抗坏血酸与DNA相互作用的电化学研究

脱氧核糖酸(DNA)贮存着生物体生命活动的所有信息,这些信息指导着细胞生长、分化、代谢、遗传和变异等重要的生命活动。DNA结构与功能的改变可引起细胞生物学行为的显著改变。DNA与抗癌药物相互作用的研究的报道较多[1,2],而与维生素类药物研究报道相对较少[3]。抗坏血酸(AA)即     

The interaction of cobalt tetrasulfophthalocyanine and octasulfophenyltetrapyrazinoporphyrazine with ascorbic acid

A comparative study of the spectral properties and association of cobalt tetrasulfophthalocyanine and octasulfophenyltetrapyrazinoporphyrazine was performed. The data obtained were compared with the results of a kinetic study of the interaction of the complexes with a biologically important compound, ascorbic acid.     

葡萄糖、肌醇与抗坏血酸的相互作用研究

利用电化学、密度泛函理论和分子中的原子理论,从微观角度研究了葡萄糖、肌醇与抗坏血酸的相互作用。两种混合体系在水溶液及磷酸盐缓冲溶液中的电化学结果表明,抗坏血酸中烯二醇羟基上的氢原子可与葡萄糖/肌醇羟基上的氧原子形成氢键,使得抗坏血酸的电氧化反应难以发生。量子化学计算进一步证明了上述两种混合体系中氢键的存在。     

Electrochemical determination of ascorbic acid using the poly-cysteine film-modified electrode

A poly(L-cysteine) thin film was prepared onto electrode surface via electropolymerization. In pH 7.0 phosphate buffer, L-cysteine was oxidized during the cyclic potential sweep between −0.60 and 2.00 V, forming a thin film at the glassy carbon electrode (GCE) surface. The electrochemical behaviors of ascorbic acid at the bare GCE and the poly(L-cysteine) film-coated GCE were investigated. The oxidation peak potential of ascorbic acid shifts to more negative potential at the poly(L-cysteine) film-modified GCE. Moreover, the oxidation peak current significantly increases at the poly(L-cysteine) film-modified GCE. These phenomena indicate that poly(L-cysteine) film shows highly-efficient catalytic activity to the oxidation of ascorbic acid. Based on this, a sensitive and simple electrochemical method was proposed for the determination of ascorbic acid. The oxidation peak current of ascorbic acid is proportional to its concentration over the range from 1.0 × 10⁻⁶ to 5.0 × 10⁻⁴ mol l⁻¹. The limit of detection is evaluated to be 4.0 × 10⁻⁷ mol l⁻¹.     

抗坏血酸在离子液体修饰玻碳电极上的电化学行为

利用离子液体1-丁基-3-甲基咪唑四氟硼酸盐(BMIMBF4)对玻碳电极(GCE)进行修饰,制备了BMI-MBF4/GCE电极.在0.1mol/L的磷酸盐缓冲溶液中,采用循环伏安法研究了抗坏血酸在BMIMBF4/GCE电极和裸玻碳电极(GCE)上的电化学行为.结果表明,pH=5.7的磷酸盐缓冲溶液为最佳测定底液,最佳富集时间为120s;BMIMBF4/GCE对抗坏血酸的氧化反应有很好的电化学催化作用.抗坏血酸的氧化峰电流与其浓度在2.0×10-4～1.0×10-2 mol/L的范围内呈良好的线性关系,相对标准偏差为4.53%(n=5).     

Studies on interaction of ferrofluid with ascorbic acid in aqueous acidic medium

The solution chemistry of the interaction of ferrofluid with ascorbic acid in dilute solutions has been investigated in the temperature range of 15–45°C. Kinetic, mechanistic and thermodynamic aspects of the reactions were studied by spectrophotometric and potentiometric techniques.     

Electrochemical synthesis of self-doped polyaniline and its use to the electrooxidation of ascorbic acid

Self-doped polyaniline (PAN) film on platinum electrode surface has been synthesized via electrochemical copolymerization of aniline with orthanilic acid (OAA). Fourier transform infrared, UV–Vis, and elemental analysis indicate the formation of the copolymer and that the copolymer has the structure of a head-to-tail coupling of aniline and OAA units. It was found that the internal doping of PAN with OAA can extend the electroactivity of PAN in neutral and even in alkaline media. The obtained self-doped PAN (PAN-OAA)-coated platinum electrode is shown to be a good surface for the electrooxidation of ascorbic acid (AA) in phosphate buffer solution of pH 7. The anode peak potential of AA shifts from 0.63 V at bare platinum electrode to 0.34 V at the PAN-OAA-modified platinum electrode with greatly enhanced current response. A linear calibration graph is obtained over the AA concentration range of 5–60 mM using cyclic voltammetry. Rotating disk electrode voltammetry and chronoamperometry have been employed to investigate the electrooxidation of AA. The PAN-OAA-modified platinum electrode shows good stability and reproducibility.     

