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211.
Lagnoux D Delort E Douat-Casassus C Esposito A Reymond JL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(5):1215-1226
Peptide dendrimers were prepared by solid-phase peptide synthesis. Monomeric dendrimers were first obtained by assembly of a hexapeptide sequence containing alternate standard alpha-amino acids with diamino acids as branching units. The monomeric dendrimers were then dimerized by disulfide-bridge formation at the core cysteine. The synthetic strategy is compatible with functional amino acids and different diamino acid branching units. Peptide dendrimers composed of the catalytic triad amino acids histidine, aspartate, and serine catalyzed the hydrolysis of N-methylquinolinium salts when the histidine residues were placed at the outermost position. The dendrimer-catalyzed hydrolysis of 7-isobutyryl-N-methylquinolinium followed saturation kinetics with a rate constant of catalysis/rate constant without catalysis (k(cat)/k(uncat)) value of 3350 and a rate constant of catalysis/Michaelis constant (k(cat)/K(M)) value 350-fold larger than the second-order rate constant of the 4-methylimidazole-catalyzed reaction; this corresponds to a 40-fold rate enhancement per histidine side chain. Catalysis can be attributed to the presence of histidine residues at the surface of the dendrimers. 相似文献
212.
Okadaic acid (OA), a lipophilic phycotoxin highly toxic to humans is produced by toxigenic dinoflagellates. The need to develop high performing methods for OA analysis able to improve the traditional ones is evident. In this work, competitive indirect enzyme-linked electrochemical immunosensor based on super paramagnetic nanobeads has been developed for the detection of OA. Streptavidin-coated magnetic beads were used as support to immobilize the biotinylated OA. Preliminary, colorimetric tests were performed in order to optimize different experimental parameters. Electrochemical detection was carried out by differential pulse voltammetry (DPV). The limit of detection (LOD) (0.38 μg L−1), the mid point value (IC50) (3.15 μg L−1) and the time needed (60 min) for analysis of a real sample validated the developed electrochemical immunosensor as a promising tool for routine use. The matrix effect and the recovery rate were also assessed, showing an excellent percentage of recovery. 相似文献
213.
Malika Berredjem Zine Regaïnia Abdelghani Djahoudi Nour-Eddine Aouf Georges Dewynter Jean-Louis Montero 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):249-264
Abstract Les carboxylsulfamides sont obtenus à partir de l'isocyanate de chlorosulfonyle, d'amines primaires et d'α-hydroxyesters. Après réduction alcaline, ces carboxylsulfamides sont cyclisés dans les conditions de la réaction de Mitsunobu pour conduire aux N-sulfamoyloxazolidinones chides avec des rendements élevés. The synthesis of carboxylsulfamides was carried out starting from chlorosulfonyl isocyanate, primary amines and α-hydroxyesters. After reduction, the carboxylsulfamides were cyclised under Mitsunobu conditions giving N-sulfamoyloxazolidinones in good yields. 相似文献
214.
A screen-printed biosensor for the detection of pesticides in water miscible organic solvents is described based on the use of p-aminophenyl acetate as acetylcholinesterase substrate. The oxidation of p-aminophenol, product of the enzymatic reaction was monitored at 100 mV vs. Ag/AgCl screen-printed reference electrode. Miscible organic solvents as ethanol and acetonitrile were tested. The acetylcholinesterase (AChE) was immobilised on a screen-printed electrode surface by entrapment in a PVA-SbQ polymer and the catalytic activity of immobilised AChE was studied in the presence of different percentages of organic solvents in buffer solution. The sensor shows good characteristics when experiments were performed in concentrations of organic solvents below 10%. No significant differences were observed when working with 1 and 5% acetonitrile in the reaction media. Detection limits as low as 1.91x10(-8) M paraoxon and 1.24x10(-9) M chlorpyrifos ethyl oxon were obtained when experiments are carried out in 5% acetonitrile. 相似文献
215.
216.
Interference-free biosensor based on screen-printing technology and sol-gel immobilization for determination of acetaldehyde in wine 总被引:1,自引:0,他引:1
Noguer T Tencaliec A Calas-Blanchard C Avramescu A Marty JL 《Journal of AOAC International》2002,85(6):1382-1389
A monoenzymatic amperometric biosensor was developed for the detection of acetaldehyde. The sensor is based on the association of screen-printed carbon electrodes and aldehyde dehydrogenase immobilized by a sol-gel entrapment method. Modification of screen-printed carbon electrodes with Reinecke salt of Meldola's Blue (MBRS) resulted in highly sensitive and interference-free nicotinamide-adenine dinucleotide (NADH) detectors. Based on MBRS-mediated oxidation of NADH at -150 mV versus pseudo Ag/AgCl, acetaldehyde was determined in the range 10-260 microM, compatible with wine quality monitoring. The method of immobilization based on sol-gel entrapment was optimized to obtain the best compromise between sensitivity and operational stability. The sensor response was stable for 40 consecutive assays with methyltrimethoxysilane used as alkoxide precursor, thus allowing a possible calibration of the sensor before each measurement. The biosensors were used to analyze French wines. The method was validated with a commercially available enzymatic kit based on a standard spectrophotometric method. 相似文献
217.
