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Uma perspectiva computacional sobre catálise enzimática; A computational perspective on enzymatic catalysis

ARANTES, Guilherme M.
Fonte: Sociedade Brasileira de Química Publicador: Sociedade Brasileira de Química
Tipo: Artigo de Revista Científica
POR
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Enzymes are extremely efficient catalysts. Here, part of the mechanisms proposed to explain this catalytic power will be compared to quantitative experimental results and computer simulations. Influence of the enzymatic environment over species along the reaction coordinate will be analysed. Concepts of transition state stabilisation and reactant destabilisation will be confronted. Divided site model and near-attack conformation hypotheses will also be discussed. Molecular interactions such as covalent catalysis, general acid-base catalysis, electrostatics, entropic effects, steric hindrance, quantum and dynamical effects will also be analysed as sources of catalysis. Reaction mechanisms, in particular that catalysed by protein tyrosine phosphatases, illustrate the concepts.; Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Nanostructured copper thin film used for catalysis

CARVALHO, Alexsander Tressino de; LIMA, Roberto da Rocha; SILVA, Lilian Marques; FACHINI, Estevao; SILVA, Maria Lucia Pereira da
Fonte: ELSEVIER SCIENCE SA Publicador: ELSEVIER SCIENCE SA
Tipo: Artigo de Revista Científica
ENG
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Catalytic properties of copper thin films deposited in small channels and cavities were tested using Raman microscopy and mass spectroscopy (MS) techniques, mainly. The catalytic surface conditions were addressed visually and chemically by optical microscopy and X-ray photoelectron spectroscopy (XPS), respectively. The experimental conditions of present work induced copper oxidation; eventually a number of carbon species and graphite remained on the catalytic surface. Quartz crystal microbalance and mass spectroscopy data support both adsorption and catalysis phenomena. MS showed CO2 formation during n-hexane heating process but not to 2-propanol, probably due to redox reactions. XPS of copper surface present in the cavity after catalysis tests detected Cu2O and a range of possible carbon species. The adsorption and catalytic performance of copper films deposited in cavities and microchannels were quite similar. A simple miniaturized device for microanalysis was proposed. (C) 2007 Elsevier B.V. All rights reserved.

New insights on reaction pathway selectivity promoted by crown ether phase-transfer catalysis: Model ab initio calculations of nucleophilic fluorination

Pliego, Josefredo R., Jr.; Riveros, Jose M.
Fonte: ELSEVIER SCIENCE BV; AMSTERDAM Publicador: ELSEVIER SCIENCE BV; AMSTERDAM
Tipo: Artigo de Revista Científica
ENG
Relevância na Pesquisa
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Crown ethers have the ability of solubilizing inorganic salts in apolar solvents and to promote chemical reactions by phase-transfer catalysis. However, details on how crown ethers catalyze ionic S(N)2 reactions and control selectivity are not well understood. In this work, we have used high level theoretical calculations to shed light on the details of phase-transfer catalysis mechanism of KF reaction with alkyl halides promoted by 18-crown-6. A complete analysis of the of the model reaction between KF(18-crown-6) and ethyl bromide reveals that the calculations can accurately predict the product ratio and the overall kinetics. Our results point out the importance of the K* ion and of the crown ether ring in determining product selectivity. While the K* ion favors the S(N)2 over the E2 anti pathway, the crown ether ring favors the S(N)2 over E2 syn route. The combination effects lead to a predicted 94% for the S(N)2 pathway in excellent agreement with the experimental value of 92%. A detailed analysis of the overall mechanism of the reaction under phase-transfer conditions also reveals that the KBr product generated in the nucleophilic fluorination acts as an inhibitor of the 18-crown-6 catalyst and it is responsible for the observed slow reaction rate. (C) 2012 Elsevier B.V. All rights reserved.; Brazilian Research Council (CNPq); Brazilian Research Council (CNPq); Brazilian Office of Higher Education (CAPES); Brazilian Office of Higher Education (CAPES); Fundacao de Amparo a Pesquisa do Estado de Minas Gerais (FAPEMIG); Fundacao de Amparo a Pesquisa do Estado de Minas Gerais (FAPEMIG); Institute for Science and Technology of Materials (INOMAT); Institute for Science and Technology of Materials (INOMAT)

