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31.
István Szilágyi László. Horváth Imre Labádi Klara Hernadi István Pálinkó Tamás Kiss 《Central European Journal of Chemistry》2006,4(1):118-134
An imidazolate-bridged copper(II)-zinc(II) complex (Cu(II)-diethylenetriamino-μ-imidazolato-Zn(II)-tris(2-aminoethyl)amine perchlorate (denoted as “Cu,Zn complex”) and a simple copper(II) complex (Cu(II)-tris(2-aminoethyl)
amine chloride (“Cu-tren”) were prepared and immobilised on silica gel (by hydrogen or covalent bonds) and montmorillonite
(by ion exchange). The immobilised substances were characterised by FT-IR spectroscopy and their thermal characteristics were
also studied. The obtained materials were tested in two probe reactions: catalytic oxidation of 3,5-di-tert-butyl catechol (DTBC) (catecholase activity) and the decomposition of hydrogen peroxide (catalase activity). It was found
that the catecholase activity of the Cu,Zn complex increased considerably upon immobilization on silica gel via hydrogen bonds and intercalation by ion exchange among the layers of montmorillonite. The imidazolate-bridged copper(II)-zinc(II)
complex and its immobilised versions were inactive in hydrogen peroxide decomposition. The Cu(II)-tris(2-aminoethyl)amine
chloride complex displayed good catalase activity; however, immobilisation could not improve it. 相似文献
32.
33.
The phenomenological amplitude for the reaction πN→ππN fixed by fittings to the experimental data in the energy region 0.300 ≤P
Lab≤ 500 MeV/c is used for modelling the Chew–Low extrapolation and Olsson–Turner threshold approach. It is shown that the uncritical
application of the former results in enermous theoretical errors, the extracted values being in fact random numbers. The results
of the Olsson–Turner method are characterized by significant systematic errors coming from unknown details of the isobar physics.
Received: 10 December 1997 相似文献
34.
We summarize some recent results related to fluctuation-induced kinetics of diffusion-controlled processes. We show that kinetic behavior can be drastically changed due to fluctuation effects, spatial correlations between particles, and anomalous transport properties. In addition, we show that correlation-induced kinetics in some systems can govern the temporal evolution over the entire time domain. 相似文献
35.
R. B. King 《Russian Chemical Bulletin》1993,42(11):1772-1781
Reactions of disodium tetracarbonylferrate, Na2Fe(CO)4, with sterically hindered dialkylaminodichlorophosphines, R2NPCl2 (R2N=diisopropylamino, dicyclohexylamino, and 2,2, 6, 6-tetramethylpiperidino) in diethyl ether lead to the air-stable phosphorus-bridging carbonyl derivatives (R2NP)2COFe2(CO)6 as the major products. The phosphorus-bridging carbonyl group in (i-Pr2NP)2COFe2(CO)6 has been found to undergo the following types of reactions: 1)Reduction, 2)Acylation, 3)Extrusion of the carbonyl group. The mechanisms of the reactions have been considered.This work was presented at the Workshop «The Modern Problems of Heteroorganic Chemistry» held on the ship «Nikolai Bauman» during the period May 8–13, 1993.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1858–1867, November, 1993. 相似文献
36.
Bruce J. West Raoul Kopelman Katja Lindenberg 《Journal of statistical physics》1989,54(5-6):1429-1439
The conditions for macroscopic segregation ofA andB in a steady-stateA+B 0 reaction are studied in infinite systems. Segregation occurs in one and two dimensions and is marginal ford=3. We note the dependence of these results on the precise experimental conditions assumed in the theory. We also note the difference between these results and our earlier ones for finite systems where the critical dimension isd=2. 相似文献
37.
M. A. Massiah V. Saraswat H. F. Azurmendi A. S. Mildvan 《Journal of Molecular Structure》2004,700(1-3):247-254
The MutT pyrophosphohydrolase from E. coli (129 residues) catalyzes the hydrolysis of nucleoside triphosphates (NTP), including 8-oxo-dGTP, by substitution at Pβ, to yield NMP and pyrophosphate. The product, 8-oxo-dGMP is an unusually tight binding, slowly exchanging inhibitor with a KD=52 nM, (ΔG°=−9.8 kcal/mol) which is 6.1 kcal/mol tighter than the binding of dGMP (ΔG°=−3.7 kcal/mol). The higher affinity for 8-oxo-dGMP results from a more favorable ΔHbinding (−32 kcal/mol) despite an unfavorable −TΔS°binding (+22 kcal/mol). The solution structure of the MutT–Mg2+-8-oxo-dGMP complex shows a narrowed, hydrophobic nucleotide-binding cleft with Asn-119 and Arg-78 among the few polar residues. The N119A, N119D, R78K and R78A single mutations, and the R78K+N119A double mutant all showed largely intact active sites, on the basis of small changes in the kinetic parameters of dGTP hydrolysis and in 1H–15N HSQC spectra. However, the N119A mutation profoundly weakened the active site binding of 8-oxo-dGMP by 4.3 kcal/mol (1650-fold). The N119D mutation also weakened 8-oxo-dGMP binding but only by 2.1 kcal/mol (37-fold), suggesting that Asn-119 functioned both as a hydrogen bond donor to C8=O, and a hydrogen bond acceptor from N7H of 8-oxo-dGMP, while aspartate at position −119 functioned as an acceptor of a single hydrogen bond. Much smaller weakening effects (0.3–0.4 kcal/mol) on the binding of dGMP and dAMP were found, indicating specific hydrogen bonding of Asn-119 to 8-oxo-dGMP. While formation of the wild type MutT–Mg2+-8-oxo-dGMP complex slowed the backbone NH exchange rates of 45 residues distributed throughout the protein, the same complex of the N119A mutant slowed the exchange rates of only 11 residues at or near the active site, indicating an increase in conformational flexibility of the N119A mutant. The R78K and R78A mutations weakened the binding of 8-oxo-dGMP by 1.7 and 1.1 kcal/mol, respectively, indicating a lesser role of Arg-78 than of Asn-119 in the selective binding of 8-oxo-dGMP, likely donating a single hydrogen bond to its C6=O. The R78K+N119A double mutant weakened the binding of 8-oxo-dGMP (KIslope=3.1 mM) by 6.5±0.2 kcal/mol which overlaps, within error with the sum of the effects of the two single mutants (6.0±0.3 kcal/mol). Such additive effects of the two single mutants in the double mutant are most simply explained by the independent functioning of Asn-119 and Arg-78 in the binding of 8-oxo-dGMP. Independent functioning of these two residues in nucleotide binding is consistent with their locations in the MutT–Mg2+-8-oxo-dGMP complex, on opposite sides of the active site cleft, with a distance of 8.4±0.5 Å between their side chain nitrogens. 相似文献
38.
39.
过氧化物模拟酶在介体型生物传感器方面应用初探 总被引:2,自引:0,他引:2
meso-四(4-磺基苯)卟啉锰(Ⅲ)作为过氧化物模拟酶可催化H_2O_2与K_4Fe(CN)_6反应。电流响应与H_2O_2浓度在3.0×10~(-4)~1.0×10~(-3)mol/L范围内呈线性关系。重现性和回收率良好。抗坏血酸和DL-半胱氨酸干扰严重。 相似文献
40.
In the absence of any trapping agent, stable neopentyl-Pd intermediates can terminate a catalytic cycle by undergoing a regioselective C-H activation, leading to various spiro or fused cyclopropane derivatives in a straightforward manner. If the neopentyl-Pd intermediate contains a heteroatom at a suitable position, C-H activation does not occur and stable palladacycles are isolated. 相似文献