZero, in the city of Goiânia and wat were reasons for discontinuation? Is it worthwhile to invest in zero waste programs? The data obtained suggest a shift from preconceived ideas in various ways: Families living in houses do not necessary adhere better to the program; people with less formal education don’t show less ecological conscience and people with lower income do not necessarily show more interest in recycling urban waste. Considering that the use of the compost produced by recycling urban organic waste is still a new paradigm in Brazil and that many doubts remain concerning its use in agriculture, we propose, in this dissertation, to adopt sampling method to investigate the obtained compost, to understand its characteristics, including the presence of dangerous substances, and thus securing the adequate use in organic agriculture, to guarantee all benefits of this practice and avoiding damage to food producers and consumers. / O processo produtivo de orgânicos, não está somente atrelado à oferta de alimentos de alta qualidade, mas também à sustentabilidade ambiental - eliminando o uso de agrotóxico e de adubos minerais solúveis, bem como ao uso equilibrado dos recursos naturais. Sendo assim, a utilização do composto orgânico e do biofertilizante derivados da compostagem, se apresenta como prática fundamental, integrada ao processo produtivo. Não só no meio rural, como também na agricultura urbana e periurbana - que desenvolvem hortas em espaços públicos ou não, com a prática de plantio “limpo”, combinando uma visão de mundo comum e o desejo de uma alimentação mais saudável. Nesse contexto de expansão da cultura orgânica, com a adesão da sociedade aos programas ancorados no tema da sustentabilidade e da qualidade de vida, novas iniciativas surgem. A presente pesquisa verificou qual foi o interesse que levou 100 famílias a aderirem ao projeto piloto de compostagem domestica Residência ResíduoZero, na cidade de Goiânia um projeto de compostagem doméstica, os motivos de persistência/desistência no projeto, como também a destinação do produto da compostagem para aplicação a agricultara orgânica ou para outros fins e finalmente, lança a discussão acerca de uma nova preocupação: É possível que a compostagem que utiliza como matéria prima resíduos de alimentos que às vezes carregam em si altas doses de contaminantes, possam produzir adubos orgânicos igualmente contaminados e que serão utilizados na produção de alimentos “orgânicos”, contrariando suas normas? O método da pesquisa consistiu numa análise do banco de dados do projeto e de dados obtidos por contato pessoal com participantes do projeto piloto. Verificou-se que vinte por cento dos participantes iniciais desistiu. Verificou-se que os motivos mais importantes para adesão são realizar a reciclagem de resíduos de alimentos e produzir adubo e biofertilizante de baixo custo para uso próprio e para doação. O motivo mais importante de desistência é falto de tempo, o que aponta um problema que deve ser abordado no recrutamento para projetos futuros. A destinação mais comum do adubo produzido é o cultivo de plantas de casa, enquanto o uso para hortas domésticas ou horas comunitárias se mostra menos frequente. Observe-se que uma parte pequena da produção segue a ser comercializada. Os resultados obtidos sugerem quebra de paradigmas de conceitos pré-concebidos em vários aspectos: famílias que moram em casas, não necessariamente tem mais adesão ao programa; pessoas de menor escolaridade não mostram menor consciência ecológica e pessoas de maior renda não possuem necessariamente maior interesse pela reciclagem do resíduo urbano. Considerando que a utilização do composto produzido pela reciclagem de resíduos orgânicos urbanos ainda é um paradigma novo para o país e que muitas incertezas permanecem trazendo insegurança quanto a sua utilização na agricultura, é que propomos adotar metodologia de amostragem para o composto obtido, para conhecer as características do adubo, inclusive quanto a presença de substancias danosas no composto e assim, assegurar a utilização apropriada e segura na agricultura orgânica, garantindo todos os benefícios dessa prática e evitando prejuízos tanto para os produtores como para os consumidores desses alimentos.