Hydrophilic interaction liquid chromatography method for the determination of ascorbic acid

Hydrophilic interaction liquid chromatography (HILIC) method using internal standard for the determination and stability study of ascorbic acid was developed. HILIC method was very fast and simple using the following analytical conditions: ZIC HILIC (150 x 2.1 mm, 3.5 microm) chromatographic column and mobile phase composed of ACN and 50 mM ammonium acetate buffer pH 6.8 (78:22 v/v). Diode array detection was performed and chromatograms were processed at 268 nm, the maximum wavelength of absorbance of ascorbic acid. An extensive stability study of ascorbic acid as a function of various factors including temperature, stabilizing agents, oxygen presence and its concentration in solution was performed in order to gain information about the quantitative influence of individual stability factors. Low temperature and stabilizing agents (o-phosphoric acid and oxalic acid) were found to be key factors enabling substantial enhancement of the stability of ascorbic acid.     

抗坏血酸在石墨烯微片修饰玻碳电极上的电化学行为及其测定

基于石墨烯微片修饰玻碳电极对抗坏血酸的电催化作用,建立了测定抗坏血酸的电化学分析方法。石墨烯微片修饰玻碳电极与裸玻碳电极相比,显著提高了抗坏血酸的氧化峰电流,降低了氧化峰电位,提高了测定的灵敏度。该电极测定抗坏血酸的线性范围为5.0×10-5～2.5×10-2mol/L,最低检测限为6.5×10-7mol/L(信噪比=3)。     

Electrochemical studies on the interaction of l-cysteine with metallic copper in sulfuric acid

Amino acids have been widely used as green corrosion inhibitors for an array of metals. Considering its importance in corrosion chemistry, studies were undertaken with the objective to discovering the inhibitory effect of a sulfur-containing amino acid, l-cysteine, on copper in different concentrations of sulfuric acid (0.5, 1.0, and 1.5 M) at different temperatures. Techniques like the weight loss method, electrochemical impedance spectroscopy, potentiodynamic polarization (Tafel), and adsorption studies were employed. Results revealed that l-cysteine do offer an attractive inhibition efficiency. However, with an increase in the concentration of the inhibitor, corrosion rates decreased irrespective of the temperature gradients. This is due to surface adsorption of the inhibitor molecules on the metal which has contributed to a decreased double-layer capacitance and increased polarization resistance. With the increase in the concentration of the medium, the corrosion rate was also enhanced and this is due the liberation of a high quantum of H⁺ ions. Based on the results of Tafel polarization studies, it is evident that the amino acid, l-cysteine, could act as a mixed type inhibitor. The importance of l-cysteine in the corrosion of copper metal has been highlighted in this paper.     

Catalytic determination of vanadium with the bromate/iodide/ascorbic acid landolt reaction and conductometric monitoring

Vanadium (0–1 mg l^?1) is determined in solutions by a catalytic procedure with conductometric detection. Reaction times of the bromate/iodide/ascorbic acid Landolt reaction are evaluated from conductance vs. time traces, obtained with an instrument with compensation facilities. Results are evaluated by means of calibration graphs, where the t(0)/t(c) ratios are plotted against the concentration of vanadium. Kinetics and mechanism of the reactions are discussed and values for the rate coefficients as well as entropies and enthalpies of activation are presented.     

Potentiometric and multinuclear NMR studies on the interaction of aluminum with ascorbic acid in acidic aqueous solution

The complex-formation equilibria between aluminum(III) ion and L-(+)-ascorbic acid (AA) in 0.1 M KCl ionic medium at 25 degrees C and 0.15 M NaCl ionic medium at 37 degrees C were studied by glass electrode pH-metric measurements. The obtained experimental results were explained by the formation of the following complexation species: a weak mononuclear 1:1 species AlL(2+) together with two trinuclear mixed-hydroxo species Al(3)H(-5)L(4) and Al(3)H(-5)L(3+) in acidic aqueous solutions. Meanwhile, the formation of the complexes and structures of Al with AA were proved by multinuclear (1H, 13C, 27Al) NMR spectra in the pH range 2.0-5.0. It is supposed that Al directly coordinates with AA at O-3 moiety; also, Al can coordinate with the O-1 and O-2 moieties of ascorbate ion through the weakly binding and the intramolecular hydrogen bonding in acidic aqueous solutions.     

Electrochemical flow-through detector for the determination of cystine and related compounds

An electrochemical double cell for the detection of cystine in aqueous liquid streams is described. A column electrode of amalgamated silver powder is used to reduce cystine quantitatively to cysteine, which is detected amperometrically at a mercury electrode. The double cell is applied to the detection of cystine, cysteine and penicillamine in high-pressure liquid chromatography and to the selective determination of cystine and cysteine by flow-injection analysis.     

