硫代硫酸盐在铂电极上的电化学氧化行为

用循环伏安法测定了硫代硫酸盐在铂电极上的电化学氧化行为, 结果表明, 其电化学氧化行为与体系的pH和扫描速度密切相关. 当pH为5~6时, 硫代硫酸盐的循环伏安曲线出现三个氧化峰, 峰电位分别在0.05 V、0.58 V和1.02 V附近, 随pH值升高和扫描速度的降低, 0.05 V附近的氧化峰逐渐变得明显, 同时各氧化峰的峰电位与扫描速度的对数, 峰电流与扫描速度的平方根均成很好的线性关系；当pH为8~9时, 硫代硫酸盐的循环伏安曲线出现三个明显的氧化峰, 峰电位分别在0.05 V、0.91 V和1.22 V附近. 随扫描速度降低, 循环伏安曲线出现交叉, 体系呈现明显的电化学振荡行为；但当pH=10时, 1.22 V附近的氧化峰消失. 硫代硫酸盐的电化学氧化行为非常复杂, 电化学氧化机制随体系pH的变化而变化.     

Peaks in capillary zone electrophoresis: fact or fiction

Non-steady-state electrophoretic processes can be estimated by a repeated application of a steady-state model based on the electroneutrality equation, the modified version of Ohm's law, and the mass balances of the co- and counterions. With such a mathematical model, all parameters in sample zones in capillary zone electrophoresis (CZE) can be calculated. The relationships between the calculated parameters for sample zones in CZE, such as the pH, concentrations of co- and counterions, and the ratio E1m1/E2m2 versus the mobilities of both anionic and cationic analytes can be visualized in a SystChart, a set of eight panels, for a given background electrolyte (BGE). All properties of a zone, such as the fronting/tailing character and the question of peaks/dips can be read from such a SystChart. Applying n coions, n-1 discontinuities are present in such a SystChart, indicating the presence of system peaks applying that BGE. For BGEs with one coion, no system peaks (discontinuities) exist at moderate pH values. SystCharts calculated for BGEs with a low pH do show discontinuities, however, which indicates that system peaks are present in electropherograms applying BGEs at low pH. Experimentally, it is shown that system peaks are indeed present in electropherograms applying BGEs with one coion at low pH and the mobilities of the system peaks generally increase with decreasing pH. Hydrogen ions seem to act as a second coionic species. Of course, these system peaks are only visible in the UV signal if the BGE has UV-absorbing properties.     

Electrochemical behaviour of rosmanol 9-ethyl ether,a diterpene lactone antioxidant isolated from sage

The electrochemical behaviour and mechanism of the redox process of the natural antioxidant rosmanol 9-ethyl ether, isolated fromSaliva officinalis L., were studied. The cyclic voltammograms of rosmanol 9-ethyl ether (R9EE), at characteristic pH values, and the electrochemical parameters for all investigated pH values were measured. Three characteristic pH regions, each with different behaviour of R9EE, were identified. In regions of pH < 4 and pH > 5 only one anodic peak appeared, whereas in the solutions of pH 4–5 two anodic peaks could be noted. The overall oxidation mechanism at pH < 4 is an e.H.e.H. oxidation mechanism, which as a final product gives a quinonic molecule. The influence of pH on the second oxidation peak potential tends towards zero in accordance with the preceding dissociation of the one of phenolic groups, thus suggesting an e.e.H. mechanism at pH > 5. This means that at the pH values expected in plant cells, R9EE has an unexpected structure, making this substance a potent antioxidant. Electrochemical and spectrophotometric measurements enabled us to establish an extremely low pK _a value (4.35) for R9EE.     

