Mechanistic studies

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  • This chapter aims to cover theoretical and computational studies on or- ganometallic molecules. Section 2 covers the s-block elements, Section 3 covers the p-block metals and Section 4 covers the d- and f-block metals. Clusters, carbonyls and metal-metal bonded systems containing M-C bonds are included. Cyanide complexes, metal fullerene derivatives, extended systems and organic species on metal surfaces are excluded except where calculations have been performed on model complexes designed to mimic solid state and surface chem- istry....

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  • Acyl-CoA dehydrogenases constitute a family of flavopro-teins that catalyze the a,b-dehydrogenation of fatty acid acyl-CoA conjugates. While they differ widely in their spe-cificity, they share the same basic chemical mechanism ofa,b-dehydrogenation. Medium chain acyl-CoAdehydro-genase is probably the best-studiedmember of the class and serves as a model for the study of catalytic mechanisms.

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  • Peroxidases perform the nitration of tyrosine and tyrosyl residues in proteins, in the presence of nitrite and hydrogen peroxide. The nitrating species is still unknown but it is usually assumed to be nitrogen dioxide. In the present investigation, the nitration of phenolic compounds derived from tyrosine by lactoperoxidase and horseradish peroxi-dasewas studied, with the aimof elucidating themechanism of the reaction.

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  • MicroRNAs (miRNAs) are noncoding regulatory RNAs that function via the degradation of target mRNAs and inhibition of translation. They are found widely in higher eukaryotic organisms, and in several species that have been closely examined, hundreds of miRNAs have thus far been discovered with mechanistically conserved, yet functionally diverse, roles necessary for the proper development, homeostasis and metabolism of the organisms.

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  • Cytosolic 5¢-nucleotidase/phosphotransferase specific for 6-hydroxypurine monophosphate derivatives (cN-II), belongs to a class of phosphohydrolases that act through the formation of an enzyme–phosphate intermediate. Sequence alignment with members of the P-type ATPases/L-2-halo-acid dehalogenase superfamily identified three highly con-served motifs in cN-II and other cytosolic nucleotidases. Mutagenesis studies at specific amino acids occurring in cN-II conservedmotifswereperformed.

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  • It is my great honor and pleasure to introduce this comprehensive book to readers who are interested in carbohydrates. This book contains 23 excellent chapters written by experts from the fields of chemistry, glycobiology, microbiology, immunology, botany, zoology, as well as biotechnology. According to the topics, methods and targets, the 23 chapters are further divided into five independent sections. In addition to the basic research, this book also offers much in the way of experiences, tools, and technologies for readers who are interested in different fields of Glycobiology.

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  • Sleep-related breathing disorders have been recognized and described by astute clinicians for millennia. The past several decades have witnessed intensive and accelerating investigation into the epidemiology, genetics, pathophysiology, and clinical as well as behavioral consequences of sleeprelated breathing disorders. The Lung Biology in Health and Disease series has played an important role in consolidating the accumulating knowledge in this area and in providing a focused view of the state of the art.

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  • question which every author ought to ask of himself before he sends forth his work, and one which must occur to every thoughtful reader, is the inquiry, Cui bono?--what justification has one for treating the subject at all, and why in the particular way which he has chosen? To the pertinency of this question to the present treatise the author has been deeply sensible, and therefore cannot forbear a few prefatory words of explanation of his object and method.

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  • Two ORFs encoding a protein related to bacterial dimethylglycine oxidase were cloned from Pyrococcus furiosus DSM 3638. The protein was expressed in Escherichia coli, purified, and shown to be a flavoprotein amine dehydrogenase. The enzyme oxidizes the secondary aminesl-proline, l-pipecolic acid and sarcosine, with optimal catalytic activity towards l-proline.

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  • Mass Spectrometry of Carbohydrates Derivatized with Biotinamidocaproyl Hydrazide 55 Stephanie Bank and Petra Kapková Investigation of Carbohydrates and Their Derivatives as Crystallization Modifiers 81 Josef Jampílek and Jiří Dohnal Glycosidases – A Mechanistic Overview 117 Natércia

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  • The Arabidopsis FAE1 b-ketoacyl-CoA synthase (FAE1 KCS) catalyzes the condensation of malonyl-CoA with longchain acyl-CoAs. Sequence analysis of FAE1 KCS predicted that this condensing enzyme is anchored to a membrane by two adjacent N-terminal membrane-spanning domains. In order to characterize the FAE1 KCS and analyze its mechanism, FAE1 KCS and its mutants were engineered with a His6-tag at their N-terminus, and expressed in Saccharomyces cerevisiae. The membrane-bound enzyme was then solubilized and purified to near homogeneity on a metal affinity column.

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  • Escherichia colifatty acid cyclopropane synthase (CFAS) was overproduced and purified as a His6 -tagged protein. This recombinant enzyme is as active as the native enzyme with aKmof 90lMforS-AdoMet and a specific activity of 5·10 )2 lmolÆmin )1 Æmg )1 . The enzyme is devoid of organic or metal cofactors and is unable to catalyze the wash-out of themethyl protons ofS-AdoMet to the solvent, data that do not support the ylidemechanism. Inactivationof the enzyme by 5,5¢-dithiobis-(2-nitrobenzoic acid) (DTNB), a pseudo first-order process with a rate constant of 1.

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  • Hydrogenation is one of the most intensively studied fields of metal complex catalyzed homogeneous transformations. There are several reasons for such a strong interest in this reaction. First of all, there are numerous important compounds which can be produced through hydrogenation, such as pharmaceuticals, herbicides, flavors, fragrances, etc [1-3]. Activation of is involved in other important industrial processes, such as hydroformylation, therefore the mechanistic conclusions drawn from hydrogenation studies can be relevant in those fields, as well.

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  • As the origin of a life-and-death signal detected from systemic arterial pressure, which sequentially increases (pro-life) and decreases (pro-death) to reflect progressive dysfunction of central cardiovascular regulation during the advancement towards brain stem death in critically ill patients, the rostral ventrolateral medulla (RVLM) is a suitable neural substrate for mechanistic delineation of this fatal phenomenon.

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  • Despite its clinical importance, a dearth of information exists on the cellular and molecular mechanisms that underpin brain stem death. A suitable neural substrate for mechanistic delineation on brain stem death resides in the rostral ventrolateral medulla (RVLM) because it is the origin of a life-and-death signal that sequentially increases (pro-life) and decreases (pro-death) to reflect the advancing central cardiovascular regulatory dysfunction during the progression towards brain stem death in critically ill patients.

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  • The conformationally coupled mechanism by which ATP is utilized by yeast Hsp90 is now well characterized. In contrast, ATP utilization by human Hsp90s is less well studied, and appears to operate differently. To resolve these conflicting models, we have conducted a side-by-side biochem-ical analysis in a series of mutant yeast and human Hsp90s that have been both mechanistically and structurally characterized with regard to the crys-tal structure of the yeast Hsp90 protein.

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  • Penicillin acylase catalyses the hydrolysis and synthesis of semisyntheticb-lactam antibiotics via formation of a cova-lent acyl-enzyme intermediate. The kinetic and mechanistic aspects of these reactions were studied. Stopped-flow experiments with the penicillin and ampicillin analogues 2-nitro-5-phenylacetoxy-benzoic acid (NIPAOB) and D-2-nitro-5-[(phenylglycyl)amino]-benzoic acid (NIPGB) showed that the rate-limiting step in the conversion of penicillin G and ampicillin is the formation of the acyl-enzyme....

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