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21.
The electroanalytical method described for the simultaneous determination of concentration, the number of electrons involved in the redox process and diffusion coefficient is based on evaluation of the ratios between the currents recorded for the analyte and for an easily standardized reference species dissolved in the same medium. Three different electroanalytical techniques are used in which the currents exhibit, for two techniques at least, different dependences on both the diffusion coefficient and electron number. The approach is applicable to diffusion-controlled processes, regardless of the degree of reversibility involved. Reliability tests with electroactive organic compounds dissolved in dimethyl sulphoxide show that both accuracy and precision are within 10% depending on the chosen combination of techniques. 相似文献
22.
2-and 4-Ethoxymethoxybenzyl methyl ethers were employied as useful starting materials for the synthesis of 1,2- or 1,4-dicarbo-substituted benzenes. The proposed reaction sequence involves connection between the reductive lithiation of benzyl alkyl ethers and the metal-catalyzed cross-coupling reaction of aromatic triflates. 相似文献
23.
Salvatore Daniele Maria-Antonietta Baldo Paolo Ugo Gian-Antonio Mazzocchin 《Analytica chimica acta》1989
Differential-pulse anodic stripping voltammetry with a mercury microelectrode is used for the determination of zinc, cadmium, lead and copper in wine at its natural pH without pretreatment. The effects of the matrix on the stripping peaks are studied in detail by varying the concentration of the metals. Intermetallic (CuZn) interferences and the effects of oxygen are described. The results obtained for the labile metal contents varied from 2 μg l?1 for cadmium to 148 μg l?1 for zinc; standard addition plots were linear over about two orders of magnitude above these levels, demonstrating the negligible effect of organic matter. Acidification of the sample with hydrochloric acid to pH 1 allowed the total metal contents to be determined. The reliability of the method was tested by comparison with the results obtained with atomic absorption spectrometry; the differences were within 10–20%. 相似文献
24.
Haplotype studies support slippage as the mechanism of germline mutations in short tandem repeats 总被引:1,自引:0,他引:1
Klintschar M Dauber EM Ricci U Cerri N Immel UD Kleiber M Mayr WR 《Electrophoresis》2004,25(20):3344-3348
Germline mutations of human short tandem repeat (STR) loci are expansions or contractions of repeat arrays which are not well understood in terms of the mechanism(s) underlying such mutations. Although polymerase slippage is generally accepted as a mechanism capable to explain most features of such mutations, it is still possible that unequal crossing over plays some role in those events, as most studies in humans could not exclude unequal crossing over (UCO). Crossing over can be studied by analyzing haplotypes using flanking markers. To check for UCO in mutations, we have analyzed 150 paternity cases for which more than the usual trio (mother, child, and father) were available for testing by analyzing 16 STR loci. In a total of 4900 parent-child allele transfers four mutations were observed at different loci (D8S1179, D18S51, D21S11, and SE33/ACTBP2). To identify the mutated allele and to check for UCO, we typed at least four informative loci flanking the mutated locus and used the pedigree data to establish haplotypes. By doing so we were able to exclude UCO in each case. Moreover, we were able to identify the mutations as one-repeat contractions/expansions. Our data thus support slippage as the mechanism of germline mutations in STRs. 相似文献
25.
α-Acetoxy acid methyl esters are prepared in excellent yields by treating aliphatic α-acetoxy dimethyl acetals with trichloroisocyanuric acid in DMF. 相似文献
26.
27.
A Wiener-type condition for the continuity at the boundary points of Q-minima, is established, in terms of the divergence of a suitable Wiener integral. 相似文献
28.
This review deals with recent advances in bioelectroanalytical applications of nanostructured electrodes, in particular nanoelectrode ensembles (NEEs) and arrays (NEAs). First, nanofabrication techniques, principles of function, and specific advantages and limits of NEEs and NEAs are critically discussed. In the second part, some recent examples of bioelectroanalytical applications are presented. These include use of nanoelectrode arrays and/or ensembles for direct electrochemical analysis of pharmacologically active organic compounds or redox proteins, and the development of functionalized nanoelectrode systems and their use as catalytic or affinity electrochemical biosensors. 相似文献
29.
Ugo Bussy Illa Tea Véronique Ferchaud-Roucher Michel Krempf Virginie Silvestre Nicolas Galland Denis Jacquemin Moa Andresen-Bergström Ulrik Jurva Mohammed Boujtita 《Analytica chimica acta》2013
The coupling between an electrochemical cell (EC) and a mass spectrometer (MS) is a useful screening tool (EC-MS) to study the oxidative transformation pathways of various electroactive species. For that purpose, we showed that the EC-MS method, carried out in the presence and absence of isotope 18O labeled water leads not only to a fast identification of oxidation products but also leads to a fast elucidation of the mechanism pathway reaction. We examined herein the case of the electrochemical hydrolysis of activated aromatic ether. Acebutolol (β-blockers) was selected herein as model of activated aromatic ether, and its electrochemical oxidation was examined in both the presence and absence of isotope 18O labeled water. To elucidate electrochemical hydrolysis pathway reaction: O-dealkylation or O-dealkoxylation, our approach was used to prove its applicability. The electrochemical oxidation mechanism was then elucidated showing an O-dealkoxylation reaction. In addition, density functional theory (DFT) calculations fully support the experimental conclusions. 相似文献
30.
Dr. Antonello Di Crescenzo Dr. Luca Bardini Dr. Bruna Sinjari Dr. Tonino Traini Dr. Lisa Marinelli Dr. Mauro Carraro Prof. Raimondo Germani Dr. Pietro Di Profio Prof. Sergio Caputi Prof. Antonio Di Stefano Prof. Marcella Bonchio Prof. Francesco Paolucci Prof. Antonella Fontana 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(48):16415-16423
Novel hydrogel phases based on positively charged and zwitterionic surfactants, namely, N‐[p‐(n‐dodecyloxybenzyl)]‐N,N,N‐trimethylammonium bromide (pDOTABr) and p‐dodecyloxybenzyldimethylamine oxide (pDOAO), which combine pristine carbon nanotubes (CNTs), were obtained, thus leading to stable dispersions and enhanced cross‐linked networks. The composite hydrogel featuring a well‐defined nanostructured morphology and an overall positively charged surface was shown to efficiently immobilise a polyanionic and redox‐active tetraruthenium‐substituted polyoxometalate (Ru4POM) by complementary charge interactions. The resulting hybrid gel has been characterised by electron microscopy techniques, whereas the electrostatic‐directed assembly has been monitored by means of fluorescence spectroscopy and ζ‐potential tests. This protocol offers a straightforward supramolecular strategy for the design of novel aqueous‐based electrocatalytic soft materials, thereby improving the processability of CNTs while tuning their interfacial decoration with multiple catalytic domains. Electrochemical evidence confirms that the activity of the catalyst is preserved within the gel media. 相似文献