Catálise oxidativa de clusters de rutênio e porfirinas supramoleculares; Oxidative catalysis of ruthenium clusters and supramolecular porphyrins

Nunes, Genebaldo Sales
Fonte: Biblioteca Digitais de Teses e Dissertações da USP Publicador: Biblioteca Digitais de Teses e Dissertações da USP
Tipo: Tese de Doutorado Formato: application/pdf
Publicado em 11/07/2005 PT
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A atividade catalítica de clusters trigonais de acetato de rutênio e porfirinas supramoleculares contendo quatro unidades de clusters periféricos ou complexos de bis(bipiridina)rutênio, na oxidação de substratos orgânicos por iodosil-benzeno ou terc-butil-hidroperóxido, é abordada nesta tese. Foram feitos estudos cinéticos para elucidar o mecanismo de catálise, com especial destaque para duas espécies supramoleculares isoméricas representadas por Mn(3-TRPyP) ou Mn(4-TRPyP), nos quais os complexos de bis(bipiridina)(cloro)rutênio se coordenam à tetrapiridilporfirina através das posições meta ou para da ponte piridínica, respectivamente. Além da maior seletividade proporcionada pelos catalisadores supramoleculares, a substituição do íon cloreto pela água nos complexos periféricos de rutênio, intensificou a atividade catalítica, gerando novos sítios ativos, do tipo Ru(IV)=O. Também foram estudados clusters trinucleares de rutênio, altamente reativos, no estado Ru(III)Ru(IV)Ru(IV)=O. Estes foram gerados eletroquimicamente em solução aquosa, apresentando pronunciada atividade catalítica na oxidação do alcool benzílico. Finalmente, uma espécie dimérica de cluster, ainda inédita, com ponte oxo, foi caracterizada e investigada do ponto de vista catalítico.; The catalytic activity of trinuclear ruthenium clusters and supramolecular tetrapyridylporphyrins containing four peripheral cluster units or bis(bipyridine)ruthenium complexes...

Aplicação da catálise de trasnferência de fase na avaliação de rotas alternativas para obtenção industrial da dicicloverina caramifeno e amiodarona; The use of phase transfer catalysis, in the development of alternative routes for industrial production of dicycloverine, caramiphen and amiodarone

Polakiewicz, Bronislaw
Fonte: Biblioteca Digitais de Teses e Dissertações da USP Publicador: Biblioteca Digitais de Teses e Dissertações da USP
Tipo: Tese de Doutorado Formato: application/pdf
Publicado em 20/12/1994 PT
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O emprego da catálise de transferência de fase substituindo uma ou mais etapas da síntese de um fármaco, pode ser um recurso vantajoso sob o ponto de vista tecnológico. Empregado na síntese de importantes fármacos que são a dicicloverina, caramifeno eamiodarona, a catálise de transferência de fase revelou-se muito vantajosa na síntese dos dois primeiros. A dicicloverina e o caramifeno tiveram as suas rotas de obtenção verticalizadas, com bons resultados e custos bem mais baixos quando comparados com os atualmente adquiridos no exterior. Ficou evidente que a catálise de transferência de fase pode ser aplicada com sucesso na produção destes e outros fármacos em associação com técnicas já conhecidas com ótimos resultados.; The phase transfer catalysis application replacing one or more steps in the drug synthesis, can be of advantage in the technologycal approach. Applied to the synthesis of important drugs such as diciclomine, caramiphen,and amiodarone, the phase transfer catalysis resulted in a very advantageous method in the first two drugs. The diciclomine and the caramiphen, gets their obtention routes from raw materiaIs wi th good resul ts and low coasts, when compared wi th the drugs presently purchassed in foreign countries. It is clear that the phase transfer catalysis...

