Mechanistic Studies Using Kinetic Isotope Effects PDF Download
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Author: Brian E. Schulmeier
Publisher:
ISBN:
Category :
Languages : en
Pages : 86
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Author: Brian E. Schulmeier
Publisher:
ISBN:
Category :
Languages : en
Pages : 86
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Author: Finley Eugene McFarlane
Publisher:
ISBN:
Category :
Languages : en
Pages :
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Author: Zhihong Wang
Publisher:
ISBN:
Category :
Languages : en
Pages :
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Several organic reactions that could potentially involve coarctate transition states were investigated by a combination of experimental and theoretical studies. In the thermal fragmentation of [delta]-1,3,4-oxadiazolines, the mechanism supported by kinetic isotope effects and theoretical calculations is a three-step process that does not demonstrate any special stabilization in coarctate transition states. Rather than undergoing a direct coarctate conversion to product, the mechanism avoids coarctate steps. The last step is a concerted coarctate reaction, but being concerted may be viewed as being enforced by the necessity to avoid high-energy intermediates. In the deoxygenation of epoxides with dichlorocarbene, the stabilization from the transition state aromaticity is not great enough to compete with the preference for asynchronous bonding changes. KIEs and calculations suggested that the reaction occurs in a concerted manner but with a highly asynchronous early transition state with much more C[alpha]-O bond breaking than C[beta]-O bond breaking. In the Shi epoxidation, a large [beta]-olefinic 13C isotope effect and small [alpha-carbon isotope effect indicated an asynchronous transition state with more advanced formation of the C-O bond to the [beta]-olefinic carbon. The calculated lowest-energy transition structures are generally those in which the differential formation of the incipient C-O bonds, the "asynchronicity," resembles that of an unhindered model, and the imposition of greater or less asynchronicity leads to higher barriers. In reactions of cis-disubstituted and terminal alkenes using Shi's oxazolidinone catalyst, the asynchronicity of the epoxidation transition state leads to increased steric interaction with the oxazolidinone when a [pi]-conjugating substituent is distal to the oxazolidinone but decreased steric interaction when the [pi]-conjugating substituent is proximal to the oxazolidinone. Dynamic effects were studied in Diels-Alder reaction between acrolein and methyl vinyl ketone. This reaction yields two products in a ratio of 3.0 " 0.5. Theoretical studies shows that only one transition structure is involved in the formation of both. Quasiclassical trajectory calculations on an MP2 surface give a prediction of a product ratio of 45:14 (3.2:1), which is in good agreement with the experimental observation.
Author: Laura E. Parmentier
Publisher:
ISBN:
Category :
Languages : en
Pages : 554
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Author: Paul F. Cook
Publisher: CRC Press
ISBN: 9780849353123
Category : Medical
Languages : en
Pages : 656
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Book Description
Isotope effects have become one of the most powerful tools available to the enzymologist for probing enzymic mechanisms. Enzyme Mechanism from Isotope Effects presents the basic theory underlying isotope effects, including the latest findings on proton tunneling and coupled atomic notions. Specific theoretical applications are emphasized in regard to the types of information that can be obtained using isotope effects. The book also examines recent theoretical treatments of the product dependence of deuterium isotope effects, multiple isotope effects and isotope effects on intermediate partitioning. Other topics include a complete discussion of methods for measuring isotope effects, including a detailed description of the use of the isotope ratio mass spectrometer to obtain isotope effects, and a review of the literature regarding mechanistic information obtained from isotope effects for individual classes of enzyme-catalyzed reactions. Enzyme Mechanism from Isotope Effects is an excellent reference source for investigators using isotope effects in their research. The book is also valuable for reference libraries and instructors teaching courses in enzyme mechanism.
Author:
Publisher: Academic Press
ISBN: 0128122749
Category : Medical
Languages : en
Pages : 634
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Book Description
Experimental Analysis of Enzyme Mechanism Using Isotope Effects, Volume 596, the latest release in the Methods in Enzymology series, continues the legacy of this premier serial with quality chapters authored by leaders in the field. Chapters in this comprehensive update include Measurement of enzyme binding isotope effects, Chemical ligation and isotope labeling to locate dynamic effects, Measurement of heavy enzyme isotope effects, Extracting kinetic isotope effects from a global analysis of reaction progress curves, KIE of metabolic flux and enzymes, Solvent and Primary KIE on Flavin Enzymes, and The Rapid Determination of Primary Deuterium Isotope Effects on Enzyme-Catalyzed Proton Transfer at Carbon in 50/50 HOH/DOD. Readers who are interested in applying or understanding this research will find useful methods currently used for measuring isotope effects on solution and enzyme reactions. Written by pioneers of modern isotope effect research Is the only collection of modern kinetic isotope effect methods currently available
Author: Gabriel Thomas Bedard
Publisher:
ISBN:
Category : Chemical reactions
Languages : en
Pages : 168
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Author: Valentin P. Ananikov
Publisher: John Wiley & Sons
ISBN: 3527678220
Category : Science
Languages : en
Pages : 483
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Book Description
Exploring and highlighting the new horizons in the studies of reaction mechanisms that open joint application of experimental studies and theoretical calculations is the goal of this book. The latest insights and developments in the mechanistic studies of organometallic reactions and catalytic processes are presented and reviewed. The book adopts a unique approach, exemplifying how to use experiments, spectroscopy measurements, and computational methods to reveal reaction pathways and molecular structures of catalysts, rather than concentrating solely on one discipline. The result is a deeper understanding of the underlying reaction mechanism and correlation between molecular structure and reactivity. The contributions represent a wealth of first-hand information from renowned experts working in these disciplines, covering such topics as activation of small molecules, C-C and C-Heteroatom bonds formation, cross-coupling reactions, carbon dioxide converison, homogeneous and heterogeneous transition metal catalysis and metal-graphene systems. With the knowledge gained, the reader will be able to improve existing reaction protocols and rationally design more efficient catalysts or selective reactions. An indispensable source of information for synthetic, analytical, and theoretical chemists in academia and industry.
Author: David A. Benko
Publisher:
ISBN:
Category : Chemical kinetics
Languages : en
Pages : 372
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Author: Amnon Kohen
Publisher: CRC Press
ISBN: 1420028022
Category : Medical
Languages : en
Pages : 1092
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Book Description
The field of isotope effects has expanded exponentially in the last decade, and researchers are finding isotopes increasingly useful in their studies. Bringing literature on the subject up to date, Isotope Effects in Chemistry and Biology covers current principles, methods, and a broad range of applications of isotope effects in the physical, biolo