17O NMR and computational study of a tetrasiliconiobate ion, [H(2+x)Si4Nb16O56](14-x)-

Rates of oxygen-isotope exchange were measured in the tetrasiliconiobate ion [H(2+x)Si(4)Nb(16)O(56)]((14-x)-) to better understand how large oxide ions interact with water. The molecule has 19 nonequivalent oxygen sites and is sufficiently complex to evaluate hypotheses derived from our previous work on smaller clusters. We want to examine the extent to which individual oxygen atoms react independently with particular attention given to the order of protonation of the various oxygen sites as the pH decreases from 13 to 6. As in our previous work, we find that the set of oxygen sites reacts at rates that vary over approximately 10(4) across the molecule at 6相似文献   

Bestimmung von Chinin in Tonic-Wässern und Limonaden mit Differential-Pulspolarographie

Zusammenfassung Eine Methode zur direkten Bestimmung von Chinin in Tonic-Wässern und Limonaden wurde ausgearbeitet. Hierzu wurde die Differential-Pulspolarographie verwendet. Chinin gibt bei dieser Methode — je nach pH-Wert-ein oder zwei Peaks. Die Höhe dieser Peaks hängt bei vorgegebenem pH von der Konzentration ab. Auch das Potential im Peakmaximum ist eine Funktion des pH. Eine maximale Detektion erhält man zwischen pH 6,5 und 9. Aus den gewonnenen Daten war auch ein Einblick in die Elektrodenreaktionen möglich.

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Determination of quinine in tonic-waters and lemonades by means of differential-pulse polarography

Summary A method for the determination of quinine in tonic-waters and lemonades was developed; an isolation of quinine is not necessary. Differential-Pulse Polarography was employed. When using this method quinine shows one or two peaks according to the pH. The height of these peaks at the selected pH depends on the concentration. The potential in the maximum of the peak is a function of the pH. The best detection is attained between pH 6,5 and 9. By means of the experimental results the electrode processes were elucidated.

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Herrn Univ.-Prof. Dr. Hans Lieb in Dankbarkeit und Verehrung zum 90. Geburtstag gewidmet.     

Development of a perfusion ion-exchange chromatography method for the separation of soybean proteins and its application to cultivar characterization

A perfusion ion-exchange chromatography method has been designed, for the first time, for the separation of soybean proteins and its application to the characterization of soybean cultivars. For that purpose, the gradient, the mobile phase composition (buffer concentration, buffer pH, and elution salt), and the temperature were optimized. The method consisted of a two-step gradient (0% B for 2 min and from 0 to 50% B in 10 min) being mobile phase A a 2 0mM borate buffer (pH 9) and mobile phase B a 20 mM borate buffer (pH 9) containing 1M sodium chloride. The procedure used for the preparation of sample solutions was significantly simpler than that proposed by other authors and basically consisted of dissolving in water. This method enabled the separation of soybean proteins from a soybean protein isolate in 11 peaks in about 9 min. The method was used to separate soybean proteins in different commercial soybeans. In general, the 11 peaks yielded by the soybean protein isolate were also observed in the chromatograms of all soybeans. However, the area percentages of every peak in every soybean enabled the differentiation between soybeans. Moreover, the method was also used to separate soybean proteins in the proteic fractions obtained from every soybean. Multivariate methods were used for patterns recognition and the classification of samples.     

Identification and simultaneous determination of Azorubin, Allura red and Ponceau 4R by differential pulse polarography: application to soft drinks

Azorubin (E 122), Ponceau 4R (E 124) and Allura red (E 129), are the most used red dyes in soft drinks manufacturing, and in some cases two dyes are present. The aim of this work is to show that using differential pulse polarography, it was possible to distinguish these synthetic dyes from the natural dyes providing from fruits. In addition, in an appropriate supporting electrolyte, identification and quantitative analysis of these three red dyes were possible, even when they were mixed. Various electrolytes were tested such as potassium chloride, which is a classical supporting electrolyte, citric acid which is one of the components of the soft beverages, sodium citrate and a phosphate buffer. It was shown that the peak intensities and potentials, and consequently their resolution, depend greatly on the pH values. In potassium chloride and sodium citrate the peaks of Azorubin, Allura red and Ponceau 4R were well separated and dyes were identified without ambiguity. Buffer solutions with pH close to 8 and 9 appeared to be appropriate, as the potentials and the intensities of the peaks were slightly changed when small amounts of soft drinks, usually at pH close to 3, were introduced in the cell. A procedure using the standard addition technique was developed, tested with model syrups and then applied to commercial syrups, soda and non-alcoholic bitters.     

