1000 resultados para Cyclopropanation énantio-et diastéréosélective


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Jean Louis Rodolphe Agassiz foi professor e naturalista suíço naturalizado americano. Nasceu em Motiers, em 28 de maio de 1807, e morreu em Cambridge, em 1873. Estudou em Universidades suíças e alemãs, doutorando-se em Medicina, em Munique, em 1830. Em 1846, fixou-se nos Estados Unidos, onde lecionou em Harvard, e, em 1861, tornou-se cidadão americano. O estudo e a classificação de espécies de peixes brasileiros despertou-lhe o interesse pelo Brasil e , em 1865, chegou ao País à frente de uma expedição científica, que ficou conhecida como Thayer Expedition, custeada pelo milionário americano Nathanael Thayer e patrocinada pelo Imperador D. Pedro II. Permaneceu no País por quinze meses, explorando o Rio Amazonas e o interior cearense, período em que classificou 1.800 espécies da fauna ictiológica. Dessa viagem, resultou o livro A journey in Brasil. Seus estudos de Zoologia e Paleontologia, assim como os dos glaciares da Europa e da América, tornaram-se célebre. A obra científica de Agassiz é constituída por mais de quatrocentos volumes.

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Notas tipográficas retiradas de Brunet, v. 2, col. 1780.

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Nota de conteúdo : V.1. Memoire en reponse aux allegations de la France, accompagne de quelques cartes -- V. 2-3. Documents accompagnes de notes explicatives ou rectificatives, 1. ptie, 1536-1713 ; 2. ptie, 1713-1896 -- V. 4. Texte original de documents traduits dans les tomes 2 et 3 -- V. 5. Album : fac-simile de quelques documents reproduits aux tomes 2, 3 et 4 -- V. 6. Atlas : contenant 86 cartes.

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Folgende Kernbehauptungen bzw. Hypothesen werden in dem Worm-et-al.-Artikel aufgestellt: -Der Verlust an Biodiversität (Artenzahl) in einem Meeresgebiet reduziert tief greifend seine Produktivität und seine Stabilität in Stressperioden, hervorgerufen u.a. durch Überfischung und Klimaänderung. -Die Zahl der kollabierten Arten nimmt zu. Dieser Trend projeziert den Kollaps aller wildlebenden Arten und Bestände, die gegenwärtig befischt werden, auf das Jahr 2048. -Diese Entwicklung ist zum gegenwärtigen Zeitpunkt reversibel, denn das Meer besitzt noch ein großes Potential sich zu regenerieren. Dazu ist aber mehr Umweltschutz notwendig.

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Ouvrage enrichi d'un superbe atlas, compose de 41 planches gravées en taille-douce, et de trois carte.

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(PDF contains 267 pages)

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Presentado en el IIe Colloque International de l'IEHA: « Un aliment sain dans un corps sain ». Perspectives historiques - «Healthy Food in a Healthy Body», organizado por el Institut Européen d'Histoire de l'Alimentation y celebrado en Tours los días 14 y 15 de diciembre de 2002.

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Synthetic biology promises to transform organic synthesis by enabling artificial catalysis in living cells. I start by reviewing the state of the art in this young field and recognizing that new approaches are required for designing enzymes that catalyze nonnatural reactions, in order to expand the scope of biocatalytic transformations. Carbene and nitrene transfers to C=C and C-H bonds are reactions of tremendous synthetic utility that lack biological counterparts. I show that various heme proteins, including cytochrome P450BM3, will catalyze promiscuous levels of olefin cyclopropanation when provided with the appropriate synthetic reagents (e.g., diazoesters and styrene). Only a few amino acid substitutions are required to install synthetically useful levels of stereoselective cyclopropanation activity in P450BM3. Understanding that the ferrous-heme is the active species for catalysis and that the artificial reagents are unable to induce a spin-shift-dependent increase in the redox potential of the ferric P450, I design a high-potential serine-heme ligated P450 (P411) that can efficiently catalyze cyclopropanation using NAD(P)H. Intact E. coli whole-cells expressing P411 are highly efficient asymmetric catalysts for olefin cyclopropanation. I also show that engineered P450s can catalyze intramolecular amination of benzylic C-H bonds from arylsulfonyl azides. Finally, I review other examples of where synthetic reagents have been used to drive the evolution of novel enzymatic activity in the environment and in the laboratory. I invoke preadaptation to explain these observations and propose that other man-invented reactions may also be transferrable to natural enzymes by using a mechanism-based approach for choosing the enzymes and the reagents. Overall, this work shows that existing enzymes can be readily adapted for catalysis of synthetically important reactions not previously observed in nature.

