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1.
The sensitivity of an enzyme to its environment has provoked much interest both for its immediate relevance to biochemistry and for the use of enzymes in chemical synthesis. The intercellular or extracellular environment in which an enzyme naturally operates is crowded with macromolecular, small-molecule, and ionic solutes and hence is markedly different from the dilute aqueous buffer solutions commonly cited for comparisons of biochemical processes. We report the results of a kinetic study into the effects of such a crowded solution on the rate of an enzyme-mediated process-the trypsin-catalyzed hydrolysis of a nonnatural substrate ester. The catalytic rate constant decreases linearly with solvent polarity, but substrate binding is independent of the concentration of added crowding agent up to 395 g/L.  相似文献   
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Abstract

In the present investigation, the authors could obtain a new series of spiranes (1) through the reaction of the high potential quinone tetrachloro-o-benzoquinone with 2-aryl-3-phenyl-3H-quinazoline-4-thiones. Thus, 2,3-diphenyl- (2a), 2-p-tolyl-3-phenyl- (2b) and 2-p-anisyl-3-phenyl- (2c)-3H-quinazoline-4-thiones react readily with tetrachloro-o-benzoquinone, in boiling toluene, to give the corresponding spiro-1,3-benzodioxole-2,4′-(3′H)-quinazolines (1a-c), respectively.  相似文献   
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We get new characterizations of finite supersolvable groups based on the structure of the generalized Fitting subgroup. Then we extend our results to the saturated formations containing the class of all supersolvable groups. Authors’ addresses: M. Asaad, Department of Mathematics, Faculty of Science, Cairo University, Giza, Egypt; Piroska Cs?rg?, Department of Algebra and Number Theory, E?tv?s University, Pázmány Péter sétány 1/c, H-1117 Budapest, Hungary  相似文献   
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Let G be a finite group and H a subgroup of G. We say that H is s-permutable in G if HPPH for all Sylow subgroups P of G; H is s-semipermutable in G if HPPH for all Sylow subgroups P of G with (|P|, |H|) = 1. Let H s G be the subgroup of H generated by all those subgroups of G which are s-permutable in G and H sG the intersection of all such s-permutable subgroups of G contain H. We say that H is nearly s-embedded in G if G has an s-permutable subgroup T such that H sG HT and \({H \cap T \leqq H_{ssG}}\) , where H ssG is an s-semipermutable subgroup of G contained in H. In this paper, we study the structure of a finite group G under the assumption that some subgroups of prime power order are nearly s-embedded in G. A series of known results are improved and extended.  相似文献   
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The configuration interaction, applied very recently byAsaad to the calculations ofKLL-Auger spectra, could remove the large discrepancies which existed for lowZ between experimental and theoretical relative group intensities I(KL1L2,3)/I(KL1L1) and I(KL2,3L2,3)/I(KL1L1).Asaad's calculations, however, were based on binding energies E(L1) and energies of the Coulomb and spin-orbit interaction, which were not very accurate. In the present calculations use has been made of more accurate binding energies E(L1) and Coulomb and spin-orbit interaction energies. It is shown that the absolute error in the results of the new calculations is less than 10%. From this it follows that the remaining discrepancies between theoretical and experimental values of the group intensities for 10≦Z<25 may be solely attributed to the inadequacy of the calculated transition probabilities. This calls for calculations of transition amplitudes of the KLL-process with more accurate wave functions for Z<25, in particular for Z=10.  相似文献   
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Expressions for the line intensities in theL 2 MM andL 3 MM spectra of elements of lowZ are given. For such elements the inner shell vacancy is given inj-j notation whereas the final double vacancy in the outer shell is given in Russell-Saunders coupling. Line intensities in theL 2 MM andL 3 MM spectra of argon are calculated using the transition amplitudes computed byRubenstein. No configuration interaction is considered.  相似文献   
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The two enantiomers of a compound often have profoundly different biological properties and thus their liability to racemisation in aqueous solutions is an important piece of information. The authors reviewed the available data concerning the process of racemisation in vivo, in the presence of biological molecules (e.g., racemase enzymes, serum albumin, cofactors and derivatives) and under purely chemical but aqueous conditions (acid, base and other aqueous systems). Mechanistic studies are described critically in light of reported kinetic data. The types of experimental measurement that can be used to effectively determine rate constants of racemisation in various conditions are discussed and the data they provide is summarised. The proposed origins of enzymatic racemisation are presented and suggest ways to promote the process that are different from processes taking place in bulk water. Experimental and computational studies that provide understanding and quantitative predictions of racemisation risk are also presented.  相似文献   
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