Cheung, Chi Wai. / "December 2010." / Thesis (Ph.D.)--Chinese University of Hong Kong, 2011. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese.

by Chan Sau Han. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2001. / Includes bibliographical references. / Abstracts in English and Chinese. / ABSTRACT --- p.i / 摘要 --- p.ii / ACKNOWLEDGMENT --- p.iii / CONTENTS --- p.iv / ABBREVIATIONS --- p.vi / Chapter CHAPTER 1 --- General Introduction / Chapter 1-A. --- Role of Copper in Biology --- p.1 / Chapter 1-B. --- A Brief Review on Radical Copper Proteins --- p.4 / Chapter 1-C. --- Objectives of This Work --- p.12 / Chapter 1-D. --- References --- p.13 / Chapter CHAPTER 2 --- Copper(II) and Zinc(II) Complexes containing N3O Tetradentate Ligands / Chapter 2-A. --- Introduction Results and Discussion --- p.14 / Chapter 2-B. --- Preparation of Tetradentate Ligands and Complexes --- p.27 / Chapter 2-C. --- Characterization --- p.36 / Chapter 2-D. --- Generation of Metal Phenoxyl Radical Species --- p.51 / Chapter 2-E. --- Summary --- p.57 / Chapter 2-F. --- References --- p.59 / Chapter CHAPTER 3 --- Copper(I) Complexes with N30 Tetradentate Ligands / Chapter 3-A. --- Introduction Results and Discussion --- p.62 / Chapter 3-B. --- Preparation of Copper(I) Complexes with N30 Tetradentate Ligands --- p.75 / Chapter 3-C. --- Characterization --- p.79 / Chapter 3-D. --- Reactivities of 86，87 and 88 toward Dioxygen --- p.88 / Chapter 3-E. --- Summary --- p.93 / Chapter 3-F. --- References --- p.94 / Chapter CHAPTER 4 --- Experimental Sections / Chapter 4-A. --- General Preparations and Physical Measurements --- p.97 / Chapter 4-B. --- Compounds Described in Chapter2 --- p.99 / Chapter 4-C. --- Compounds Described in Chapter3 --- p.113 / Chapter 4-D. --- Oxo-Transfer to Triphenylphosphine as Described in Chapter3 --- p.117 / Chapter 4-E. --- References --- p.119 / Chapter APPENDIX A --- 1H and13 C̐ưث1H ̐ưحNMR Spectra / Chapter A-1. --- Compounds Described in Chapter2 --- p.120 / Chapter A-2. --- Compounds Described in Chapter3 --- p.127 / Chapter APPENDIX B --- Crystallographic Data / Chapter B-1. --- X-ray Crystal Structure Data for Complexes in Chapter2 --- p.131 / Chapter B-2. --- X-ray Crystal Structure Data for Complexes in Chapter3 --- p.133 / Chapter APPENDIX C --- GC-MS Spectra / Chapter C-1. --- GC-MS Spectra for Standard Samples --- p.134 / Chapter C-2. --- GC-MS Spectra for the Reactions with Triphenylphosphine Described in Chapter3 --- p.136

by Fung Chun-wah. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2002. / Includes bibliographical references (leaves 117-119). / Abstracts in English and Chinese. / Table of Contents --- p.i / Acknowledgments --- p.v / Abbreviations --- p.vi / Abstract --- p.vii / Chapter PART I: --- ACTIVATION OF CARBON-CARBON BONDS OF NITRILES BY RHODIUM PORPHYRIN RADICAL / Chapter CHAPTER 1 --- General Introduction --- p.1 / Chapter 1.1.1 --- Activation of Carbon-Carbon Bond (CCA) by Transitional Metals --- p.1 / Chapter 1.1.1.1 --- Potential Application of C-C Bond Activation --- p.1 / Chapter 1.1.1.1.1 --- Cracking --- p.1 / Chapter 1.1.1.1.2 --- Depolymerization --- p.2 / Chapter 