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151.
本文合成了2个新的三元铜(Ⅱ)配合物:[Cu(TBZ)(L-Met)(H2O)]ClO4.H2O(1)和[Cu(HPB)(L-Met)]ClO4(2)[TBZ=2-(4′-噻唑基)苯并咪唑,HPB=2-(2-吡啶)苯并咪唑,L-Met=L-蛋氨酸]。通过元素分析、摩尔电导率、IR、UV-Vis及电喷雾质谱对这些配合物进行了表征。用二倍稀释法研究了配合物的抗菌活性,发现配合物对金黄色葡萄球菌(Staphylococcus aureus,G+),枯草杆菌(Bacillussubtilis,G+),沙门氏杆菌(Salmonella,G-)和大肠杆菌(Escherichia coil,G-)具有良好的抑制作用。采用电子吸收光谱、荧光光谱、粘度测定及琼脂凝胶电泳方法研究了配合物与DNA的相互作用,结果表明,配合物以插入方式与DNA作用,在维生素C存在下通过羟自由基.OH,单线态氧1O2或者1O2类似物如Cu-O2,切割pBR322 DNA双螺旋结构。 相似文献
152.
This work describes the performance of poly(methyl methacrylate) (PMMA) microfluidic DNA purification devices with embedded microfabricated posts, functionalized with chitosan. PMMA is attractive as a substrate for creating high surface area (SA) posts for DNA capture because X-ray lithography can be exploited for extremely reproducible fabrication of high SA structures. However, this advantage is offset by the delicate nature of the posts when attempting bonding to create a closed system, and by the challenge of functionalizing the PMMA surface with a group that invokes DNA binding. Methods are described for covalent functionalization of the post surfaces with chitosan that binds DNA in a pH-dependent manner, as well as for bonding methods that avoid damaging the underlying post structure. A number of geometric posts designs are explored, with the goal of identifying post structures that provide the requisite surface area without a concurrent rise in fluidic resistance that promotes device failure. Initial proof-of-principle is shown by recovery of prepurified human genomic DNA (hgDNA), with real-world utility illustrated by purifying hgDNA from whole blood and demonstrating it to be PCR-amplifiable. 相似文献
153.
Bani-Yaseen AD Kawaguchi T Price AK Culbertson CT Jankowiak R 《Analytical and bioanalytical chemistry》2011,399(1):519-524
Catechol estrogen-derived DNA adducts are formed as a result of the reaction of catechol estrogen metabolites (e.g., catechol
estrogen quinones) with DNA to form depurinating adducts. Developing a new methodology for the detection of various DNA adducts
is essential for medical diagnostics, and to this end, we demonstrate the applicability of on-chip capillary electrophoresis
with an integrated electrochemical system for the separation and amperometric detection of various catechol estrogen-derived
DNA adducts. A hybrid PDMS/glass microchip with in-channel amperometric detection interfaced with in situ palladium decoupler
is utilized and presented. The influence of buffer additives along with the effect of the separation voltage on the resolving
power of the microchip is discussed. Calibration plots were constructed in the range 0.4–10 μM with r
2 ≥ 0.999, and detection limits in the attomole range are reported. These results suggest that on-chip analysis is applicable
for analyzing various DNA adducts as potential biomarkers for future medical diagnostics. 相似文献
154.
单调性条件在Fourier级数收敛性中的最终推广:历史、发展、应用和猜想 总被引:1,自引:0,他引:1
为了对Fourier级数进行近似计算和有效应用,必须研究其收敛性,这个课题有长久的历史,形成了数学分析中吸引包括许多著名数学家在内的学者研究的一条热烈但困难的主流.其中,在三角级数(Fourier级数)一致收敛性和平均收敛性问题中人们一直关心Fourier系数的单调递减条件最终的推广.这个开始于英国Chaundy-Jollife(1916年)和Young(1913年)的工作最近出现了突破性的进展,产生了许多完善的结果.本文将对这方面的历史、发展给出综述,并重点介绍最近的应用成果,并对以后的工作给出研究思路和线索. 相似文献
155.
Southon PD Price DJ Nielsen PK McKenzie CJ Kepert CJ 《Journal of the American Chemical Society》2011,133(28):10885-10891
The metal-organic host material [{Co(III)(2)(bpbp)(O(2))}(2)bdc](PF(6))(4) (1·2O(2); bpbp(-) = 2,6-bis(N,N-bis(2-pyridylmethyl)aminomethyl)-4-tert-butylphenolato; bdc(2-) = 1,4-benzenedicarboxylato) displays reversible chemisorptive desorption and resorption of dioxygen through conversion to the deoxygenated Co(II) form [{Co(II)(2)(bpbp)}(2)bdc](PF(6))(4) (1). Single crystal X-ray diffraction analysis indicates that the host lattice 1·2O(2), achieved through desorption of included water guests from the as-synthesized phase 1·2O(2)·3H(2)O, consists of an ionic lattice containing discrete tetranuclear complexes, between which lie void regions that allow the migration of dioxygen and other guests. Powder X-ray diffraction analyses indicate that the host material retains crystallinity through the dioxygen desorption/chemisorption processes. Dioxygen chemisorption measurements on 1 show near-stoichiometric uptake of dioxygen at 5 mbar and 25 °C, and this capacity is largely retained at temperatures above 100 °C. Gas adsorption isotherms of major atmospheric gases on both 1 and 1·2O(2) indicate the potential suitability of this material for air separation, with a O(2)/N(2) selectivity factor of 38 at 1 atm. Comparison of oxygen binding in solution and in the solid state indicates a dramatic increase in binding affinity to the complex when it is incorporated in a porous solid. 相似文献
156.