Produção de polímeros derivados de fontes renováveis via catálise enzimática; Production of polymers derived from renewable sources by enzyme catalysis

Juais, Danielle
Fonte: Biblioteca Digitais de Teses e Dissertações da USP Publicador: Biblioteca Digitais de Teses e Dissertações da USP
Tipo: Dissertação de Mestrado Formato: application/pdf
Publicado em 17/04/2009 PT
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A busca por materiais derivados de fontes renováveis e com características como biocompatibilidade e biodegradabilidade tem crescido significativamente nos últimos anos. A utilização de enzimas na polimerização representa um grande passo para a obtenção destes, visto que possibilitam a produção de polímeros evitando a utilização de catalisadores tóxicos e, assim, melhorando sua biocompatibilidade. O presente trabalho descreve a utilização de monômeros funcionais derivados de fontes renováveis na produção de poliésteres hidrolisáveis via catálise enzimática. As sínteses de polímeros produzidos a partir de isosorbídeo e ácidos dicarboxílicos ou derivados - como seus ésteres alquílicos e vinílicos - foram feitas utilizando a lipase de Candida antarctica Fração B como catalisador. As polimerizações foram realizadas por policondensações em massa e em solução, utilizando-se diferentes solventes e diferentes técnicas para remoção de subprodutos de reação. A principal abordagem foi o estudo das diferentes condições reacionais realizadas, variando-se o tempo de reação, tipo do monômero, solvente utilizado (se for o caso) e tipo de técnica para remoção de subprodutos visando o aumento da massa molar dos polímeros. A condição que forneceu os materiais com maiores massas molares foi a policondensação em solução...

Catálise assimétrica no Brasil : desenvolvimento e potencialidades para o avanço da indústria química brasileira; Asymmetric catalysis in Brazil : development and potential for advancement of brazilian chemical industry

Braga, Antonio Luiz; Lüdtke, Diogo Seibert; Schneider, Paulo Henrique; Andrade, Leandro Helgueira de; Paixão, Marcio W.
Fonte: Universidade Federal do Rio Grande do Sul Publicador: Universidade Federal do Rio Grande do Sul
Tipo: Artigo de Revista Científica Formato: application/pdf
POR
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The preparation of enantiomerically pure or enriched substances is of fundamental importance to pharmaceutical, food, agrochemical, and cosmetics industries and involves a growing market of hundreds of billions of dollars. However, most chemical processes used for their production are not environmentally friendly because in most cases, stoichiometric amounts of chiral inductors are used and substantial waste is produced. In this context, asymmetric catalysis has emerged as an efficient tool for the synthesis of enantiomerically enriched compounds using chiral catalysts. More specifically, considering the current scenario in the Brazilian chemical industry, especially that of pharmaceuticals, the immediate prospect for the use of synthetic routes developed in Brazil in an enantioselective fashion or even the discovery of new drugs is practically null. Currently, the industrial production of drugs in Brazil is primarily focused on the production of generic drugs and is basically supported by imports of intermediates from China and India. In order to change this panorama and move forward toward the gradual incorporation of genuinely Brazilian synthetic routes, strong incentive policies, especially those related to continuous funding...

Hybrid organic-inorganic materials: application in oxidative catalysis

Rocha, G M S R O
Fonte: Nova Science Publishers Publicador: Nova Science Publishers
Tipo: Parte de Livro
ENG
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Oxidative catalysis has been and will be playing an important role in the production of large quantities of intermediates. This technology has a great potential for improvement and this has led to a series of better processes, including the development of a great diversity of suitable catalysts. Within these compounds, metal phosphates and phosphonates possessing layered and pillared structures were found to constitute a very good alternative as catalysts to be used in oxidative catalysis. Metal phosphates and phosphonates can be considered as strong inorganic solid acids and much of their catalytic activity has been attributed to the Brønsted acidity of the interlayered hydroxyl groups and to the Lewis acidity of the metal center. Metal phosphates and phosphonates can be obtained at low temperatures, in aqueous media, using soft chemical routes and their preparation is quite accessible if the correct phosphonic acids and phophates are available. These heterogeneous materials are very interesting from the economical as well as from the environmental points of view because of the high yields and short reaction times, easy recovery from the reaction mixtures and the possibility to perform reactions in solvent-free conditions. Due to their particular physical and chemical properties and high versatility...