Azo compounds as reagents for the voltammetric determination of molybdenum(VI)

Linear sweep voltammograms of Lumogallion IREA (pH 2), Magneson IREA (pH 2), 4-(2-pyridylazo)resorcinol (pH 4.8), and 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (pH 4.8) in the presence of molybdenum(VI) exhibit peaks at potentials more negative than the potentials of reduction peaks of the reagents by approximately 0.1 V. In all of the above cases, the heights of these peaks linearly increased with an increase in the concentration of molybdenum(VI) in the range from 5 x 10^-7 to 2.5 x 10^-6 M; thus, these peaks can be used for the determination of molybdenum. The simultaneous proportional decrease in the heights of the cathodic peaks of the reagents can be used for indirect determination of molybdenum(VI). The limits of detection without preliminary accumulation at a dropping mercury electrode with a drop time of 5 s are (1.5-3.9) x 10^-7 M, depending on the nature of the reagent and the technique used for determining the concentration.     

Success and failure with phthalate buffers in capillary zone electrophoresis

Phthalate buffers are currently used in capillary electrophoresis as robust electrolyte systems for indirect detection. This contribution demonstrates that these buffers show regularly not only successful regions of mobilities of analytes (sample window) but also regions of failure where the migration of analytes is strongly deteriorated due to the presence of a system zone. System zones in phthalate buffers may be easily detected by UV detection and manifest themselves as peaks or dips. Peak shape diagrams are advantageously used for the prediction of the migration behavior of system zones in phthalate background electrolyte (BGE) systems at various pH. It is shown that the mobility of the system zone varies strongly with pH, is practically zero at pH values below 4 and above 7, and shows a maximum at pH 5. Thus, the system peak may coincide either with the peaks of various analytes or with the electroosmotic flow (EOF) peak. Experiments are given showing the effects of such coincidences as, e.g., zigzag detection patterns, double EOF peaks, and/or unusually broad peaks/dips. The message of this contribution is to show how to understand the electrophoretic properties of phthalate BGEs that, regardless of possible failure regions, may be successfully used in the analytical practice of capillary zone electrophoresis (CZE).     

Peak identification in capillary isoelectric focusing using the concept of relative peak position as determined by two isoelectric point markers

In CIEF analysis, sample peaks can be identified by their relative peak positions (RPP) that are determined using only two internal pI markers. The two internal pI marker peaks should bracket, as close as possible, the sample peaks. The RPP values of the sample peaks are then calculated using the pI values, peak positions of the two pI markers, and peak position of the sample. Use of this method can effectively compensate for pH gradient distortions that often occur as a result of salts. Also, as shown by the results of this paper, regardless of the linearity of the pH gradient established by the given carrier ampholytes, sample peaks can be identified within an SD of 0.1 pH unit in RPP (<2% RSD) as long as the sample is run using the same carrier ampholytes and maintaining salt concentrations in the range of 0-15 mM.     

Determination of selenium(IV) by differential pulse voltammetry of the 3,3′-diaminobenzidine piazselenol

The determination of selenium(IV) by voltammetry through the formation of a piazselenol with 3,3′-diaminobenzidine (DAB) is described. At pH 1.5 and with a large excess of DAB, the formation of piazselenol is quantitative. In a borate-buffered electrolyte at pH 9, the piazselenol gives reduction peaks at potentials of ?0.64 V and ?0.82 V vs. SCE. The influence of DAB concentration on the sensitivity of the method is discussed. The calibration graphs are linear over the range 0–200 μg l^?1 Se(IV) and the detection limit is 0.10 μg l^?1. Copper(II) and lead(II) are tolerated in 500-fold amounts; the method is applicable to the determination of selenium in NBS Oyster Tissue.     

