Cathodic Adsorptive Stripping Voltammetric Determination of the Antitumor Drug Rutin in Pharmaceuticals, Human Urine, and Blood Serum

Cathodic adsorptive stripping voltammetry (CASV) was applied for the determination of rutin in pharmaceuticals, human urine, and blood serum. An electrochemical stripping procedure for trace measurements of rutin was developed based on the adsorption of the Cu²⁺-rutin complex on a hanging mercury drop electrode and applied to the quantification of the drug. Cyclic voltammetry was used to characterize the interfacial and redox behavior of the adsorbed Cu²⁺-rutin complex. Experimental and instrumental parameters for quantitative determination were optimized, and a detection limit of 4.9 × 10⁻⁹ mol · L⁻¹ in presence of Cu²⁺-ions for quantification of rutin under optimum conditions was derived. The sharp peak of the adsorbed Cu²⁺-rutin complex associated with an effective interfacial accumulation of this compound facilitates the determination of rutin in biological fluids with good recoveries. The degree of interference from potentially present metal ions and organic compounds on the CASV signal for Cu²⁺-rutin complex was evaluated.     

碘酸钾存在时极谱催化波法测定甘草酸

碘酸钾存在时极谱催化波法测定甘草酸过玮，赵明仁，宋俊峰，柳芸（西北大学电分析化学研究所，西安，７１００６９）关键词甘草酸，有机去极剂，极谱催化波，药物分析有机化合物尤其是生物活性物质作为有机去极剂在氧化剂存在时有无它们自身的极谱催化波，对电分析化学和...     

碘酸钾存在下萘丁美酮的极谱催化波法测定

本文报道了灵敏、快速测定萘丁美酮的新方法。在0.10 mol.L-1HAc-NaAc(pH 4.7)支持电解质中,萘丁美酮产生一极谱波,峰电位Ep=-1.12 V(vs.SCE)。加入KIO3后,该极谱波被催化,峰电流增加约30倍,峰电位基本不变,产生一灵敏的极谱催化波。其二阶导数峰峰电流ip″与萘丁美酮浓度在2.0×10-7~4.0×10-5mol.L-1范围内呈线性关系(r=0.9970,n=8),检出限为1.0×10-7mol.L-1。该方法可用于药物制剂中萘丁美酮含量的测定。     

过硫酸钾存在下吸附缔合/平行催化波法测定酮洛芬

应用线性扫描极谱法和循环伏安法,在0.10 mol/L NH4C l-NH3.H2O(pH 9.5)-0.01 mol/L K2S2O8底液中,对酮洛芬(KPF)的电化学行为进行了研究。在该底液中KPF于峰电位-1.37 V(vs.SCE)处产生1个灵敏的吸附缔合/平行催化波。该极谱催化波中S2O82-有双重作用:①S2O82-作为配位体与吸附在电极表面的质子化KPF形成缔合物,引起峰电位负移;②S2O82-及其还原中间产物SO4-作为氧化KPF羰基经单电子单质子还原的自由基,产生了极谱催化,使峰电流显著增加。该极谱催化波的二阶导数峰峰电流与KPF浓度在1.97×10-8~3.94×10-6mol/L范围内呈线性关系,检出限为6.57×10-9mol/L(3σ)。对3.94×10-7mol/LKPF溶液进行13次平行测定,RSD为1.24%。该催化波的分析灵敏度比相应还原波提高20倍。该方法已用于药剂中KPF的测定。     

KIO3存在下溶菌酶的极谱催化波研究与应用

研究了溶菌酶(Lysozyme,LE)在KIO₃存在下的极谱催化波.在0.1mol/LHAc-NaAc(pH4.7±0.1)缓冲液中,LE有1个由Cys6～Cys127间双硫键还原产生的可逆波.其峰电位为-0.51V(vs.Ag/AgCl).当KIO₃存在时,在原电位处产生了LE的极谱催化波.该催化波是由于KIO₃及其中间价态衍生质点(包括自由基IO^-·,IO_{2^{-·)氧化LE还原产物巯基成双硫键所致.这是蛋白质极谱催化波的一种新类型.在0.1mol/LHAc-NaAc(pH4.7±0.1)-1×10-3mol/LKIO3支持电解质中,LE催化波的灵敏度比其还原波的高两个数量级,峰电流与LE浓度在2×10-7～1.0×10-6mol/L范围内有线性关系.100倍半胱氨酸和胱氨酸不干扰1.0×10-6mol/LLE的测定.}}     