1.1.1.2 --- Thermodynamic and Kinetic Considerations in CCA --- p.3 / Chapter 1.1.1.3 --- C-C Bond Activation in Strained System --- p.3 / Chapter 1.1.1.4 --- C-C Bond Activation facilitated by Aromatization --- p.7 / Chapter 1.1.1.5 --- C-C Bond Activation of Carbonyl Compounds --- p.9 / Chapter 1.1.1.6 --- C-C Bond Activation of the Nitriles --- p.13 / Chapter 1.1.1.7 --- Selective C-C Bond Activation on a Multimetallic Site --- p.16 / Chapter 1.1.1.8 --- Intramolecular sp2 -sp3 C-C Bond Activation in PCP System --- p.17 / Chapter 1.1.1.9 --- CCA in N-Heterocyclic Carbene --- p.18 / Chapter 1.1.1.10 --- CCA in Pt(0) complexes bearing Chelating P´ةN- and P´ةP- Ligands --- p.19 / Chapter 1. 1.1.11 --- CCA of Alkyne via Hydroiminoacylation by Rh(I) Catalyst --- p.20 / Chapter I. 1.1.12 --- CCA in Homoallylic Alcohol by β-Allyl Elimination --- p.21 / Chapter I. 1.1.13 --- C-C Bond Activation by Metathesis of Alkanes --- p.23 / Chapter I.1.2 --- Structural Features of Rhodium Porphyrins --- p.25 / Chapter I.1.3 --- Objective of the Work --- p.27 / Chapter CHAPTER 2 --- Carbon-Carbon Bond Activation (CCA) of Nitriles by Rhodium Porphyrin Radical --- p.28 / Chapter I.2.1 --- Introduction --- p.28 / Chapter I.2.1.1 --- CCA of Nitroxides by Rhodium(II) Porphyrin Radical Rh(por) --- p.28 / Chapter I.2.2 --- CCA of Nitriles by Rh(tmp) Radical --- p.29 / Chapter I.2.2.1 --- Synthesis of Rh(tmp)Me --- p.29 / Chapter I.2.2.2 --- Synthesis of Rh(tmp) Radical --- p.30 / Chapter I.2.2.3 --- Ligand effect on CCA --- p.31 / Chapter I.2.2.3.1 --- Synthesis of Phosphines --- p.31 / Chapter I.2.2.3.2 --- Reactions between Rh(tmp) and Phosphines --- p.32 / Chapter I.2.2.3.3 --- Synthesis of Alkyl Rh(tmp) --- p.35 / Chapter I.2.2.4 --- CCA of Nitriles by Rh(tmp) with PPh3 added --- p.36 / Chapter I.2.2.4.1 --- Synthesis of Nitrile --- p.36 / Chapter I.2.2.4.2 --- Reactions between Rh(tmp) and Nitriles --- p.37 / Chapter I.2.3.4 --- Proposed Mechanism of CCA --- p.44 / Chapter CHAPTER 3 --- Experimental Section --- p.46 / Conclusion --- p.63 / References --- p.64 / Chapter PART II --- ACTIVATION OF CARBON-SILICON BONDS OF NITRILES BY RHODIUM PORPHYRIN RADICAL --- p.71 / Chapter CHAPTER 1 --- General Introduction --- p.71 / Chapter II. 1.1 --- Carbon-Silicon Bond Activation by Transitional Metals --- p.71 / Chapter II. 1.1.1 --- Potential Application of C-Si Bond Activation --- p.72 / Chapter II.l. l.2 --- C(sp3)-Si Bond Activation --- p.73 / Chapter II. 1.1.2.1 --- Intermolecular C(sp3)-Si Bond Activation in Strained System --- p.73 / Chapter II. 1.1.2.2 --- Intermolecular C(sp3)-Si Bond Activation in Unstrained System --- p.76 / Chapter II. 1.1.3 --- C(sp2)-Si Bond Activation --- p.78 / Chapter II. 1.1.3.1 --- Intermolecular C(aryl)-Si Bond Activation --- p.78 / Chapter II. 1.1.3.2 --- Intramolecular C(aryl)-Si Bond Activation --- p.84 / Chapter II. 1.1.3.3 --- C(vinyl)-Si Bond Activation --- p.87 / Chapter II. 1.1.4 --- C(sp)-Si Bond Activation --- p.89 / Chapter II. 1.2 --- Objective of the Work --- p.92 / Chapter CHAPTER 2 --- Carbon-Silicon Bond Activation (CSA) of Nitriles --- p.93 / Chapter II.2.1 --- Introduction --- p.93 / Chapter II.2.2 --- Reactions between Rh(tmp) Radical and Silylnitriles --- p.93 / Chapter II.2.2.1 --- Investigation the CSA of Trimethylsilylcyanide by Rh(tmp) --- p.93 / Chapter II.2.2.1.1 --- Synthesis of Rh(tmp)SiMe3 --- p.93 / Chapter II.2.2.1.2 --- Synthesis of Rh(tmp)CN --- p.94 / Chapter II.2.2.1.3 --- Reactions between Rh(tmp) and Trimethylsilylcyanide --- p.95 / Chapter II.2.2.1.4 --- Ligands effect on CSA of Trimethylsilylcyanide by Rh(tmp) --- p.98 / Chapter II.2.2.1.5 --- Temperature effect on CSA --- p.101 / Chapter II.2.2.2 --- Reactions between Rh(tmp) and other Silylnitriles --- p.102 / Chapter II.2.3 --- Mechanism of CSA of Trimethylsilylcyanide --- p.103 / Chapter II.2.3.1 --- Proposed Mechanism of CSA of Trimethylsilylcyanide by Rh(tmp) --- p.104 / Chapter II.2.4 --- A Comparison of CSA and CCA of Nitriles --- p.105 / Chapter CHAPTER 3 --- Experimental Section --- p.107 / Conclusion --- p.116 / References --- p.117 / List of Spectra --- p.120 / Spectra --- p.121

Radical cyclizations have been proven to be extremely important in organic synthesis. However, their reliance on toxic trialkyltin hydrides has precluded their practical applications in pharmaceutical manufacturing. Many tin hydride substitutes have been suggested but none of them are adequate alternates to the traditional tin reagent. Transition-metal hydrides have been shown to catalyze the hydrogenation and hydroformylation of unsaturated carbon-carbon bonds. Theses reactions begin with a Hydrogen Atom Transfer (HAT) from a metal to an olefin, generating a carbon-centered radical. The cyclization of that radical is an effective route to five- and six-membered rings. The HAT will be fastest if the M–H bond is weak. However, making the reaction catalytic will require that the hydride can be regenerated with H2. HCr(CO)3Cp has proven to be a good catalyst for such cyclizations, but it suffers from air sensitivity. The yield of the cyclization product depends on how the rate of radical cyclization compares with the rates of side reactions (hydrogenation and isomerization), so special substituents on a substrate are best installed to increase the cyclization rate. In attempting to improve the efficiency of radical cyclization I have studied the effect of substituents on the target double bond on the rate of cyclization. A single phenyl substituent has proven to stabilize a radical better than two phenyls. This stabilization leads to faster cyclizations and a higher cyclization yield. I also have found that Co(dmgBF2)L2 (L = THF, H2O, MeOH…) under H2 is an effective hydrogen atom donor. I have monitored by NMR the catalysis by the system of the hydrogenation of stable radicals (trityl radical and TEMPO radical) and found the rate-determining step to be the activation of hydrogen gas by CoII. The reactive form of the complex is five-coordinated cobalt complex Co(dmgBF2)2L. The Co/H2 system can also transfer hydrogen atom to C=C bonds, thus initiate radical cyclizations. The resting state of the cobalt is the CoII metalloradical, so a cycloisomerization is obtained. Such a reaction neither loses nor adds any atom and has 100% atom economy.

