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991.
Hiratake J 《Chemical record (New York, N.Y.)》2005,5(4):209-228
Carefully designed molecules that are intimately related to the reaction mechanism of enzymes are often highly selective and potent inhibitors that serve as extremely useful chemical probes for understanding the reaction mechanism and structure of enzymes. This article describes the design, synthesis, and applications of specific inhibitors of two mechanistically distinct groups of enzymes, ATP-dependent amide ligases and Ser- and Thr-hydrolases. Our strategy is based on the premise that stable analogues of the transition state (transition-state analogues) are highly potent inhibitors that serve as good mechanistic probes, and that a key structure of a good inhibitor of one enzyme is also utilized for the inhibitors of other enzymes that share the same chemistry in their catalyzed reactions, irrespective of the degree of structural similarity and evolutionary link between the enzymes. According to these principles, we designed and synthesized a series of phosphinate- and sulfoximine-based transition-state analogue inhibitors of glutathione synthetase, gamma-glutamylcysteine synthetase and asparagine synthetase. For the second group of enzymes, we synthesized a gamma-monofluorophosphono glutamate analogue for mechanism-based affinity labeling of gamma-glutamyltranspeptidase and fluorescent phosphonic acid esters for the active-site titration of lipase. These inhibitors were used successfully as ligands for detailed kinetic analyses, X-ray crystallography, and mass analysis of the enzymes to identify the key amino acid residues responsible for catalysis and substrate recognition in the transition state. 相似文献
992.
V. V. Nikitenko A. I. Martynenko S. A. Ostrovsky V. V. Rusak V. V. Kryuchkov D. A. Topchiev 《Russian Chemical Bulletin》1993,42(2):378-380
3-Methyl-l-vinylpyrazole (M3VP) and 5-methyl-1-vinylpyrazole (M5VP) were isolated as individual substances by vacuum rectification of their mixture (M3VP: M5VP 60 40). For each of them the kinetics of free-radical polymerization in MeOH were measured at low conversions. In both cases the rate of polymerization is proportional to 0.5 order with respect to the initiator (AIBN) concentration. On the other hand, a first order of reaction with respect to monomer concentration is observed only when the latter is relatively low (3M). At higher initial concentrations of monomers the order of reaction becomes less than unity. The overall rate of polymerization for M5VP was higher than for M3VP, whereas the initiation rate remained constant in the whole range of monomer concentrations and did not depend on the exact structure of the monomer. The difference in the rates of polymerization observed for M3VP and M5VP is probably connected with the difference in the key parameterk
p/k
t
1/2
for each of the two isomers. It is concluded that the correct kinetic information about homo- and co-polymerization of M3VP and M5VP cannot be obtained without their adequate separation.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 413–415, February, 1993. 相似文献
993.
高效液相色谱法测定小麦幼苗中植物生长调节剂 总被引:3,自引:0,他引:3
介绍了高效液相色谱法测定麦苗中植物生长调节剂(赤霉素GA3),3-吲哚乙酸(IAA)的方法,用国产预处理小柱处理样品,并以甲醇:1%,冰乙酸=12:88(V/V)为流动相,色谱柱为ZorbaxC18,在210nm紫外检测。 相似文献
994.
N. Bélaïd-Drira H. Zamali M. Jemal 《Journal of Thermal Analysis and Calorimetry》1996,46(5):1449-1458
Phase diagram of the binary system LiNO3-NaNO3 has been obtained by using direct and differential thermal analysis between 323 and 623 K. This system is characterized by an eutectic plateau at 467 K. The eutectic point is at 0.465 mole NaNO3. A peritectic appears at 550 K. There is no miscibility in the solid state. These findings associated with some other thermodynamic results have been used to calculate the activities of the constituents along the liquids curve and the excess thermodynamic functions at 618 K. The constituents seem not to have a symmetrical influence on the thermodynamic quantities. 相似文献
995.
N-取代吩噻嗪和DDQ的电荷转移络合作用 总被引:1,自引:0,他引:1
具有盼嘤酸化学结构的化合物有广泛的用途I‘-\其中吩嘤埃衍生物在医学上用作抗精神病药物特别受到药理学家们的注意,发现其药理作用与其分子提供电子的能力有关卜‘」但是我们应该注意到,作为抗精神病药物的吩嚷嚷衍生物,其吩座爆分子的氮原子都连有一个叔胺基链问,例如氯丙障(I)和奋乃静(11).而我们知道,胺类特别是叔胺类有强的提供电子的能力*;在上述的药物分子中是主要的提供电子因素,因此以这类化合物作为给体研究其供电子能力,是不能实际反映吩嘤嗓分子本身的给电子能力的.吩嘤噪类属于二苯并杂环化合物,分子中既… 相似文献
996.
As an extension of previous reports, the barium carbonate procedure has been optimized in detail for the preparation of apolar columns. The aim was to produce optimum overall column characteristics, and to maintain them unchanged under the prolonged influence of the highest possible temperature. The main parameters under optimization were glass variety, leaching of glass surface with aqueous HCl, and amount of barium carbonate deposited, while deactivation and coating were kept constant. The basic column characteristics were adsorption properties and thermostability of deactivation, acid/base behaviour and separation efficiency. They were determined by a new, quantitative testing procedure. Intense leaching was able to eliminate almost totally the differences between glass varieties and to create a well-defined glass surface. While untreated glass, leached glass, and barium carbonate treated glass showed specific weak points in the respective column quality, the combination of leaching and barium carbonate treatment yielded the highest and most stable quality. Some technical modifications of the preparation procedure are described, including deactivation in the gas phase, and use of pentane as a solvent for static coating. 相似文献
997.
Hitoshi Shimizu Kazuki Shimizu Atsuko Sugita Tsuyoshi Yamauchi Kazumi Morikawa 《Tetrahedron letters》2004,45(42):7837-7841
Two 21-nor-22-oxa-1α,25-dihydroxyvitamin D3 derivatives have been synthesized in quest of a drug with lower calcemic activity than Maxacalcitol, 22-oxa-1α,25-dihydroxyvitamin D3, being used as antihyperparathyroidism and antipsoriatic drug. Of two 21-nor products obtained, the product carrying one carbon elongated side chain with diethylcarbinol moiety has been found to exhibit comparable differentiation-inducing activity to Maxacalcitol with much lower exhibition of calcemic activity. 相似文献
998.
Tomoyuki Yoshimura 《Tetrahedron letters》2004,45(50):9241-9244
Diastereoselective construction of the 19-epi-C18-C25 segment of (−)-lasonolide A was achieved using a 5-exo-trigonal mode of radical cyclization for the creation of the contiguous quaternary and tertiary stereogenic centers at C22 and C23 as the key reaction step. During the dehydration stage, it was found that an unusual inversion of configuration took place. 相似文献
999.
5-Amino-4-cyano-8-isobutyl-7-isopropyl-6-thiocarbamoyl-2-azabicyclo[2.2.2]oct-5-en-3-thione was synthesized by the condensation of isovaleryl aldehyde with cyanothioacetamide. The structure of the product was established by X-ray crystallography. 相似文献
1000.
通过镁离子内扩散铌酸锂单晶光纤,以改变晶纤表层的折射率,首次在国内实现了沿不同轴向生长、不同掺杂的铌酸锂单晶光纤的芯-包层波导结构。通过匹配扩散温度、扩散时间、MgO膜厚等扩散参数及选择合适的晶纤直径,实现了晶纤具有阶跃和抛物折射率分布的包层,并对包层晶纤的模式特性进行了观察,得到低次模传输。 相似文献