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1.
Microwave Activation of Processes in Mesopores: The Thiourea Electrooxidation at Mesoporous Platinum
《Electroanalysis》2006,18(8):793-800
In situ microwave activation is applied to the electrochemical oxidation of thiourea at low surface area (polished polycrystalline) and at high surface area (electrodeposited mesoporous platinum coated) platinum microelectrodes. The one electron oxidation of thiourea to formamidine disulfide is monitored as a function of the different activation parameters. In the absence of microwaves (ambient temperature, low mass transport) increasing the surface area (roughness) increases the thiourea oxidation response predominantly due to adsorption effects. In the presence of high microwave intensities, high mass transport and thermal effects further increase the oxidation current at mesoporous platinum. The most effective thickness of the mesoporous platinum film for the thiourea oxidation process is estimated as 3 μm independent of electrode diameter, temperature, or mass transport effects. 相似文献
2.
本文研究了鸟瞟呤(Gua)和次黄嘌呤(Hxa)铜络合物在悬汞电极(HMDE)上的吸附作用和电极反应机理,溶液中形成的1:1络合物有强烈吸附性,通过分子结构的比较,推断出Cu~(2+)与Gua和Hxa的咪唑环N(7)和外环氧O(6)原子结合形成封闭的五元环。嘌呤环的π-电子有使分子呈平面吸附的趋势,但是Gua络合物分子优先取“倾斜”定向;随着表面吸附浓度增加,Hxa络合物分子存在从“平面”向“垂直”的再定向作用。本文测定了单层吸附浓度、包含的电量和每个分子占据的面积。络合物吸附得到S形等温线,它与Frumkin吸附等温线接近。本文还列出有关吸附参数B、a、△G_A~O和θ~*的计算结果。 相似文献
3.
Electrochemical oxidation of thio/carbohydrazide and their hydrazone derivatives Benzaldehyde thiocarbohydrazone [BTCH] diacetylene
thiocarbohydrazone [DATCH] have been studied in Brit-ton Robinson buffer in aqueous and nonaqueous media at a glassy carbon
electrode. The effects of pH, sweep rate, concentration, temperature and surfactants have been studied. The complex bis (carbo/thiocabohydrazide) Zn(II) chloride was also subjected to voltammetric analysis in order to understand the reactivity
both in free and metal bound states. The reaction conditions were optimized for the determination of above compounds in micrograms
quantities by differential pulse voltammetry, analytical utility of this investigation is also highlighted. 相似文献
4.
《Electroanalysis》2005,17(11):997-1002
Binding reactions of toluidine blue (TB) with herring fish DNA in pH 6.0 Britton–Robinson (B–R) buffer solution have been investigated by cyclic voltammetry and linear‐sweep voltammetry at a glassy carbon electrode. TB has a couple of well‐defined redox peaks. The addition of DNA into the TB solution resulted in the decrease of the redox‐peak currents and the shift negatively of the anodic peak potential. The values of the electrochemical parameters such as the electron number of the electrochemical reaction, the electron transfer coefficient and the electrochemical reaction standard rate constant in the absence and presence of DNA, as well as the values of binding constant and binding ratio of DNA with TB were obtained. Almost unchanged values of the electrochemical parameters in the absence and presence of DNA show that nonelectroactive complexes were formed when TB interacted with DNA. DNA concentration can be determined by the decrease of the peak current of TB. The binding mode of TB with DNA was discussed. 相似文献
5.
提出了裸GCE不需任何处理测定甲氰咪胍的方法,浓度在3×10^-7-6×10^-5g/mL,范围内与峰电流呈线性关系,RSD为2.2%,回收率为96%-102%。该方法操作简便快速,大多数金属离子和多种有机生化物质不干扰测定,方法用于片剂和加标尿样中甲氰咪胍的测定与药典方法对照,获得满意结果,并对电极反应进行了初步探讨。 相似文献
6.
《Electroanalysis》2005,17(20):1886-1894
Lamivudine (LAM) is a synthetic nucleoside analogue with activity against human immunodeficiency virus‐type 1 (HIV‐1) and Hepatitis B virus (HBV). The aim of this study was to determine LAM levels in serum and pharmaceutical formulations, by means of electrochemical methods using hanging mercury drop electrode (HMDE). On this electrode, LAM undergoes irreversible reduction at the peak potential near Ep?1.26 V (vs. Ag/AgCl/3 M KCl). Reduction LAM signals were measured by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and square‐wave voltammetry (OSW). DPV and OSW techniques for the determination of LAM in acetate buffer at pH 4.5, which allows quantitation over the 4×10?6 to 1×10?4 M range in supporting electrolyte for both methods, were proposed. The linear response was obtained in acetate buffer in the ranges of 2×10?6 to 2×10?4 M for spiked serum samples at pH 4.5 for both techniques. The repeatability and reproducibility of the methods for all media were determined. The standard addition method was used in serum. Precision and accuracy were also checked in all media. No electroactive interferences from the endogenous substances were found in serum. With respect to side effects of high doses and short half‐life of LAM, a fast and simple detection method is described in this study. 相似文献
7.