This Thesis describes the activity and mechanism of alkaline earth organohydroborate, tetrahydroborate and alkoxide catalysts for the ring-opening polymerisation (ROP) of cyclic esters including rac-, L-, D- and meso-lactide (LA), and rac-β-butyrolactone (rac-BBL). <b>Chapter One</b> introduces cyclic esters and general mechanisms for their ROP to give polyesters. Living and immortal ROP, an overview of stereocontrolled ROP, and determination of polylactide (PLA) stereosequences are given. Various techniques for polymer characterisations are also described. <b>Chapter Two</b> describes the activity and mechanism of heavy alkaline earth organohydroborate complexes for the ROP of LA. The synthesis and characterisation of alkaline earth alkoxide complexes serving as model species are also described, together with their activities for the ROP of LA. <b>Chapter Three</b> describes the activity and mechanism of a cyclic organohydroborate calcium complex for the ROP of LA. The role of borinic esters as chain transfer agents in the ROP of rac-LA is also discussed. <b>Chapter Four</b> describes the activity and mechanism of heavy alkaline earth tetrahydroborate complexes for the ROP of LA. The immortal ROP of rac-LA using heavy alkaline earth alkoxide complexes and borate esters as chain transfer agents is discussed. <b>Chapter Five</b> describes the activity and mechanism of alkaline earth organohydroborate, tetrahydroborate and alkoxide complexes for the ROP of rac-BBL. <b>Chapter Six</b> presents experimental procedures and characterising data for new complexes reported.

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

Made available in DSpace on 2014-12-17T15:42:08Z (GMT). No. of bitstreams: 1 GenicksonBC_DISSERT.pdf: 3221273 bytes, checksum: 93f5a94a8d409de3a6c9189089010e14 (MD5) Previous issue date: 2012-02-29 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / This work involved the synthesis, characterization and proposing the molecular structure of coordination compounds involving ligands pyrazine-2-carboxamide (PZA) and 4- hydrazide acidic pyridine carboxylic (INH) and metals of the first transition series (M = Co2+, Ni2+ and Cu2+). For the characterization of the compounds used were analytical techniques such as infrared absorption spectroscopy average (FT-IR) molar conductivity measurements, CHN elemental analysis, EDTA Complexometric, measurement of melting point, X-ray diffraction by powder method, Thermogravimetry (TG) and Differential Thermal Analysis (DTA) and Simultaneous Differential Scanning Calorimetry (DSC). The absorption spectra in the infrared region suggested that the ligand coordination to the metal center occurs through the carbonyl oxygen atom and nitrogen alpha pyrazine ring to those complexes formed with PZA. For INH complexes with metal-ligand coordination is through the carbonyl oxygen and nitrogen of the terminal hydrazide grouping. The conductivity measurements of the complexes in aqueous solution they suggest to all behavior of the type 1:2 electrolytes, and conduct of non-electrolytes in acetonitrile. The results obtained by CHN elemental analysis and EDTA Complexometric allowed to infer the stoichiometry of the compounds synthesized. For all of the complexes obtained was possible to record the melting points, neither of which melted near the melting temperature of the free ligands. The X-ray diffraction showed that the complexes of pyrazinamide exhibited diffraction lines, suggesting that these compounds are crystalline, while compounds of isoniazid, with the exception of cobalt, exhibited diffraction lines, indicating that they are crystalline. The results from the TG-DTA and DSC allowed information regarding the dehydration and thermal decomposition of these complexes / Este trabalho consistiu na s?ntese, caracteriza??o e proposi??o da estrutura molecular de compostos de coordena??o envolvendo os ligantes pirazina-2-carboxamida (PZA) e 4- hidrazida ?cida piridincarbox?lica (INH) e os metais da primeira s?rie de transi??o (M = Co2+, Ni2+ e Cu2+). Para a caracteriza??o dos compostos foram utilizadas t?cnicas de an?lise como: Espectroscopia de