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71.
The kinetics of substitution reactions of [η-CpFe(CO)3]PF6 with PPh3 in the presence of R-PyOs have been studied. For all the R-PyOs (R = 4-OMe, 4-Me, 3,4-(CH)4, 4-Ph, 3-Me, 2,3-(CH)4, 2,6-Me2, 2-Me), the reactions yeild the same product [η5-CpFe(CO)2PPh3]PF6, according to a second-order rate law that is first order in concentrations of [η5-CpFe(CO)3]PF6 and of R-PyO but zero order in PPh3 concentration. These results, along with the dependence of the reaction rate on the nature of R-PyO, are consistent with an associative mechanism. Activation parameters further support the bimmolecular nature of the reactions: ΔH≠ = 13.4 ± 0.4 kcal mol−1, ΔS≠ = −19.1 ± 1.3 cal k−1 mol−1 for 4-PhPyO; ΔH≠ = 12.3 ± 0.3 kcal mol−1, ΔS≠ = 24.7 ±1.0 cal K−1 mol−1 for 2-MePyO. For the various substituted pyridine N-oxides studied in this paper, the rates of reaction increase with the increasing electron-donating abilities of the substituents on the pyridine ring or N-oxide basicities, but decrease with increasing 17O chemical shifts of the N-oxides. Electronic and steric factors contributing to the reactivity of pyridine N-oxides have been quantitatively assessed. 相似文献
72.
Chyi-Liang Chen Li-Kwan Chang Yu-Sun Chang Shih-Tung Liu Johannes Scheng-Ming Tschen 《Molecular & general genetics : MGG》1995,248(2):121-125
A total of 20Bacillus subtilis F29-3 mutants defective in fengycin biosynthesis was obtained by Tn917 mutagenesis. Cloning and mapping results showed that the transposon in these mutants was inserted in eleven different locations on the chromosome. We were able to use the chromosomal sequence adjacent to the transposon as a probe to screen for cosmid clones containing the fengycin biosynthesis genes. One of the clones obtained, pFC660, was 46 kb long. Eight transposon insertion sites were mapped within this plasmid. Among the eleven different mutants analyzed, four mutants had Tn917 inserted in regions which encoded peptide sequences similar to part of gramicidin S synthetase, surfactin synthetase, and tyrocidine synthetase. Our results suggest that fengycin is synthesized nonribosomally by the multienzyme thiotemplate mechanism. 相似文献
73.
W. A. Fenton A. L. Horwich 《Protein science : a publication of the Protein Society》1997,6(4):743-760
I. Architecture of GroEL and GroES and the reaction pathway A. Architecture of the chaperonins B. Reaction pathway of GroEL-GroES-mediated folding II. Polypeptide binding A. A parallel network of chaperones binding polypeptides in vivo B. Polypeptide binding in vitro 1. Role of hydrophobicity in recognition 2. Homologous proteins with differing recognition-differences in primary structure versus effects on folding pathway 3. Conformations recognized by GroEL a. Refolding studies b. Binding of metastable intermediates c. Conformations while stably bound at GroEL 4. Binding constants and rates of association 5. Conformational changes in the substrate protein associated with binding by GroEL a. Observations b. Kinetic versus thermodynamic action of GroEL in mediating unfolding c. Crossing the energy landscape in the presence of GroEL III. ATP binding and hydrolysis-driving the reaction cycle IV. GroEL-GroES-polypeptide ternary complexes-the folding-active cis complex A. Cis and trans ternary complexes B. Symmetric complexes C. The folding-active intermediate of a chaperonin reaction-cis ternary complex D. The role of the cis space in the folding reaction E. Folding governed by a "timer" mechanism F. Release of nonnative polypeptides during the GroEL-GroES reaction G. Release of both native and nonnative forms under physiologic conditions H. A role for ATP binding, as well as hydrolysis, in the folding cycle V. Concluding remarks. 相似文献
74.
Double-gating mechanism and diversity of an adenosine triphosphate (ATP)-sensitive K~ channel in neurons acutely dissociated from rat neocortex 总被引:2,自引:0,他引:2
Classically, ion channels are classified into 2 groups: chemical-sensitive (ligand-gated) and voltage-sensitive channels. Single ATP-sensitive K (K-ATP) channel currents were recorded in acutely dissociated rat neo-cortical neurons using patch clamp technique. A type of K-ATP channel has been found to be gated not only by intra-cellular ATP, but also by membrane potential ( Vm) , and proved to be a novel mechanism underlying the gating of ion channels, namely bi-gating mechanism. The results also show that the K-ATP channels possess heterogeneity and di-versity. These types of K-ATP channels have been identified in 40.12% of all patches, which are different in activa-tion-threshold and voltage-sensitivity. The present experiment studied the type-3 K-ATP channel with a unitary con-ductance of about 80 pS in detail ( n = 15). Taking account of all the available data, a variety of K-ATP channels are suggested to exist in body, and one type of them is bi-gated by both chemical substances and membrane poten 相似文献
75.