Separation of homologues and isomers of linear alkylbenzenesulfonates by capillary electrophoresis with sodium dodecyl sulfate,carboxylic acids and bile salts

The ability of several anionic compounds, including carboxylic and dicarboxylic acids, sodium dodecyl sulfate (SDS), and sodium deoxycholate (SDC) and other bile salts, to separate the C(10)-C(13) homologues and the corresponding 20 positional isomers of linear alkylbenzenesulfonates (LAS) by capillary electrophoresis was studied. Up to 19 peaks and a shoulder were observed with a background electrolyte (BGE) containing 10 mM phosphate (pH 6.8), 30% acetonitrile and 40 mM SDS, and 18 peaks were obtained with a BGE containing 10 mM borate (pH 9), 40% ethanol and 40 mM palmitic acid (PA). Resolution increased with the alkyl chain length of the carboxylic acid. Dicarboxylic acids with a short alkyl chain, as azelaic acid, were useful to separate the homologues without distinguishing between the isomers. Up to 16 peaks and a shoulder were distinguished with SDC. Resolution decreased with the other bile salts. The 6-C(11)/5-C(11) isomer pair was better resolved with SDC than with SDS, and the 2-C(12) isomer was isolated using both PA and SDC, but not with SDS. Only the 7-C(13)/6-C(13) pair could not be resolved with any of the discriminating agents used.     

Influence of ring opening-closure equilibrium of oxanine, a novel damaged nucleobase, on migration behavior in capillary electrophoresis

Oxanine (Oxa) is a novel damaged nucleobase which is generated from guanine by HNO2 or NO. As a fundamental study for detection of Oxa formed in vivo, capillary zone electrophoresis (CZE) and micellar electrokinetic chromatography (MEKC) have been tested by changing the pH of the running buffer. At pH 7, CZE did not separate Oxa from seven other nucleobases, and MEKC separated Oxa but their peaks migrated close together. In both the techniques, an extreme peak broadening occurred for Oxa around pH 9 and a good peak separation was achieved at pH 12. The behavior of the Oxa peak is discussed in relation to the unique multistep acid-base equilibria of Oxa.     

镍钴磷包覆的碳纳米管与成分关联的磁性能

用化学镀方法在碳纳米管表面沉积了具有不同镍／钴成分配比的镍钴磷合金层．讨论了Co^2＋与Ni^2＋的浓度比、镀液温度、pH值对沉积速率的影响．并利用场发射扫描电镜、透射电镜、X射线衍射仪、能谱仪和磁性测疑仪对镍钴磷包覆碳纳米管进行了系统的结构和性能表征．结果表明：当镀液中Co^2＋与Ni^2＋的浓度比为1,pH值为9时沉积速率最大;镀液温度的升高会使沉积速率增大．磁性测试结果显示碳纳米管表面镀覆Ni—Co—P镀层后,其磁性能对镀层中的Ni、Co相对含量有强烈的依赖性．当Co^2＋：Ni^2＋=2：1时,饱和磁化强度最大．矫顽力分别在Co^2＋：Ni^2＋=1：2和Co^2＋：Ni^＋2＋=4：1时有2个峰值;而磁导率分别在Co^2＋：Ni^2＋=1：4和Co^2＋：Ni^2＋=4：1时有2个峰值．     

溴甲酚紫的极谱研究

溴甲酚紫是一应用广泛的有机式剂^[1-4]。关于羟基三苯甲烷类染料的极谱研究报导不多^[5]。Ghoneim^[6]曾报导溴甲酚紫在pH<7时产生一个2电子还原波,当pH大于10时,可产生两个1电子还原波。Goel^[7]只研究了第一波的还原机理。本文用普通极谱、脉冲极谱、循环伏安等方法较详细地研究了溴甲酚紫的电还原。提出一电还原机理,解释了半波电位随pH变化的特殊规律。     

吡啶、2-甲基吡啶存在下细胞色素c碱式异构化和配体细胞色素c配合物的电化学研究

用半胱氨酸修饰的金电极研究了吡啶、2 甲基吡啶存在下细胞色素c碱式异构化和配体结合细胞色素c的电化学。在此电极上 ,细胞色素c可发生准可逆的电极反应而吡啶结合细胞色素c和 2 甲基吡啶结合细胞色素c在循环伏安图上只给出还原峰。高浓度 (1.2 7mol·L- 1)的吡啶和 2 甲基吡啶可诱导碱式细胞色素c在中性条件下生成。进一步的研究表明 ,这种诱导作用与配体和细胞色素c的键合无关     