absor??o no Infravermelho m?dio (FT-IR), medidas de condutividade molar, An?lise Elementar de CHN, complexometria com EDTA, medidas do ponto de fus?o, Difra??o de raios-X pelo m?todo do p?, Termogravimetria (TG) e An?lise T?rmica Diferencial (DTA) simult?nea e Calorimetria Explorat?ria Diferencial (DSC). Os espectros de absor??o na regi?o do infravermelho sugerem que a coordena??o do ligante ao centro met?lico ocorreu atrav?s do ?tomo de oxig?nio carbon?lico e do nitrog?nio alfa do anel piraz?nico para os complexos formados com a PZA. Para os complexos com a INH a coordena??o ligante-metal se d? pelo oxig?nio da carbonila e nitrog?nio terminal do grupamento hidrazida. As medidas de condutividade dos complexos em solu??o aquosa sugerem para todos eles comportamento de eletr?litos do tipo 1:2; e comportamento de n?o eletr?litos em acetonitrila. Os resultados obtidos pela an?lise elementar de CHN e complexometria com EDTA permitiram inferir a estequiometria dos compostos sintetizados. Para todos os complexos obtidos foi poss?vel registrar os pontos de fus?o, sendo que nenhum deles fundiu pr?ximo da temperatura de fus?o dos ligantes livres. Os difratogramas de raios-X mostraram que os complexos da pirazinamida apresentaram linhas de difra??o, sugerindo que estes compostos s?o cristalinos, enquanto os compostos da isoniazida, com exce??o ao de cobalto, apresentaram linhas de difra??o, indicando que os mesmos s?o cristalinos. Os resultados a partir das curvas TG-DTA e DSC permitiram informa??es a respeito da desidrata??o e decomposi??o t?rmica destes complexos

A soja é uma leguminosa amplamente cultivada mundialmente, sendo o Brasil o segundo maior produtor mundial. Seu alto conteúdo proteico e baixo custo são fatores potenciais para o desenvolvimento de produtos tendo como base o isolado proteico de soja ou seus derivados. Neste sentido, a partir do farelo de soja (após extração do óleo) e métodos convencionais de extração foi obtido o concentrado proteico, substrato para o desenvolvimento de hidrolisados enzimáticos parciais de proteína. Para tanto, foram avaliadas endopeptidases (Neutrase® 0,8L, Alcalase® 2,4L e papaína) e exopeptidase (Flavourzyme® 1000L). A partir do hidrolisado foram preparados complexos/quelatos de metal-peptídeo. Em cada etapa foi avaliada a viabilidade econômica do produto gerado. A condição de extração proteica que proporcionou o melhor resultado foi a relação sólido/solvente de 1:30 (m/v), pH 9,0 ajustado com NaOH 4,0 M, com tempo de extração de 45 minutos, seguido de filtração e ajuste do pH para 4,5 com HCl 2,0 M para a precipitação de proteínas. Nestas condições foi obtido rendimento aproximado de 68,6 % de extrato com teor proteico de 84 %. O processo de hidrólise que proporcionou melhor perfil de peptídeos foi obtido com a Alcalase® 2,4L, cuja relação proteína/enzima foi de 7,5 mg:10 ?L, com tempo de incubação de 30 minutos em solução de tampão fosfato de sódio 30 mM a 55 ºC. Porém, não foi possível a secagem do hidrolisado devido ao teor de glicerol oriundo da enzima. Este inconveniente foi superado com a purificação parcial da mistura enzimática em coluna de Sephadex G25, eluída com tampão acetato de sódio (50 mM, pH 5,0), obtendo assim o concentrado enzimático sem prejuízo para a atividade da enzima. O hidrolisado assim obtido representa a proteína em seu conteúdo de aminoácido tanto qualitativamente quanto quantitativamente. Na preparação dos complexos metálicos de cobre, ferro, zinco e manganês, o ponto de equivalência metal/ligante foi determinado com a utilização de métodos eletroquímicos (voltametria cíclica ou titulação potenciométrica) e a quantificação do metal por absorção atômica revelou uma quantidade de metal ligado de 15,19; 5,55; 3,13 e 2,94 % de manganês, ferro, cobre e zinco respectivamente. A análise econômica mostrou a viabilidade para a produção de complexo de zinco, porém não se descartou a viabilidade dos outros produtos mediante ao ajuste da escala produtiva. / The soybean is a legume widely cultivated worldwide, with Brazil being the second largest world producer. Its high protein content and low cost are potential factors for the