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141.
Dagmara Jacewicz Aleksandra Dąbrowska Agnieszka Łapińska Lech Chmurzyński 《Transition Metal Chemistry》2006,31(5):575-579
The cis-[Cr(phen)2(O2CO)]+ ion was prepared through the displacement of two molecules of water from the cis-[Cr(phen)2(OH2)2]3+ by the bidentate carbonate anion. It underwent two-phase hydrolysis reactions under acidic conditions (0.1 < [H+] < 2.7 m) at 5, 10, 15, 20 and 25 °C. Via slow carbonato chelate ring opening (first step k1slow) and a second fast decarboxylation(k2fast value). The first step was preceded by protonation of the coordinate bidentate carbonate ligand. The second step exhibited
no pH dependence, while k1slow values increased with acid concentration that suggested the presence of both protonated and deprotonated reactant species.
Based on these observations we have proposed a hydrolysis mechanism featuring H2O-induced ring-opening of the coordinate CO32− group in the first step k1slow followed by loss of CO32− from two intermediates, [Cr(phen)2(O2COH)]2+ (k1slow) and [Cr(phen)2(OH2)(O2COH)]2+ (k2fast). 相似文献
142.
143.
The kinetics of individual stages of thermal dissociation of basic aluminium potassium sulfate (BAPS) were studied thermogravimetrically under isobaric and isothermal conditions at a reduced pressure of the order of 10?3 hPa and in the atmosphere of gaseous products of the reaction (H2O, SO2).The kinetic parameters of all the reaction stages have been identified and the nature of the stages and the effect of changes of the reaction of conditions on the course of the processes have been determined. 相似文献
144.
Tutueva Aleksandra V. Karimov Timur I. Moysis Lazaros Nepomuceno Erivelton G. Volos Christos Butusov Denis N. 《Nonlinear dynamics》2021,104(1):727-737
Nonlinear Dynamics - One of the widely-used ways in chaos-based cryptography to generate pseudo-random sequences is to use the least significant bits or digits of finite-precision numbers defined... 相似文献
145.
Stubbs KA Scaffidi A Debowski AW Mark BL Stick RV Vocadlo DJ 《Journal of the American Chemical Society》2008,130(1):327-335
The NagZ class of retaining exo-glucosaminidases play a critical role in peptidoglycan recycling in Gram-negative bacteria and the induction of resistance to beta-lactams. Here we describe the concise synthesis of 2-azidoacetyl-2-deoxy-5-fluoro-beta-d-glucopyranosyl fluoride as an activity-based proteomics probe for profiling these exo-glycosidases. This active-site directed reagent covalently inactivates this class of retaining N-acetylglucosaminidases with exquisite selectivity by stabilizing the glycosyl-enzyme intermediate. Inactivated Vibrio cholerae NagZ can be elaborated with biotin or a FLAG-peptide epitope using the Staudinger ligation or the Sharpless-Meldal click reaction and detected at nanogram levels. This ABPP enabled the profiling of the Pseudomonas aeruginosa proteome and identification at endogenous levels of a tagged protein with properties consistent with those of PA3005. Cloning of the gene encoding this hypothetical protein and biochemical characterization enabled unambiguous assignment of this hypothetical protein as a NagZ. The identification and cloning of this NagZ may facilitate the development of strategies to circumvent resistance to beta-lactams in this human pathogen. As well, this general strategy, involving such 5-fluoro inactivators, may prove to be of general use for profiling proteomes and identifying glycoside hydrolases of medical importance or having desirable properties for biotechnology. 相似文献
146.
Electrochemical behavior and antioxidant and prooxidant activity of natural phenolics 总被引:1,自引:0,他引:1
We have investigated the electrochemical oxidation of a number natural phenolics (salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, protocatechuic acid, o-coumaric acid, m-coumaric acid, p-coumaric acid, caffeic acid, quercetin and rutin) using cyclic voltammetry. The antioxidant properties of these compounds were also studied. A structural analysis of the tested phenolics suggests that multiple OH substitution and conjugation are important determinants of the free radical scavenging activity and electrochemical behavior. Compounds with low oxidation potentials (Epa lower than 0.45) showed antioxidant activity, whereas compounds with high Epa values (>0.45) act as prooxidants. 相似文献
147.