The athermal bioeffects caused by nanosecond electromagnetic pulses with body cells was studied by using a broad band transverse EM-wave cell (BTEM CELL). The experimental system and preliminary mechanism analysis were presented. 相似文献
76.
Peter Gegenheimer 《Molecular biology reports》1995,22(2-3):147-150
Chloroplasts of land plants have an active transfer RNA processing system, consisting of an RNase P-like 5 endonuclease, a 3 endonuclease, and a tRNA:CCA nucleotidyltransferase. The specificity of these enzymes resembles more that of their eukaryotic counterparts than that of their cyanobacterial predecessors. Most strikingly, chloroplast RNase P activity almost certainly resides in a protein, rather than in an RNA protein complex as in Bacteria, Archaea, and Eukarya. The chloroplast enzyme may have evolved from a preexisting chloroplast NADP-binding protein. Chloroplast RNase P cleaves pre-tRNA by a reaction mechanism in which at least one of the Mg2+ ions utilized by the bacterial ribozyme RNase P is replaced by an amino acid side chain.Abbreviations pre-tRNA
precursor to tRNA
- pCp
cytidine 5, 3-bisphosphate
- IC50
inhibitor concentration giving 50% inhibition
- GAPDH
glyceraldehyde 3-phosphate dehydrogenase 相似文献
77.
Crystallization and preliminary X-ray analysis of fructose 6-phosphate, 2-kinase:fructose 2,6-bisphosphatase. 下载免费PDF全文
E. S. Istvan C. A. Hasemann R. G. Kurumbail K. Uyeda J. Deisenhofer 《Protein science : a publication of the Protein Society》1995,4(11):2439-2441
Diffraction-quality crystals of the bifunctional enzyme fructose 6-phosphate, 2-kinase:fructose 2,6-bisphosphatase from rat testis have been obtained. The crystals were grown in the presence of ATP gamma S, fructose 6-phosphate, the detergent n-octylglucoside, and the precipitant polyethylene glycol 4000. The crystals have the symmetry of the trigonal space group P31/221 with a = b = 83.0 A and c = 130.6 A. Flash-frozen crystals diffract to beyond 2.2 A, and native data have been collected. 相似文献
78.
79.
The blue-green alga Anabaena cylindrica is found to consume molecular hydrogen in a hydrogenase dependent reaction. This hydrogen uptake proceeds in the dark and is strictly dependent on oxygen, thus representing a Knallgas reactions. Its rate is almost as high as that of the endogenous respiration in Anabaena. Studies with inhibitors reveal that hydrogen is utilized via the complete respiratory chain providing additional energy for the alga. CO plus C2H2 completely block the Knallgas reaction which explains the previously reported considerable increase in the total H2 formation representing the difference between the nitrogenase-dependent H2-evolution and the reutilization of the gas catalysed by the hydrogenase in intact Anabaena.H2 is able to support the C2H2-reduction in the dark in a reaction again strictly dependent on oxygen. Moreover, H2 is also consumed in experiments carried out under far red light and in the presence of dichlorophenyl-dimenthyl-urea (DCMU) where the energy for nitrogen fixation is no longer provided by respiration but by cyclic photophosphorylation. Under these conditions, H2 is found to supply electrons for the formation of C2H4 from C2H2 in a reaction no longer dependent on the presence of oxygen. Moreover, in these experiments, the presence of H2 stabilizes the C2H2-reduction activity against the deleterious effect of oxygen.Thus, this communication provides evidence for a triplicate function of the H2-uptake catalysed by hydrogenase in intact Anabaena which is (a) to provide energy by the Knallgas reaction, (b) to supply reducing equivalents for nitrogenase, (c) to protect nitrogenase from damage by oxygen.Abbreviations DCMU
N-(3,4-dichlorophenyl)N,N-dimethylurea
- DNP
2-4-dinitrophenol
- FCCP
carbonylcyanid-p-trifluormethoxyphenyl-hydrazone(=p-CF3-CCP)
- Chl
chlorophyll 相似文献
80.
本文对光生物和光化学的定义,反应机制的类型和光敏化作用等做了阐述。下面例举几个光疗的成果 1.光疗牛皮癣 经常使用的8-甲氧基补骨脂素在UVA的照射下,从基态被激发到三重态。它主要和DNA中的胸腺嘧啶,其次和色氨酸进行光环合加成,形成交联,阻止DNA和RNA的合成,抑制具过度增生 2.血卟啉衍生物(HPD)治癌 HPD有定位于癌组织的能力和光动力作用,可推断病人体内癌部位。 讨论了HPD的光疗机制,和酞菁相比,有各自的优缺点。 3.竹红菌素 主要治疗妇女外阴白色病变和疤痕疙瘩,抑制癌细胞生长。 讨论了竹红菌甲素和乙素及它们的氧化物的结构和活性。 在大于510nm的光照射下,也可抑制癌细胞的生长。列举了竹红菌素的优缺点。 相似文献