Benefits of membrane electrodes in the electrochemistry of metalloproteins: mediated catalysis of Paracoccus pantotrophus cytochrome c peroxidase by horse cytochrome c: a case study

Sousa, P. M. Paes de; Pauleta, Sofia R.; Rodrigues, D.; Gonçalves, M. L. Simões; Pettigrew, G. W.; Moura, Isabel; Moura, José J. G.; Santos, M. M. Correia dos
Fonte: Springer Publicador: Springer
Tipo: Artigo de Revista Científica
Publicado em //2008 ENG
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J Biol Inorg Chem. 2008 Jun;13(5):779-87. doi: 10.1007/s00775-008-0365-8; A comparative study of direct and mediated electrochemistry of metalloproteins in bulk and membrane-entrapped solutions is presented. This work reports the first electrochemical study of the electron transfer between a bacterial cytochrome c peroxidase and horse heart cytochrome c. The mediated catalysis of the peroxidase was analysed both using the membrane electrode configuration and with all proteins in solution. An apparent Michaelis constant of 66 +/- 4 and 42 +/- 5 microM was determined at pH 7.0 and 0 M NaCl for membrane and bulk solutions, respectively. The data revealed that maximum activity occurs at 50 mM NaCl, pH 7.0, with intermolecular rate constants of (4.4 +/- 0.5) x 10(6) and (1.0 +/- 0.5) x 10(6) M(-1) s(-1) for membrane-entrapped and bulk solutions, respectively. The influence of parameters such as pH or ionic strength on the mediated catalytic activity was analysed using this approach, drawing attention to the fact that careful analysis of the results is needed to ensure that no artefacts are introduced by the use of the membrane configuration and/or promoters, and therefore the dependence truly reflects the influence of these parameters on the (mediated) catalysis. From the pH dependence...

Towards an atomic level understanding of niobia based catalysts and catalysis by combining the science of catalysis with surface science

Schmal,Martin; Freund,Hans-Joachim
Fonte: Academia Brasileira de Ciências Publicador: Academia Brasileira de Ciências
Tipo: Artigo de Revista Científica Formato: text/html
Publicado em 01/06/2009 EN
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The science of catalysis and surface science have developed, independently, key information for understanding catalytic processes. One might argue: is there anything fundamental to be discovered through the interplay between catalysis and surface science? Real catalysts of monometallic and bimetallic Co/Nb2O5 and Pd-Co/Nb2O5 catalysts showed interesting selectivity results on the Fischer-Tropsch synthesis (Noronha et al. 1996, Rosenir et al. 1993). The presence of a noble metal increased the C+5 selectivity and decreased the methane formation depending of the reduction temperature. Model catalyst of Co-Pd supported on niobia and alumina were prepared and characterized at the atomic level, thus forming the basis for a comparison with "real" support materials. Growth, morphology and structure of both pure metal and alloy particles were studied. It is possible to support the strong metal support interaction suggested by studies on real catalysts via the investigation of model systems for niobia in comparison to alumina support in which this effect does not occur. Formation of Co2+ penetration into the niobia lattice was suggested on the basis of powder studies and can be fully supported on the basis of model studies. It is shown for both real catalysts and model systems that oxidation state of Co plays a key role in controlling the reactivity in Fischer-Tropsch reactions systems and that the addition of Pd is a determining factor for the stability of the catalyst. It is demonstrated that the interaction with unsaturated hydrocarbons depends strongly on the state of oxidation.

Silica functionalized sulfonic acid catalyzed one-pot synthesis of 4,5,8a-triarylhex-ahydropyrimido[4,5-d]pyrimidine-2,7(1H,3 H)-diones under liquid phase catalysis

Gupta,Princy; Kumar,Vineet; Paul,Satya
Fonte: Sociedade Brasileira de Química Publicador: Sociedade Brasileira de Química
Tipo: Artigo de Revista Científica Formato: text/html
Publicado em 01/01/2010 EN
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SiO2-SO3H catalyzed one-pot synthesis of 4,5,8a-triarylhexahydropyrimido[4,5-d]pyrimidine-2,7(1H,3 H)-diones (4a-k) is reported under liquid phase catalysis. The catalyst is easily prepared, highly stable, very simple to handle and recycled for five times without loss of significant activity.