Relative partial ionization cross sections (PICS) for the formation of fragment ions following electron ionization of SiCl(4), in the electron energy range 30-200 eV, have been determined using time-of-flight mass spectrometry coupled with an ion coincidence technique. By this method, the contributions to the yield of each fragment ion from dissociative single, double, and triple ionization, are distinguished. These yields are quantified in the form of relative precursor-specific PICS, which are reported here for the first time for SiCl(4). For the formation of singly charged ionic fragments, the low-energy maxima appearing in the PICS curves are due to contributions from single ionization involving predominantly indirect ionization processes, while contributions to the yields of these ions at higher electron energies are often dominated by dissociative double ionization. Our data, in the reduced form of relative PICS, are shown to be in good agreement with a previous determination of the PICS of SiCl(4). Only for the formation of doubly charged fragment ions are the current relative PICS values lower than those measured in a previous study, although both datasets agree within combined error limits. The relative PICS data presented here include the first quantitative measurements of the formation of Cl(2) (+) fragment ions and of the formation of ion pairs via dissociative double ionization. The peaks appearing in the 2D ion coincidence data are analyzed to provide further information concerning the mechanism and energetics of the charge-separating dissociations of SiCl(4) (2+). The lowest energy dicationic precursor state, leading to SiCl(3) (+) + Cl(+) formation, lies 27.4 ± 0.3 eV above the ground state of SiCl(4) and is in close agreement with a calculated value of the adiabatic double ionization energy (27.3 eV). 相似文献
157.
Which, if any, hydrates will crystallise? Predicting hydrate formation of two dihydroxybenzoic acids
Braun DE Karamertzanis PG Price SL 《Chemical communications (Cambridge, England)》2011,47(19):5443-5445
A study of two dihydroxybenzoic acid isomers shows that computational methods can be used to predict hydrate formation, the compound:water ratio and hydrate crystal structures. The calculations also help identify a novel hydrate found in the solid form screening that validates this study. 相似文献
158.
Parkes MA Lockyear JF Schröder D Roithová J Price SD 《Physical chemistry chemical physics : PCCP》2011,13(41):18386-18392
The single-electron transfer reaction between NO(2+) and NO, which initially forms a pair of NO(+) ions, has been studied using a position-sensitive coincidence technique. The reactivity in this class of collision system, which involves the interaction of a dication with its neutral precursor, provides a sensitive test of recent ideas concerning electronic state selectivity in dicationic single-electron transfer reactions. In stark contrast to the recently observed single-electron transfer reactivity in the analogous CO(2)(2+)/CO(2) and O(2)(2+)/O(2) collision systems, electron transfer between NO(2+) and NO generates two product NO(+) ions which behave in an identical manner, whether the ions are formed from NO(2+) or NO. This observed behaviour is in excellent accord with the recently proposed rationalization of the state selectivity in dication-molecule SET reactions using simple propensity rules involving one-electron transitions. 相似文献
159.
Jonathan A. Kelner James R. Lee Gregory N. Price Shang-Hua Teng 《Geometric And Functional Analysis》2011,21(5):1117-1143
We present a method for proving upper bounds on the eigenvalues of the graph Laplacian. A main step involves choosing an appropriate
“Riemannian” metric to uniformize the geometry of the graph. In many interesting cases, the existence of such a metric is
shown by examining the combinatorics of special types of flows. This involves proving new inequalities on the crossing number
of graphs. 相似文献
160.
Russell G Evans Oleksiy V Klymenko Paul D Price Stephen G Davies Christopher Hardacre Richard G Compton 《Chemphyschem》2005,6(3):526-533
Measurements on the diffusion coefficient of the neutral molecule N,N,N',N'-tetramethyl-para-phenylenediamine and the radical cation and dication generated by its one- and two-electron oxidation, respectively, are reported over the range 298-348 K in both acetonitrile and four room temperature ionic liquids (RTILs). Data were collected using single and double potential step chronoamperometry at a gold disk electrode of micrometer dimension, and analysed via fitting to the appropriate analytical expression or, where necessary, to simulation. The variation of diffusion coefficient with temperature was found to occur in an Arrhenius-type manner for all combinations of solute and solvent. For a given ionic liquid, the diffusional activation energies of each species were not only closely equivalent to each other, but also to the RTIL's activation energy of viscous flow. In acetonitrile supported with 0.1 M tetrabutylammonium perchlorate, the ratio in diffusion coefficients of the radical cation and dication to the neutral molecule were calculated as 0.89 +/- 0.05 and 0.51 +/- 0.03, respectively. In contrast, amongst the ionic liquids the same ratios were determined to be on average 0.53 +/- 0.04 and 0.33 +/- 0.03. The consequences of this dissimilarity are considered in terms of the modelling of voltammetric data gathered within ionic liquid solvents. 相似文献