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991.
Maheswari PU van der Ster M Smulders S Barends S van Wezel GP Massera C Roy S den Dulk H Gamez P Reedijk J 《Inorganic chemistry》2008,47(9):3719-3727
The reactions of the ligand 2-(2-pyridyl)benzthiazole (pbt) with CuBr 2 and ZnCl 2 in acetonitrile produce the complexes [Cu(pbt)Br 2] ( 1) and [Zn(pbt)Cl 2] ( 3), respectively. When complex 1 is dissolved in DMF, complex 2 is obtained as light-green crystals. The reaction of pbt with CuBr 2 in DMF also yields the complex [Cu(pbt)Br 2(dmf)] ( 2) (dmf = dimethylformamide). Complexes 1- 3 were characterized by X-ray crystallography. Complexes 1 and 3 have distorted tetrahedral coordination environments, and complex 2 is constituted of two slightly different copper centers, both exhibiting distorted trigonal bipyramidal geometries. Complexes 1 and 2 cleave phiX174 phage DNA, both in the presence and the absence of reductant. The free ligand pbt does not show any DNA-cleaving abilities. The poor solubility of complex 3 makes it not applicable for biological tests. The occurrence of DNA breaks in the presence of various radical scavengers suggests that no diffusible radicals are involved in the DNA cleavage by complex 1, as none of the scavengers inhibit the cleavage reaction. The DNA-cleavage products are not religated with the enzyme T4 DNA ligase, which is an additional proof that the cleavage is nonhydrolytic. Most probably the cleaving reaction involves reactive oxygen species, which could not be trapped, leading to an oxidative mechanism. An easy oxidation of Cu (II)(pbt)Br 2 to Cu (III) in DMF and the reduction of the same to Cu (I), under similar electrochemical conditions may lead to the in situ activation of molecular oxygen, resulting in the formation of metal solvated nondiffusible radicals able to prompt the oxidative cleavage of DNA. Complex 1 and the pure ligand exhibit remarkable cytotoxic effects against the cancer cell lines L1210 and A2780 and also against the corresponding cisplatin-resistant mutants of these cell lines. 相似文献
992.
We present Finite Element Method (FEM) simulations of interdigitated array (IDA) electrode geometries to study and verify redox selectivity and redox cycling amplification factor. The simulations provide an adequate explanation of an earlier found, but poorly understood, high amplification factor (65×) in a 1 μm‐spaced IDA microdevice. Moreover, using the FEM calculations we present selectivity measurements with IDA electrodes in a mixture of two redox species, as for example dopamine and ferricyanide. We show that it is possible to electrochemically detect dopamine in presence of the stronger reductor ferricyanide, which is impossible with direct amperometric detection, with the use of IDA electrodes with proper polarization potential of the collector electrode. Using our simulations, we show that a theoretical selectivity of dopamine over ferricyanide of 11 can be achieved. 相似文献
993.
994.
J. Engel L. Blanchet B. Bloemen L.P. van den Heuvel U.H.F. Engelke R.A. Wevers L.M.C. Buydens 《Analytica chimica acta》2015
Many advanced metabolomics experiments currently lead to data where a large number of response variables were measured while one or several factors were changed. Often the number of response variables vastly exceeds the sample size and well-established techniques such as multivariate analysis of variance (MANOVA) cannot be used to analyze the data. 相似文献
995.
Jan Gerretzen Ewa Szymańska Jacob Bart Antony N. Davies Henk-Jan van Manen Edwin R. van den Heuvel Jeroen J. Jansen Lutgarde M.C. Buydens 《Analytica chimica acta》2016
The aim of data preprocessing is to remove data artifacts—such as a baseline, scatter effects or noise—and to enhance the contextually relevant information. Many preprocessing methods exist to deliver one or more of these benefits, but which method or combination of methods should be used for the specific data being analyzed is difficult to select. Recently, we have shown that a preprocessing selection approach based on Design of Experiments (DoE) enables correct selection of highly appropriate preprocessing strategies within reasonable time frames. 相似文献
996.
Benno van den Berg 《Archive for Mathematical Logic》2013,52(1-2):113-135
We study a new proof principle in the context of constructive Zermelo-Fraenkel set theory based on what we will call “non-deterministic inductive definitions”. We give applications to formal topology as well as a predicative justification of this principle. 相似文献
997.
The purpose of the present study was to investigate the melting behavior of polyethylene glycol 6000 (PEG 6000) as such as well as in solid dispersions containing diazepam or temazepam, prepared by solvent and fusion methods, using differential scanning calorimetry (DSC). It was shown that the melting behavior of pure PEG 6000 is influenced by the crystallization procedure applied. Fusion at 80°C followed by cooling always yielded three different crystal modifications. The rate of cooling (under controlled conditions) was found to have a significant influence on the relative distribution of the three modifications: the lower the cooling rate, the higher the relative amount of the extended modification. Crystallization from organic solution yielded mainly the once folded form. The presence of diazepam and temazepam influenced the relative amount of the different PEG 6000 modifications. Both drugs decreased the formation of the more stable modification, while the formation of the twice folded form was induced. However, in the case of temazepam the contribution of the extended form at higher drug levels increased in dispersions obtained from organic solutions. 相似文献
998.
In this note we shall determine the ambivalent groups all whose nonlinear irreducible characters have even degrees and the solvable ambivalent groups whith G' the unique minimal subgroup. 相似文献
999.
Henk Schierbeek Tanja C. W. Moerdijk‐Poortvliet Chris H. P. van den Akker Frans W. J. te Braake Henricus T. S. Boschker Johannes B. van Goudoever 《Rapid communications in mass spectrometry : RCM》2009,23(23):3824-3830
The use of stable isotope labelled glucose provides insight into glucose metabolism. The 13C‐isotopic enrichment of glucose is usually measured by gas chromatography/mass spectrometry (GC/MS) or gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). However, in both techniques the samples must be derivatized prior to analysis, which makes sample preparation more labour‐intensive and increases the uncertainty of the measured isotopic composition. A novel method for the determination of isotopic enrichment of glucose in human plasma using liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) has been developed. Using this technique, for which hardly any sample preparation is needed, we showed that both the enrichment and the concentration could be measured with very high precision using only 20 µL of plasma. In addition, a comparison with GC/MS and GC/IRMS showed that the best performance was achieved with the LC/IRMS method making it the method of choice for the measurement of 13C‐isotopic enrichment in plasma samples. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
1000.
Marc P. Baggelaar Freek J. Janssen Annelot C. M. vanEsbroeck Hans denDulk Marco Allar Sascha Hoogendoorn Ross McGuire Bogdan I. Florea Nico Meeuwenoord Hans vandenElst Gijsbert A. vanderMarel Jaap Brouwer Vincenzo DiMarzo Herman S. Overkleeft Mario vanderStelt 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2013,125(46):12415-12415