Dual bifunctional catalysis and the α-effect in the reaction of hydroxylamine with phenylacetate

Mazera,Deise J.; Pliego Jr.,Josefredo R.; Almerindo,Gizelle I.; Gesser,José C.
Fonte: Sociedade Brasileira de Química Publicador: Sociedade Brasileira de Química
Tipo: Artigo de Revista Científica Formato: text/html
Publicado em 01/11/2011 EN
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The reaction of hydroxylamine with phenyl acetate was theoretically investigated to shed light on the role of catalysis and the origin of the α-effect in this system. Calculations at the B3LYP/6-311+G(2df,2p)//HF/6-31G(d) level and the solvent effect included at the PCM/HF/6-31G(d) level predict that the direct attack of hydroxylamine to the carbonyl centre has a high ΔG‡ barrier, close to 50 kcal mol-1. A second hydroxylamine molecule can catalyse the process through bifunctional catalysis using both the NH2 and OH groups simultaneously. This dual bifunctional catalysis decreases the ΔG‡ to 19 kcal mol-1 and is able to explain the experimentally observed kinetics and product ratio.

Ionic Liquids and Catalysis

Souza,Michèle O. de
Fonte: Sociedade Brasileira de Química Publicador: Sociedade Brasileira de Química
Tipo: Artigo de Revista Científica Formato: text/html
Publicado em 01/12/2014 EN
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This paper explores the growing number of publications concerning the use of ionic liquids (ILs) in the period from 1994 to 2013. Catalysis can be identified as the area responsible for the surge of interest in ILs. The same is true for the Brazilian scientific community. The contributions of the group of Prof Roberto Fernando de Souza and those obtained through numerous collaborations are described in this context. The literature survey shows that in the studied period the significant increase in ILs publications occurs at different times depending on their applied area (catalysis, energy, materials, analytical chemistry, biomass, etc.).

Synthesis and Characterization of LaNiO3, LaNi(1-x)Fe xO3 andLaNi(1-x)Co xO3 Perovskite Oxides for Catalysis Application

Lima,Sania Maria de; Assaf,José Mansur
Fonte: ABM, ABC, ABPol Publicador: ABM, ABC, ABPol
Tipo: Artigo de Revista Científica Formato: text/html
Publicado em 01/09/2002 EN
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Mixed metal oxides with perovskite-type structure show a great potential to be used in catalysis, electrocatalysis and electronic ceramics. Perovskites oxides catalysts with the composition LaNiO3, LaNi(1-x)Fe xO3 and LaNi(1-x)Co xO3 (x = 0.4 and 0.7) have been synthesized by the precipitation method to be used in the methane reforming to produce hydrogen and synthesis gas. The compounds were characterized by X-ray diffraction, thermogravimetric and differential thermal analysis, inductively coupled plasma atomic emission spectroscopy, surface area measurements, energy dispersive X-ray spectrometry coupled to scanning electron microscopy and temperature programmed reduction. The results showed that a suitable combination of the preparation method with calcination variables (time and temperature) could result in oxides with the desired structure and with important properties at the application point of view in heterogeneous catalysis.

Asymmetric catalysis in complex target synthesis

Taylor, Mark S.; Jacobsen, Eric N.
Fonte: National Academy of Sciences Publicador: National Academy of Sciences
Tipo: Artigo de Revista Científica
EN
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This article describes three distinct strategies by which stereochemically complex molecules are synthesized and the ways asymmetric catalysis can impact on all three. The development of general methods to prepare synthetically useful building blocks leads to an expanded “chiral pool” of potential starting materials for asymmetric synthesis. The possibility of discovering new reactions to access new types of building blocks is particularly attractive and serves to help define the frontiers of the field. Asymmetric catalysis can also be applied to diastereoselective synthesis such that the stereochemistry of the catalyst, and not that of the substrate, determines the relative configuration of the product. Finally, in reactions where multiple stereocenters are generated simultaneously or in tandem, catalyst and substrate control can operate in a complementary manner to achieve one of many possible stereochemical outcomes selectively.