Humphreys AS Filipovska A Berners-Price SJ Koutsantonis GA Skelton BW White AH 《Dalton transactions (Cambridge, England : 2003)》2007,(43):4943-4950
The novel water soluble bidentate phosphine ligand 1,3-bis(di-2-pyridylphosphino)propane (d2pypp) has been synthesized by a convenient route involving treatment of 2-pyridyllithium with Cl(2)P(CH(2))(3)PCl(2) and isolation in crystalline form as the hydrochloride salt. The synthesis of the precursor Cl(2)P(CH(2))(3)PCl(2) has been optimized by the use of triphosgene as the chlorinating agent. The 2 : 1 and 1 : 2 AuCl : d2pypp adducts have been synthesized and characterized by NMR spectroscopy and single crystal X-ray studies, and shown to be of the form (AuCl)(2)(mu-d2pypp-P,P') and [Au(d2pypp-P,P')(2)]Cl(.3.75H(2)O), respectively. The latter is more lipophilic than analogous 1 : 2 adducts of gold(I) chloride with the diphosphine ligands 1,2-bis(di-n-pyridylphosphino)ethane (dnpype) for n = 2, 3 and 4, based on measurement of the n-octanol-water partition coefficient (log P = -0.46). A single crystal structure determination of the 1 : 2 Au(I) complex of the 3-pyridyl ethane ligand shows it to be of the form [Au(d3pype-P,P')(2)]Cl.5H(2)O. The in vitro cytotoxic activity of [Au(d2pypp)(2)]Cl was assessed in human normal and cancer breast cells and selective toxicity to the cancer cells found. The significance of these results to the antitumour properties of chelated 1 : 2 Au(I) diphosphine complexes is discussed. 相似文献
148.
Julia Modrzejewska Marcin Szala Aleksandra Grzelakowska Magorzata Zakos-Szyda Jacek Zielonka Radosaw Podsiady 《Molecules (Basel, Switzerland)》2021,26(19)
Derivatives of coumarin, containing oxidant-sensitive boronate group, were recently developed for fluorescent detection of inflammatory oxidants. Here, we report the synthesis and the characterization of 3-(2-benzothiazolyl)-7-coumarin boronic acid pinacol ester (BC-BE) as a fluorescent probe for the detection of peroxynitrite (ONOO–), with high stability and a fast response time. The BC-BE probe hydrolyzes in phosphate buffer to 3-(2-benzothiazolyl)-7-coumarin boronic acid (BC-BA) which is stable in the solution even after a prolonged incubation time (24 h). BC-BA is slowly oxidized by H2O2 to form the phenolic product, 3-benzothiazol-2-yl-7-hydroxy-chromen-2-one (BC-OH). On the other hand, the BC-BA probe reacts rapidly with ONOO−. The ability of the BC-BA probe to detect ONOO– was measured using both authentic ONOO– and the system co-generating steady-state fluxes of O2•– and •NO. BC-BA is oxidized by ONOO– to BC-OH. However, in this reaction 3-benzothiazol-2-yl-chromen-2-one (BC-H) is formed in the minor pathway, as a peroxynitrite-specific product. BC-OH is also formed in the reaction of BC-BA with HOCl, and subsequent reaction of BC-OH with HOCl leads to the formation of a chlorinated phenolic product, which could be used as a specific product for HOCl. We conclude that BC-BA shows potential as an improved fluorescent probe for the detection of peroxynitrite and hypochlorite in biological settings. Complementation of the fluorescence measurements by HPLC-based identification of oxidant-specific products will help to identify the oxidants detected. 相似文献
149.
Wanda Mczka Anna Duda-Madej Aleksandra Grny Magorzata Grabarczyk Katarzyna Wiska 《Molecules (Basel, Switzerland)》2021,26(16)
One of the primary reasons for the search for new antimicrobial agents is the increasing and spreading resistance of microorganisms to previously used drugs. This is particularly important in the case of rapidly progressing infections that require the rapid administration of an appropriately selected antibiotic. However, along with the administration of antibiotics, complications in the disease-weakened body may arise in the form of systemic mycoses, viral infections, and protozoan infections. Therefore, there is an increasing interest among researchers focusing on the use of naturally occurring terpenic compounds in stand-alone or combined therapies with antibiotics. In this publication, the aim of our work is to present the results of a literature review on the antimicrobial activity of eucalyptol. 相似文献
150.
The present paper contains theoretical analysis and a thorough discussion of the applicability of Fick’s approach to modelling
CO2 and CH4 diffusion in heterogeneous coal, especially with regard to the estimation of a single diffusion coefficient from the dependence
defined by a number series. The computations were performed for high rank coal depending on the grain size of coal samples
and within a narrow range of temperature − 293 and 303 K.
The results of the model’s application to the experimental data show that the method of estimation of the diffusion coefficient
is very important. Our results also show that the diffusion coefficient changes are closely related with the one-parameter
analysis of coal grain size distribution. 相似文献