A simple oxydative procedure converted Z-L-threonine methyl ester into the corresponding (2S)-β-keto ester: Starting material for the synthesis of labelled threonine derivatives. 相似文献
218.
Negrerie M Cianetti S Vos MH Martin JL Kruglik SG 《The journal of physical chemistry. B》2006,110(25):12766-12781
Cytochrome c (Cyt c) is a heme protein involved in electron transfer and also in apoptosis. Its heme iron is bisaxially ligated to histidine and methionine side chains and both ferric and ferrous redox states are physiologically relevant, as well as a ligand exchange between internal residue and external diatomic molecule. The photodissociation of internal axial ligand was observed for several ferrous heme proteins including Cyt c, but no time-resolved studies have been reported on ferric Cyt c. To investigate how the oxidation state of the heme influences the primary photoprocesses, we performed a comprehensive comparative study on horse heart Cyt c by subpicosecond time-resolved resonance Raman and femtosecond transient absorption spectroscopy. We found that in ferric Cyt c, in contrast to ferrous Cyt c, the photodissociation of an internal ligand does not take place, and relaxation dynamics is dominated by vibrational cooling in the ground electronic state of the heme. The intermolecular vibrational energy transfer was found to proceed in a single phase with a temperature decay of approximately 7 ps in both ferric and ferrous Cyt c. For ferrous Cyt c, the instantaneous photodissociation of the methionine side chain from the heme iron is the dominant event, and its rebinding proceeds in two phases, with time constants of approximately 5 and approximately 16 ps. A mechanism of this process is discussed, and the difference in photoinduced coordination behavior between ferric and ferrous Cyt c is explained by an involvement of the excited electronic state coupled with conformational relaxation of the heme. 相似文献
219.
Aggregation numbers of cationic oligomeric surfactants: a time-resolved fluorescence quenching study
Wattebled L Laschewsky A Moussa A Habib-Jiwan JL 《Langmuir : the ACS journal of surfaces and colloids》2006,22(6):2551-2557
The micelle aggregation numbers (N(agg)) of several series of cationic oligomeric surfactants were determined by time-resolved fluorescence quenching (TRFQ) experiments, using advantageously 9,10-dimethylanthracene as fluorophore. The study comprises six dimeric ("gemini"), three trimeric, and two tetrameric surfactants, which are quaternary ammonium chlorides, with medium length spacer groups (C(3)-C(6)) separating the individual surfactant fragments. Two standard cationic surfactants served as references. The number of hydrophobic chains making up a micellar core is relatively low for the oligomeric surfactants, the spacer length playing an important role. For the dimers, the number decreases from 32 to 21 with increasing spacer length. These numbers decrease further with increasing degree of oligomerization down to values of about 15. As for many conventional ionic surfactants, the micelles of all oligomers studied grow only slightly with the concentration, and they remain in the regime of small micelles up to concentrations of at least 3 wt %. 相似文献
220.
Maury J Feray L Bazin S Clément JL Marque SR Siri D Bertrand MP 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(5):1586-1595
The reactions of dialkylzincs (Me(2)Zn, Et(2)Zn, and nBu(2)Zn) with oxygen have been investigated by EPR spectroscopy using spin-trapping techniques. The use of 5-diethoxyphosphoryl-5-methyl-1-pyrrroline N-oxide (DEPMPO) as a spin-trap has allowed the involvement of alkyl, alkylperoxyl, and alkoxyl radicals in this process to be probed for the first time. The relative ratio of the corresponding spin-adducts depends strongly on the nature of the R group, which controls the C-Zn bond dissociation enthalpy, and on the experimental conditions (excess of spin-trap compared with R(2)Zn and vice versa). The results have demonstrated that Et(2)Zn and, to a lesser extent, nBu(2)Zn are much better traps for oxygen-centered species than Me(2)Zn. When the dialkylzincs were used in excess with respect to the spin-trap, the concentration of the oxygen-centered radical adducts of DEPMPO was much lower for Et(2)Zn and nBu(2)Zn than for Me(2)Zn. A detailed reaction mechanism is discussed and C-Zn, O-Zn, and O-O bond dissociation enthalpies for the proposed reaction intermediates were calculated at the UB3LYP/6-311++G(3df,3pd)//UB3LYP/6-31G(d,p) level of theory to support the rationale. 相似文献