Mutagenesis Studies of Substrate Recognition and Catalysis in the Sortase A Transpeptidase from Staphylococcus aureus*

Bentley, Matthew L.; Lamb, Erin C.; McCafferty, Dewey G.
Fonte: American Society for Biochemistry and Molecular Biology Publicador: American Society for Biochemistry and Molecular Biology
Tipo: Artigo de Revista Científica
Publicado em 23/05/2008 EN
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The Staphylococcus aureus transpeptidase sortase A (SrtA) is responsible for anchoring a range of virulence- and colonization-associated proteins to the cell wall. SrtA recognizes substrates that contain a C-terminal LPXTG motif. This sequence is cleaved following the threonine, and an amide bond is formed between the threonine and the pentaglycine cross-bridge of branched lipid II. Previous studies have implicated the β6/β7 loop region of SrtA in LPXTG recognition but have not systematically characterized this domain. To better understand the individual roles of the residues within this loop, we performed alanine-scanning mutagenesis. Val-168 and Leu-169 were found to be important for substrate recognition, and Glu-171 was also found to be important, consistent with its hypothesized role as a Ca2+-binding residue. Gly-167 and Asp-170 were dispensable for catalysis, as was Gln-172. The role of Arg-197 in SrtA has been the subject of much debate. To explore its role in catalysis, we used native chemical ligation to generate semi-synthetic SrtA in which we replaced Arg-197 with citrulline, a non-ionizable analog. This change resulted in a decrease of <3-fold in kcat/Km, indicating that Arg-197 utilizes a hydrogen bond, rather than an electrostatic interaction. Our results are consistent with a model for LPXTG recognition wherein the Leu-Pro sequence is recognized primarily by hydrophobic contacts with SrtA Val-168 and Leu-169...

Force-Clamp Spectroscopy Detects Residue Co-evolution in Enzyme Catalysis*S⃞

Perez-Jimenez, Raul; Wiita, Arun P.; Rodriguez-Larrea, David; Kosuri, Pallav; Gavira, Jose A.; Sanchez-Ruiz, Jose M.; Fernandez, Julio M.
Fonte: American Society for Biochemistry and Molecular Biology Publicador: American Society for Biochemistry and Molecular Biology
Tipo: Artigo de Revista Científica
Publicado em 03/10/2008 EN
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Understanding how the catalytic mechanisms of enzymes are optimized through evolution remains a major challenge in molecular biology. The concept of co-evolution implicates that compensatory mutations occur to preserve the structure and function of proteins. We have combined statistical analysis of protein sequences with the sensitivity of single molecule force-clamp spectroscopy to probe how catalysis is affected by structurally distant correlated mutations in Escherichia coli thioredoxin. Our findings show that evolutionary anti-correlated mutations have an inhibitory effect on enzyme catalysis, whereas positively correlated mutations rescue the catalytic activity. We interpret these results in terms of an evolutionary tuning of both the enzyme-substrate binding process and the chemistry of the active site. Our results constitute a direct observation of distant residue co-evolution in enzyme catalysis.

Escherichia coli DNA Adenine Methyltransferase: THE STRUCTURAL BASIS OF PROCESSIVE CATALYSIS AND INDIRECT READ-OUT