The reduction of microcrystalline C60
fullerene, adhered at a carbon electrode and immersed in aqueous electrolyte, has been studied under various voltammetric conditions. This work reports mainly the voltammetric studies carried out principally in electrolyte containing potassium ions. Comparison of adherence techniques, such as solvent casting and mechanical transfer methods, are made to assess if the type of adhered techniques has any significant influence on the observed electrochemistry. The solvent casting method is found to produce three peaks in the potential for C600/n- redox couple as compared to a single and large peak produced when a mechanical transfer technique is employed. When the reduction potential of microcrystalline C60 in the presence of K+ is compared with other cations, such as Li, Na, Rb and Cs, it is observed that the shift of reduction potential follows the change in the hydration energy in the order Cs>Rb>K>Na>Li. In a mixed electrolyte study of CsCl/KCl, the reduction potential and peak shape of C600/n- redox couple during cyclic voltammetry is observed to change with concentration of the cations and the observed electrochemistry can be attributed to a cation-exchange mechanism. The reduction of C60 is irreversible in aqueous electrolyte containing alkaline cations as the re-oxidation process does not produce any observed electro-activity. Evidence of the formation of a passive coating of K n
C60 fulleride, which does not appear to undergo dissolution is obtained under cyclic voltametric conditions. This coating remains electrochemically active in the presence of tetrabutylammonium ions in acetonitrile. Scan rate, chronocoulometric, and scanning electron microscopic studies provide evidence of the presence of a surface process involving solid–solid transformation. 相似文献
8.
Petr Zuman 《Microchemical Journal》2002,72(3):241-250
Applications of chromatographic and atomic absorption methods are compared with those of electroanalytical techniques. The limitations of electroanalytical procedures and their advantages, such as speed, sensitivity and speciation are discussed. Among applications of polarography and voltammetry to a solution of basic problems, attention has been paid to the possibility to distinguish the degree of conjugation (e.g. of compounds containing the grouping CNNC), to a contribution to understanding of solution chemistry of mitomycin C and to processes involved in the reduction of cephalosporins. Among practical applications, the possibility to analyze suspensions, which can be carried out without separation offers advantages. Examples are interactions in suspensions of bile salts in the presence of metal (II) ions, adsorptions of various pesticides and other toxic materials on lignin and the possibility to follow alkaline cleavage of lignin in buffers pH 8-12 at 25 °C. Most of these studies would not be possible to carry out using other techniques. 相似文献
9.
Kazuharu Sugawara Tatsuya Shirotori Naoto Kamiya Shunitz Tanaka 《Analytica chimica acta》2004,523(1):75-80
Formation of avidin-biotin complex was investigated using bisbiotinyl thionine (BBT) by means of voltammetric techniques. Thionine is an electroactive compound and has two amino groups that are necessary for the reaction with a biotinylation reagent. The biotinylation of thionine produces a new reagent with two biotin moieties at each end of thionine. Three BBTs of different lengths of the spacer that connects the biotin moiety to the thionine moiety were prepared. The avidin-biotin binding assay was achieved by measuring the electrode response of the thionine moiety in BBT. The binding affinity and the conformation of complex, which depended on the length of spacer, are discussed. BBT in which the spacer is shortest (BBT-S, distance between carbonyl group of the two biotin moieties: 11 Å) binds with only one avidin molecule. BBT with medium length of spacer (BBT-M, 28.8 Å) forms the complex with two avidin molecules. BBT with the longest spacer (BBT-L, 46.6 Å) allows binding with two avidin molecules as well as intramolecular binding within one avidin molecule. The affinity constants of BBT-S, BBT-M and BBT-L for avidin were estimated to be 7.0 × 1012 M−1, 3.2 × 1012 M−1 and 4.0 × 1012 M−1, respectively. 相似文献
10.
Mikkelsen Ø Skogvold SM Schrøder KH Gjerde MI Aarhaug TA 《Analytical and bioanalytical chemistry》2003,377(2):322-326
Evaluation of different solid electrode systems for detection of zinc, lead, cobalt, and nickel in process water from metallurgical nickel industry with use of differential pulse stripping voltammetry has been performed. Zinc was detected by differential pulse anodic stripping voltammetry (DPASV) on a dental amalgam electrode as intermetallic Ni–Zn compound after dilution in ammonium buffer solution. The intermetallic compound was observed at –375 mV, and a linear response was found in the range 0.2–1.2 mg L–1 (r2=0.98) for 60 s deposition time. Simultaneous detection of nickel and cobalt in the low g L–1 range was successfully performed by use of adsorptive cathodic stripping voltammetry (AdCSV) of dimethylglyoxime complexes on a silver–bismuth alloy electrode, and a good correlation was found with corresponding AAS results (r2=0.999 for nickel and 0.965 for cobalt). Analyses of lead in the g L–1 range in nickel-plating solution were performed with good sensitivity and stability by DPASV, using a working electrode of silver together with a glassy carbon counter electrode in samples diluted 1:3 with distilled water and acidified with H2SO4 to pH 2. A new commercial automatic at-line system was tested, and the results were found to be in agreement with an older mercury drop system. The stability of the solid electrode systems was found to be from one to several days without any maintenance needed. 相似文献