抗坏血酸在聚阿魏酸修饰玻碳电极上的电化学行为研究

研究了抗坏血酸(AA)在聚阿魏酸修饰电极上的电化学性质。在AA存在的条件下,电极过程由扩散控制,测得扩散系数为8.18×10-8cm2/s。AA浓度在0.01~5.0 mmol/L范围内与峰电流呈现良好的线性关系。通过计时安培法测得催化速率常数为8.6×103mol-1.L.s-1。     

Electrochemical and ultraviolet-visible spectroscopic studies on the interaction of deoxyribonucleic acid with vitamin B6

Studies on the interaction of DNA with vitamin B(6) were carried out with a DNA-modified electrode by electrochemistry and Ultraviolet-visible spectroscopy. The results showed that there exists the supra-molecule interaction between base groups on DNA and vitamin B(6) by forming hydrogen binding, the binding equilibrium constant of the interaction is equal to 115.3 M(-1), the binding ratio of nucleotide to vitamin B(6) is 5:1. Based on the electrochemical and Ultraviolet-visible spectrum studies the interaction mode of DNA with vitamin B(6) was explored.     

尿酸和抗坏血酸在CPB现场修饰碳糊电极上的电化学行为

研究了尿酸(UA)和抗坏血酸(AA)在裸碳糊电极(CPE)和溴化十六烷基吡啶CPB)现场修饰碳糊电极(CPB/CPE)上的电化学行为,研究结果表明在PBS(pH=6.8)缓冲溶液中,UA和AA在CPE和CPB/CPE电极上的氧化均为一不可逆过程,在CPB/CPE上UA和AA的氧化峰电位负移,氧化峰电流增大,CPB/CPE对UA和AA的电化学氧化产生了促进作用。用电化学方法测得了UA和AA在CPE和CPB/CPE上的动力学参数如电荷转移系数α,扩散系数D,反应级数和反应速率常数k1。     

Determination of ascorbic acid with ferricyanide

Ascorbic acid can be determined by titration with potassium ferricyanide in sulphuric, phosphoric or hydrochloric acid media. Twelve indicators, including ferroin and some triphenylmethane and thiazine dyes, have been found suitable. The method has been successfully applied to assay of commercial products for vitamin C. Several organic substances likely to be associated with ascorbic acid in preparations and plant tissues do not interfere.     

Microtitration of ascorbic acid with copper

Summary A new titrimetric method for the microdetermination of ascorbic acid has been developed. It is based on the oxidation of ascorbic acid to dehydroascorbic acid with copper(II) in presence of ammonium thiocyanate; potassium iodide and starch are used as indicator. The method is especially suitable for dilute solutions (<0.05N) and can be used over the pH range 1–7. Glucose, fructose, aspirin, caffeine, rutin and calcium gluconate do not interfere, and neither do citrate, oxalate and tartrate if the titration is done at pH 1-2. Bisulphite can be masked with acetone, but novalgin must be absent. The method is simple, sensitive and accurate.

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Mikrotitration von Askorbinsäure mit Kupfer

Zusammenfassung Eine neue maßanalytische Methode zur Mikrobestimmung von Askorbinsäure wurde ausgearbeitet. Sie beruht auf deren Oxydation zu Dehydroaskorbinsäure mit Kupfer(II) in Gegenwart von Ammoniumrhodanid; Kaliumjodid und Stärke dienen als Indikator. Das Verfahren eignet sich besonders für verdünnte Lösungen (<0,05N) und ist im pH-Gebiet 1-7 anwendbar. Glukose, Fructose, Aspirin, Coffein, Rutin und Calciumglukonat stören nicht, ebenso wenig Zitrat, Oxalat und Tartrat, soferne bei pH 1-2 titriert wird. Bisulfit kann mit Aceton maskiert werden, aber Novalgin darf nicht anwesend sein. Das Verfahren ist einfach, empfindlich und genau.

     

电化学活化碳纤维微电极和脑神经递质及抗坏血酸在体测定

本文采用一种简单电化学方法,即恒电流法处理自制碳纤维电极,在脑神经递质测定中显示了很高的灵敏度和分辨能力.活化后的电极对多巴胺的检测限达5×10^-8mol.dm^-3,对多巴胺和抗坏血酸的伏安峰分离达170mV.作者使用该电极,采用半微分伏安法测定了活体大鼠脑内抗坏血酸,3,4-二羟苯乙酸和5-羟吲哚乙酸的浓度分别为1.7×10^-4,2.1×10^-5和 3.3×10^-6mol·dm^-3.本文对电极的制作,活化条件,伏安峰判别,在体药物实验和电极活化机理等进行了研究和探讨.     

Determination of ascorbic acid with o-iodosobenzoate: analysis of mixtures of ascorbic acid with methionine and cysteine or glutathione

Ascorbic acid has been determined in pure solutions, pharmaceutical preparations, food-stuffs and biological fluids by titration with o-iodosobenzoate, with visual or photometric detection of the end-point, with leuco-2,6-dichlorophenolindophenol plus potassium iodide as indicator. Cysteine and glutathione, which interfere quantitatively, are masked by cyanoethylation; the cyanoethylated product and methionine have been determined with o-iodosobenzoate in the presence of acidified potassium bromide, with Methyl Red as indicator. Procedures are given for the analysis of mixtures of ascorbic acid with sulphur-containing amino-acids.