Coffin, Stephanie R.; Reich, Norbert O.
Fonte: American Society for Biochemistry and Molecular Biology Publicador: American Society for Biochemistry and Molecular Biology
Tipo: Artigo de Revista Científica
EN
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We have investigated the structural basis of processive GATC methylation by the Escherichia coli DNA adenine methyltransferase, which is critical in chromosome replication and mismatch repair. We determined the contribution of the orthologically conserved phosphate interactions involving residues Arg95, Asn126, Asn132, Arg116, and Lys139, which directly contact the DNA outside the cognate recognition site (GATC) to processive catalysis, and that of residue Arg137, which is not conserved and contacts the DNA backbone within the GATC sequence. Alanine substitutions at the conserved positions have large impacts on processivity yet do not impact kcat/KmDNA or DNA affinity (KDDNA). However, these mutants cause large preferences for GATC sites varying in flanking sequences when considering the pre-steady state efficiency constant kchem/KDDNA. These changes occur mainly at the level of the methylation rate constant, which results in the observed decreases in processive catalysis. Thus, processivity and catalytic efficiency (kcat/KmDNA) are uncoupled in these mutants. These results reveal that the binding energy involved in DNA recognition contributes to the assembly of the active site rather than tight binding. Furthermore, the conserved residues (Arg95...

I. Engaging Cationic Intermediates in Asymmetric Catalysis: Enantioselective Reactions of Carbenium Ions and N,N-Dialkyliminium Ions II. Enantioselective Catalysis of the Cope-Type Hydroamination by H-Bond Donors

Brown, Adam Ross
Fonte: Harvard University Publicador: Harvard University
Tipo: Thesis or Dissertation
EN_US
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The research described here explores the ability of dual H-bond donor catalysts to induce asymmetry in a variety of synthetically useful transformations that proceed via diverse reactive intermediates. In Chapters 1-3, we investigate ureas and thioureas as anion-binding catalysts for asymmetric reactions that proceeed via cationic intermediates with little precedent as electrophiles in asymmetric catalysis. Chapter 4 details our application of H-bond donor catalysis to the Cope-type hydroamination. Chapter 1 describes the development of an asymmetric aldehyde alkylation catalyzed by a bifunctional primary aminothiourea. A variety of 2-aryl propionaldehydes are alkylated with benzhydryl bromides in moderate to good yields and good enantioselectivities. Catalyst structure-activity relationship studies of the alkylation pointed towards electrophile activation by the dual H-bond donor moiety. Experiments aimed at gaining a better understanding of the electophile activation mode and characterizing the activated electrophilic intermediate in the alkylation reaction are described in Chapter 2. The development of an enantioselective cyanide addition to N,N-dialkyliminium intermediates is the subject of Chapter 3. A variety of strategies for accessing N...

Mononuclear Ruthenium Complexes and their Application in Homogeneous and Heterogeneous Catalysis

Vaquer Malia, Lydia
Fonte: [Barcelona] : Universitat Autònoma de Barcelona, Publicador: [Barcelona] : Universitat Autònoma de Barcelona,
Tipo: Tesis i dissertacions electròniques; info:eu-repo/semantics/doctoralThesis; info:eu-repo/semantics/publishedVersion Formato: application/pdf
Publicado em //2011 ENG
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La tesis presentada es un estudio basado en la síntesis, caracterización espectrocópica y electroquímica y aplicaciones en catálisis de nuevos complejos mononucleares de rutenio con una amplia variedad de ligandos polipiridílicos. La influencia de las propiedades electrónicas de los ligandos coordinados al centro metálico sobre las propiedades redox de los complejos resultantes y su comportamiento en catálisis de oxidación ha sido estudiada y racionalizada. De la familia de complejos Ru-OH2 sintetizados y estudiados, unos pocos fueron seleccionados para desarrollar sistemas más complejos y poder ser utilizados para (a) catálisis heterogénea (obteniendo sistemas catalíticos fácilmente reciclables) y (b) catálisis supramolecular (para poder llevar a cabo oxidaciones regioselectivas de sustratos orgánicos). Para el desarrollo de catálisis heterogénea, nanopartículas magnéticas (NPs) de óxidos de hierro fueron seleccionadas como soporte y los sistemas resultantes NP-Ru presentaron una buena dispersión en disolventes orgánicos y pudieron ser fácilmente separados y reutilizados, obteniendo así un sistema casi-homogéneo, en el que las ventajas de ambos procesos homogéneo y heterogéneo fueron combinados. Como último capítulo de la tesis...