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11.
Gold electrodes were chemically modified with thioctic acid monolayer designed to mimic biological ion-channel membranes. The technique was then used in the determination of alkali, alkaline earth, thallium(I), and lanthanum metal cations as analytes. Cyclic voltammograms (CV) of [Fe(CN)6]3− an electroactive marker, were measured in the presence of the various types of analyte cations. In the absence of the analyte cation, electrostatic repulsion between the marker anions and the carboxylate groups of the receptor monolayer hindered the approach of the marker anion to the electrode surface and hence hindered its reduction. The modified electrodes responded well to the metal cations except the alkali metal cations. The sensors could detect the trivalent cation La3+ at concentrations as low as 10−8 M. The response of the sensor to the metal cations increase in the order alkali metal3+ can be discriminated in the ratio 1:100. This makes it possible to determine the trivalent ion in a sample matrix containing monovalent and divalent cations. Thallium(I) ion showed marked deviation in its response as compared to monovalent ions of the alkali metals. The ion-channel sensor based on self-assembled monolayer of thioctic acid therefore offers a potential alternative technique for the selective determination of metal ions. 相似文献
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《Electroanalysis》2003,15(14):1192-1197
The investigation of the electrochemical reduction processes of C6H5SSC6H5 and C6H5SH in CH3CN using cyclic voltammetry indicates a different behavior on GC and Au electrodes. On GC surface adsorption phenomena are absent, the electrochemical reduction process is irreversible and diffusion controlled. For both the starting molecules the same species, C6H5S?, is formed upon reduction. The E° values of the reduction processes were determined by convolution method and the standard free energy of the S? S bond of C6H5SSC6H5 estimated. On Au surface instead, a self‐assembled monolayer of C6H5SAuads originated after the S? S or S? H bond breaking can be observed by simply dipping the electrode in solution of C6H5SSC6H5 and C6H5SH, respectively. The properties of the SAM were investigated by electrochemical reduction of the adsorbed thiolates. On Au electrode the reduction processes involve C6H5SAuads and give rise to desorbed C6H5S?. A neutral radical is obtained by electrochemical oxidation of thiolate anion. It reacts rapidly with the electrode surface to give the S‐Au bond again. 相似文献
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15.
Dispersion of copper(Ⅱ) phthalocyanine (CuPc), copper(Ⅱ) phthalocyaninesulfonate (CuPcS) and cobalt(Ⅱ)phthalocyaninetetrasulfonate (CoPcTS) on the surface of titanium dioxide was investigated by XRD, XPS, FT-IR and UV-Vis techniques. Results show that interaction between CuPc and TiO2 was very weak and CuPc was difficult to disperse on the surface of the support. While partly sulfurized CuPcS could be dispersed on the surface of support through sulfo-groups and its dispersion capacity was determined to be 0.085 g CuPcS/g TiO2. Completely sulfurlzed CoPcTS could also be dispersed on the surface of TiO2 as a monolayer and its dispersion capacity was 0.12 g CoPcTS/g TiO2. Interactions of the sulfo-groups as well as the electrons of CoPcTS with the surface of TiO2 could be evidenced by FT-IR characterization. Therefore, it was suggested that CoPcTS molecules be adsorbed on the surface of TiO2 in a flat-lying mode while CuPcS in a slanting one. UV-Vis spectra show that the dispersed CuPcS and CoPcTS molecules exist in both forms of monomers and dimers. 相似文献
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17.
The surface pressure vs. mokcular surface area relations for dipalmitoyl phosphatidylcholine (DPPC) insoluble monolayer and sodium deoxycholate (SDC) adsorbed monolayer,L and D1, respectively, were obtained from the analyses of surface tensions measured by the Wilhelmy glass plate. Also, D1 was obtained by a drop-weight method. Next, the surface pressure time course,(t), of the SDC aq. was measured by the Wilhelmy plate before and after DPPC was spread on the liquid surface. At DPPC spreading,(t) jumped to a maximum,, and decreased along an exponential curve. The values of with various surface amounts of DPPC and bulk concentrations of SDC were analyzed using a dual surface-region model. The model enabled the estimation of. For better fitting, modified relations were constructed in place of D1. The exponential decrease of(t) was also observed on the SDC adsorbed monolayer which was rapidly compressed by a moving barrier. The(t) relaxation rate constants of the SDC monolayers which were compressed by DPPC spreading and the moving barrier agreed with each other, suggesting a desorption of SDC from the surface. 相似文献
18.
In situ polarized Fourier transform IR external reflection spectra of Langmuir monolayers of zinc stearate and zinc 12-hydroxystearate
on a water surface were recorded for various surface areas, and their molecular structures were estimated. In the zinc stearate
monolayer, the wavenumbers and the absorbances of the antisymmetric and symmetric methylene stretching bands did not change
during monolayer compression, which means that orientational and conformational changes of the hydrocarbon chain did not occur.
However, wavenumber changes of the antisymmetric and symmetric carboxylate stretching bands were observed during surface compression.
The change in the binding nature of the zinc cation to the carboxylate group was speculated. Moreover, it was elucidated that
the structure of the hydrocarbon chain in the zinc 12-hydroxystearate monolayer was different from that in the zinc stearate
monolayer.
Received: 21 March 2001 Accepted: 6 July 2001 相似文献
19.
自组装合成纳米复合TiO2-ZnO介孔材料及其光催化性能 总被引:8,自引:0,他引:8
以TiCl4, ZnSO4•7H2O为原料, 尿素为沉淀剂, 利用可溶性淀粉大分子链的空间位阻效应和高分子网络的阻隔作用, 以纳米级碳黑为模板, 采用微波加热、均相沉淀法合成出了一系列纳米TiO2-ZnO复合介孔材料. XRD分析证明反应前驱体为非晶态, 500 ℃以上转变为锐钛矿结构的TiO2和ZnTiO3, 当Ti∶Zn=1(摩尔比)时, 产物全部为ZnTiO3 (TiO2•ZnO). TEM形貌观察结合N2吸附表明, 基本粒子为球形, 粒径15~20 nm. 最可几孔径8~10 nm. EDS分析证明产品中Ti∶Zn的分析测定值与实际的投料值基本一致, 并且掺杂均匀性好. 光吸收及光催化实验发现Zn含量为50%时, 光催化效果最好, 在日光照射90 min后, 此TiO2-ZnO复合材料对藏蓝染料溶液降解率可达到100%, 其光催化反应符合一级动力学方程. 相似文献
20.
XRD,DTA,比表面测定等结果表明,制备方法对MoO3/ZrO2结构有决定性影响.仲钼酸铵浸渍仅经干燥的Zr(OH)4再经高温焙烧所得团体超强酸MoO3/ZrO2(Ⅰ)与浸渍晶态ZrO2所得部分氧化催化剂MoO3/ZrO2(Ⅱ)的载体形态有明显不同.(1)MoO3/ZrO2(Ⅰ)的比表面数倍于MoO3/ZrO2(Ⅱ);(2)MoO3含量增加时,MoO3/ZrO2(Ⅰ)的比表面逐步增大至一极大值再缓缓下降,而MoO3/ZrO2(Ⅱ)的比表面随MoO3含量增加而单调下降;(3)在MoO3/ZrO2(Ⅰ)中,ZrO2以介稳四方相存在,而在MoO3/ZrO2(Ⅱ)中则是稳定的单斜相.在此基础上研究了事先引入的活性组分在载体织构形成过程中的作用,包括延迟ZrO2晶化,阻碍晶粒长大及与之相关的相变等,并讨论了MoO3/ZrO2(Ⅰ)中MoO3最佳含量的科学含义. 相似文献