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The cytochromes P450 (P450s) are a remarkable class of heme enzymes that catalyze the metabolism of xenobiotics and the biosynthesis of signaling molecules. Controlled electron flow into the thiolate-ligated heme active site allows P450s to activate molecular oxygen and hydroxylate aliphatic C–H bonds via the formation of high-valent metal-oxo intermediates (compounds I and II). Due to the reactive nature and short lifetimes of these intermediates, many of the fundamental steps in catalysis have not been observed directly. The Gray group and others have developed photochemical methods, known as “flash-quench,” for triggering electron transfer (ET) and generating redox intermediates in proteins in the absence of native ET partners. Photo-triggering affords a high degree of temporal precision for the gating of an ET event; the initial ET and subsequent reactions can be monitored on the nanosecond-to-second timescale using transient absorption (TA) spectroscopies. Chapter 1 catalogues critical aspects of P450 structure and mechanism, including the native pathway for formation of compound I, and outlines the development of photochemical processes that can be used to artificially trigger ET in proteins. Chapters 2 and 3 describe the development of these photochemical methods to establish electronic communication between a photosensitizer and the buried P450 heme. Chapter 2 describes the design and characterization of a Ru-P450-BM3 conjugate containing a ruthenium photosensitizer covalently tethered to the P450 surface, and nanosecond-to-second kinetics of the photo-triggered ET event are presented. By analyzing data at multiple wavelengths, we have identified the formation of multiple ET intermediates, including the catalytically relevant compound II; this intermediate is generated by oxidation of a bound water molecule in the ferric resting state enzyme. The work in Chapter 3 probes the role of a tryptophan residue situated between the photosensitizer and heme in the aforementioned Ru-P450 BM3 conjugate. Replacement of this tryptophan with histidine does not perturb the P450 structure, yet it completely eliminates the ET reactivity described in Chapter 2. The presence of an analogous tryptophan in Ru-P450 CYP119 conjugates also is necessary for observing oxidative ET, but the yield of heme oxidation is lower. Chapter 4 offers a basic description of the theoretical underpinnings required to analyze ET. Single-step ET theory is first presented, followed by extensions to multistep ET: electron “hopping.” The generation of “hopping maps” and use of a hopping map program to analyze the rate advantage of hopping over single-step ET is described, beginning with an established rhenium-tryptophan-azurin hopping system. This ET analysis is then applied to the Ru-tryptophan-P450 systems described in Chapter 2; this strongly supports the presence of hopping in Ru-P450 conjugates. Chapter 5 explores the implementation of flash-quench and other phototriggered methods to examine the native reductive ET and gas binding events that activate molecular oxygen. In particular, TA kinetics that demonstrate heme reduction on the microsecond timescale for four Ru-P450 conjugates are presented. In addition, we implement laser flash-photolysis of P450 ferrous–CO to study the rates of CO rebinding in the thermophilic P450 CYP119 at variable temperature. Chapter 6 describes the development and implementation of air-sensitive potentiometric redox titrations to determine the solution reduction potentials of a series of P450 BM3 mutants, which were designed for non-native cyclopropanation of styrene in vivo. An important conclusion from this work is that substitution of the axial cysteine for serine shifts the wild type reduction potential positive by 130 mV, facilitating reduction by biological redox cofactors in the presence of poorly-bound substrates. While this mutation abolishes oxygenation activity, these mutants are capable of catalyzing the cyclopropanation of styrene, even within the confines of an E. coli cell. Four appendices are also provided, including photochemical heme oxidation in ruthenium-modified nitric oxide synthase (Appendix A), general protocols (Appendix B), Chapter-specific notes (Appendix C) and Matlab scripts used for data analysis (Appendix D).

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A description of the cyanobacteriae Anabaena circinalis Rabenhorst and Anabaena flos aquae Brebisson, ex Bornet et Flanault is given. Illustrations are included.

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Species of Pithophora occasionally appear in Europe and are associated mostly with the tropical, higher water plants, cultivated in numerous botanical gardens. In June 1973 pale green, branched threads were discovered in the pond of the Wroclaw Botanical Garden, amongst filaments of Spirogyra crassa (Kutz.) Czurda emend. and Cladophora glomerata (L.) Kutz. floating on the water surface. They were maintained for several weeks in crude cultures and produced numerous, dark akinetes tightly packed with reserve material. This collected material was found to be a member of the family Pithophora, Wittr. Further examinations identified the material as Pithophora oedogonia. The findings point out that it is probable, that species of Pithophora Wittr. can become acclimatized in Europe, primarily in ponds of botanical gardens, where consequently they are able to tangle easily with higher tropical plants.

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Analyse about all the economical connexions between the European Union and Algeria since 1962 until 2014.

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Utilization of the heavy isotope of nitrogen as a tracer has found numerous applications in soil biology. It allows better definition of different stages of the nitrogen cycle, in particular the immobilization-mineralization cycle. In this work, the authors report the results of calculations of natural isotope ratios of nitrogen in samples of water, soil and vegetation prevailing in Dombes and discuss the possibilities of errors and coefficients of fractionation.

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During hydrographic and plankton studies carried out since 1960 in the coastal zone between the Ebro and Castellon (western Mediterranean), data has been collected which confirms the importance of ciliates in the composition and activity of the plankton. The ciliates in 413 samples of 100 ml of water were counted, having been examined with the Utermohl microscope after sedimentation. The samples studied were distributed according to the density of their population. subject for study. The author concludes that recognition of the role of ciliates as an important link in the food chain of the sea would simplify the interpretation of certain problems posed by the nutrition of certain groups of planktonic animals.

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Ce rapport présente les activités et les résultats de l’atelier Vision 2050: Changement climatique, pêche et aquaculture en Afrique de l’Ouest. Les objectifs de l’atelier étaient de discuter les questions critiques et les incertitudes auxquelles est confronté le secteur de la pêche et de l’aquaculture au Ghana, au Sénégal et en Mauritanie, d’élaborer des scénarios sectoriels pour 2050 et de discuter de l’implication de ces scénarios dans le contexte du changement climatique pour ces pays et la région ouest africaine.