Linear sweep voltammetry of 9-β- -ribofuranosyluric acid 5′-monophosphate in aqueous and micellar media

Linear sweep voltammetric behaviour of 9-β- -ribofuranosyluric acid 5′-monophosphate (UA-9R-5′-P) has been studied in phosphate buffers of pH 3.0 and 7.0 at the pyrolytic graphite electrode in aqueous and micellar media. At pH 3.0 in the presence of non-ionic and anionic surfactants, UA-9R-5′-P exhibited a single well-defined 2e, 2H⁺ oxidation peak, whereas in the presence of cationic surfactant (CTAB) the oxidation peak I_a showed a tendency to split into two peaks indicating that the 2e, 2H⁺ oxidation of UA-9R-5′-P in peak I_a reaction occurs in two 1e steps. The effect of cationic surfactant at pH 3.0 is explained on the basis of hydrophobic penetration of cationic species in cationic micelles. The products of electrode reaction in micellar medium were found as alloxan, urea and ribosyl phosphate at pH 3.0 and ribose, allantoin and 5-hydroxyhydantoin 5-carboxamide at pH 7.0 and were similar to those observed in aqueous media.     

The influence of pH and complex formation on the ASV peaks of Pb, Cu and Cd

The effects of pH, electrolyte composition and complex formation on the size and position of the ASV peaks of Pb, Cu and Cd have been systematically evaluated, with an instrument equipped with a mercury thin-film electrode and by applying a linear ramp voltage scan. The peak heights change with pH and the magnitude of the pH effect varies with base electrolyte composition. Anions such as chloride and acetate reduce the signal, as does the presence of excess of ligands such as 2,2'-bipyridyl, NTA and EDTA. Formation of stable chelates (e.g., with EDTA) can lead to total loss of signal, but dissociation of labile complexes can be enhanced by reducing the pH and/or increasing the magnitude of the applied deposition potential, thus producing measurable peaks. The peak potentials vary with pH, and in copper systems there are additional shifts in the presence of citrate, 2,2'-bipyridyl and chloride. With the last two, double peaks are formed and these are attributed to the formation of both Cu(I) and Cu(II) oxidation products. The varied response, particularly in the case of copper, which can follow changes in the base electrolyte composition, supports the need for careful control of the chemical environment in quantitative determination, and raises some queries about the feasibility of using direct ASV for speciation purposes.     

Peak distortion in the column liquid chromatographic determination of omeprazole dissolved in borax buffer.

Injection of a sample containing omeprazole dissolved in borax buffer (pH 9.2) into a reversed-phase liquid chromatographic system consisting of a mixture of acetonitrile and phosphate buffer (pH 7.6) as the mobile phase and a C18 surface-modified silica as the solid phase resulted under special conditions in split peaks of omeprazole. The degree of peak split and the retention time of omeprazole varied with the concentration of borax in the sample solution and the ionic strength of the mobile phase buffer as well as with the column used. Borax is eluted from the column in a broad zone starting from the void volume of the column. The retention is probably due to the presence of polyborate ions. The size of the zone varies with the concentration of borax in the sample injected. In the borax zone the pH is increased compared with the pH of the mobile phase, and when omeprazole (a weak acid) is co-eluting in the borax zone its retention is affected. In the front part and in the back part of the borax zone, pH gradients are formed, and these gradients can induce the peak splitting. When the dissolving medium is changed to a phosphate buffer or an ammonium buffer at pH 9 no peak distortion of omeprazole is observed.     

氯过氧化物酶在碳纳米管修饰电极上的直接电化学研究

将氯过氧化物酶固定到单壁碳纳米管修饰玻碳电极,其循环伏安曲线出现一对准可逆氧化还原峰,说明碳纳米管能够很好地促进氯过氧化物酶在电极表面的直接电子传递.该过程与溶液pH值有关,可指认氯过氧化物酶在电极表面发生的是一电子一质子传递反应.该修饰电极制作简单,性能稳定,且对氧还原具有很好的电催化效应.