development of products based on isolated soybean protein or its derived products. In this way, from the soybean meal ( after oil extraction ) and conventional extraction methods, the protein concentrate was obtained, which is a substrate for the development of partial hydrolysates of protein. For this, were evaluated endopeptidases (Neutrase® 0.8L, Alcalase® 2.4L and papain) and a exopeptidase (Flavourzyme® 1000L). From the hydrolysate were prepared metal-peptide complexes / chelates. At each stage were evaluated the economic feasibility of the generated product. The protein extraction condition which provided the best result was the relationship solid/solvent 1:30 (w/v), pH 9.0 adjusted with 4.0 M NaOH, with extraction time of 45 minutes, followed by filtration and pH adjustment to 4.5 with 2.0 M HCl for proteins precipitation. In these conditions was obtained an income of about 68.6 % of extract with 84% of protein content. The hydrolysis process which provided the best peptides profile was obtained with Alcalase® 2.4L, whose ratio of protein / enzyme was 7.5 mg:10 ?L, with incubation time of 30 minutes in a buffer solution of sodium phosphate 30 mM at 55 º C. However, the drying of the hydrolyzed was not possible due to the glycerol content coming from the enzyme. This drawback was overcome by partial purification of the enzyme mixture on a column of Sephadex G25, eluted with sodium acetate buffer (50 mM, pH 5.0), thus obtaining the enzymatic concentrate without any loss to the enzyme activity. The thus obtained hydrolysate represents the protein in its amino acid content qualitatively and quantitatively. In the preparation of metal complexes of copper, iron, zinc and manganese, the equivalence point metal / ligand was determined using electrochemical methods (cyclic voltammetry or potentiometric titration) and metal quantification by atomic absorption revealed an amount of bounded metal of the 15.19; 5.55; 3.13 e 2.94 % of manganese, iron, copper and zinc respectively. The economic analysis showed the feasibility for the production of zinc complex, but not dismissed the feasibility of using the other products adjusting the scale of production.

Le design de complexes luminescents hétérobimétalliques a suscité un intérêt croissant ces dernières années en raison de leurs propriétés photophysiques uniques. Dans ces complexes de Nd (III) ou Yb (III) associés à des chromophores du bloc d, la forte émission du métal de transition dans le visible est utilisée pour sensibiliser de façon efficace les niveaux f-f du lanthanide(III) qui émet à son tour dans le visible ou l'IR selon la terre rare. Plus spécifiquement l'attention s'est focalisée sur le développement de complexes hétérobimétalliques d-f pour l'émission dans le proche infrarouge (NIR). En effet le proche infrarouge, comparé à l'UV, pénètre plus facilement les tissus biologiques humains notamment la peau. Bien que de telles propriétés confèrent à ces complexes bimétalliques un fort potentiel pour le diagnostic médical, aucun complexe hétérobimétallique d-f greffé de façon covalente à une matrice de silice n'a été décrit. Dans ce travail de nouveaux complexes hétérobimétalliques d-f contenant des ligands silylés ont été préparés et greffés sur la silice. Les complexes monomères [Ru(bpy)2(bpmd)]Cl2 (noté Ru), [Ru(bpy)(bpy-Si)(bpmd)]Cl2 (noté RuL) et [Ln(TTA-Si)3] (noté LnL3) et les complexes hétérobimétalliques d-f Ru-LnL3 et Ln-RuL (Ln = Nd3+, Yb3+) ont été préparés. La caractérisation des complexes a été effectuée par spectroscopie Raman, RMN 1H et 13C RMN. Les spectres RMN 1D 1H et 13C NMR ainsi que 2D de corrélation HSQC confirment les structures proposées. L'étude des propriétés photophysiques met en évidence l'émission de l'élément lanthanide dans le proche infrarouge ainsi que l'efficacité du processus de transfert d'énergie Ru-Ln qui est facilité par le ligand (2,2'-bipyrimidine). Les mesures de durée de vie et de rendement quantique (ΦET) pour le transfert d'énergie indiquent des valeurs remarquables comprises entre 30 et 84 %. La valeur du rendement quantique (ΦET) du complexe d'Yb-RuL, 73,4 %, est à ce jour la plus grande valeur rapportée pour un complexe hétérobimétallique Ru (II)-Yb (III). Le greffage sur différentes matrices de silice, mésoporeuse SiO2 ou dense SiO2 d, a été réalisé. Les nanohybrides SiO2-RuL, SiO2-NdL3 et SiO2-YbL3 ont été obtenus avec des taux de greffage allant de 0,08 à 0,18 mmol de complexe par gramme de silice. [...] / The design of heterobimetallic luminescent complexes has gained growing interest in recent years due to their unique photophysical properties. More specifically, the development of heterobimetallic complexes using d-block chromophores to sensitize the near-infrared (NIR) emission of lanthanide complexes (such as Nd(III) and Yb(III)) has received significant attention taking into account their longer emission wavelengths and the interest of the NIR emission which penetrates human tissue more effectively than UV light. These properties give them potential applications in medical diagnostics or biomedical assays. Transitions to excited state levels of transition metal complexes occurring in the visible and characterized by large absorption coefficients, could efficiently sensitize f-f levels of Ln(III) ions. In this work new d-f heterobimetallic complexes containing silylated ligands were prepared supported on silica materials. [Ru(bpy)2(bpmd)]Cl2 (labeled Ru), [Ru(bpy)(bpy-Si)(bpmd)]Cl2 (labeled RuL) and [Ln(TTA-Si)3] (labeled LnL3) and d-f heterobimetallic complexes, Ru-LnL3 and Ln-RuL (Ln = Nd3+, Yb3+) were prepared. Structural characterization was carried out by Raman Scattering, 1H and 13C NMR spectroscopies. Results obtained from 1H-13C HMBC and HSQC correlation NMR spectra confirm the formation of proposed complexes. Photophysical properties studies highlight the efficiency of Ru-Ln energy transfer processes in NIR-emitting lanthanide complexes mediated by conjugated bridging ligand (2,2'-bipyrimidine). Lifetime measurements were carried out and values of quantum yield for energy transfer (?ET) between 30 and 84 % could be evaluated. ?ET of 73.4 % obtained for the Yb-RuL complex is the largest value reported for Ru(II)-Yb(III) heterobimetallic complexes so far. Grafting on different silica matrix was also demonstrated. SiO2-Ru, SiO2-NdL3 and SiO2-YbL3 nanohybrids were obtained with grafting efficiencies from 0.08 to 0.18 mmol g-1 of silica.[...]

Imidazolium trans-[tetrachloro (dimethyl sulfoxide)(imidazole)ruthenate(III)], NAMI-A, is an experimental metastasis inhibitor whose specific mechanism of activation and action remains to be elucidated. In the nucleophilic and reducing physiological environment; it is anticipated that the most relevant and available reductants upon introduction of NAMI-A as a therapeutic agent will be the biologically-relevant free thiols. The kinetics and mechanisms of interaction of NAMI-A with biologically-active thiols cysteamine, glutathione, cysteine and a popular chemoprotectant, 2-mercaptoethane sulfonate (MESNA) have been studied spectrophotometrically under physiologically-relevant conditions. The reactions are characterized by initial reduction of NAMI-A with simultaneous formation of dimeric thiol and subsequent ligand exchange with water to various degrees as evidenced by Electospray Ionization Mass Spectrometry. Stoichiometry of reactions shows that one molecule of NAMI-A reacted with one mole of thiol to form corresponding disulfide cystamine, dimeric MESNA, oxidized glutathione and cystine. Observed rate constants, ko, for the reaction of NAMI-A with cysteamine, MESNA, GSH and cysteine were deduced to be 6.85 + 0.3 x 10-1, 9.4 + 0.5 x 10-2 , 7.42 + 0.4 x 10-3 and 3.63 + 0.3 x 10-2 s-1 respectively. Activation parameters determined from Arrhenius plots are indicative of formation of associative intermediates prior to formation of products. A negative correlation was obtained from the Brønsted plot derived from observed rate constants and the pKa of the different thiols demonstrating significant contribution of thiolate species towards the rate. In conclusion, interactions of NAMI-A with biologically-active thiols are kinetically and thermodynamically favored and should play significant roles in in vivo metabolism of NAMI-A.