Polarographic Behavior of Gemfibrozil in the Presence of Dissolved Oxygen and Its Analytical Application

The polarographic behavior of gemfibrozil is investigated in 0.2 mol L^?1 KH₂PO₄‐Na₂HPO₄ (pH 5.8±0.1)‐8% ethanol supporting electrolyte in the absence and the presence of dissolved oxygen. The results demonstrate that the polarographic reduction peak at ca. ?1.17 V is a catalytic hydrogen wave after deaeration, and the enhanced reduction peak in the presence of dissolved oxygen is the so‐called parallel catalytic hydrogen wave. Based on the parallel catalytic hydrogen wave, a novel method has been developed for the determination of gemfibrozil by single sweep polarography. Calibration plot is linear in the range of 1.8×10^?7–2.4×10^?6 mol L^?1 and detection limit is 9.0×10^?8 mol L^?1. The proposed method is applied to the direct determination of the gemfibrozil in pharmaceutical preparations. The proposed method is simpler, faster and more sensitive than the known methods for gemfibrozil analyses.     

极谱催化波法测定土霉素

H2 O2 存在时 ,产生土霉素的极谱催化波 ,该催化波的灵敏度比相应土霉素的还原波高 8倍 ,据此拟定了测定土霉素的新方法。在 0 .1 0mol LKH2 PO4 Na2 HPO4(pH 7.4± 0 .2 ) - 1 .6× 1 0 -3 mol LH2 O2 底液中 ,催化波峰电流与土霉素浓度在 5 .0× 1 0 -7～ 9.0× 1 0 -6mol L范围内呈线性关系 (n =1 0 ,r=0 9996)。检出限为 1 .0× 1 0 -7mol L。     

过硫酸钾存在下人血清白蛋白的极谱平行催化氢波及其应用

报道 Ｋ２Ｓ２Ｏ８存在下人血清白蛋白（ＨＳＡ）的极谱平行催化氢波。在 ０．４ ｍｏｌ／Ｌ　ＮＨ３－ＮＨ４Ｃｌ（ｐＨ ８．５８）－０．０１ ｍｏｌ／Ｌ Ｋ２ｓ２Ｏ８支持电解质中，ＨＳＡ产生一个平行催化氢波，峰电位为－１．８５ Ｖ（ｖｓＡｇ／ＡｇＣｌ）。该平行催化氢波二阶导数峰电流与 ＨＳＡ浓度在 ２．６ × １０－９～９．６ × １０－９ｍｏｌ／Ｌ范围呈线性关系。用于人血清样和尿样中ＨＳＡ的测定，结果满意。     

Polarographic analysis of the reduction waves of Pt(II)-SATSC complex

A polarographic study of the Pt(II)-salicylaldehyde thiosemicarbazone complex in sodium perchlorate as supporting electrolyte is described. In addition to the reduction wave of the complex, a catalytic hydrogen wave is also recorded. The characteristics of this catalytic hydrogen wave are studied under different experimental conditions such as varying acid/complex/supporting electrolyte/surfactant concentrations and also with mercury droptime. Based on these, a probable mechanism for the electrode process has been postulated. Presented at the 12th Annual Symposium in Chemistry held at the Indian Institute of Technology, Madras in March 1987.     

平行催化氢波法测定双氯酚酸钾

双氯酚酸钾(d iclofenac potassium,DK),化学名称为[邻-(2,6-二氯苯胺)]苯乙酸钾(见图1),是图1双氯酚酸钾结构式F ig·1 Structural formu la ofd ic lofenac potassium一种有效的非甾体抗炎药物,具有显著的消炎、镇痛及解热作用,广泛地用于风湿性或类风湿性关节炎和其它关节疾     

双氧水存在下平行催化氢波法快速测定四丁基卤化铵

发现在氨性缓冲溶液中有H2 O2 存在时 ,四丁基卤化铵 (TBAH)的催化氢波能被H2 O2 进一步催化 ,产生较灵敏的平行催化氢波。拟定了直接测定TBAH的新方法。在 0 .2mol LNH3·H2 O NH4 Cl (pH 9.2± 0 .1) 6 .0× 10 - 3mol LH2 O2 底液中 ,TBAH平行催化氢波的二阶导数峰峰电流与其浓度在 8.0× 10 - 7～ 9.6× 10 - 6mol L范围内呈线性关系 (r =0 .9988,n =7) ;检出限为 4 .0× 10 - 7mol L。本方法简便快速 ,选择性良好 ,其灵敏度比TBAH单纯催化氢波法提高约 2 0倍 ,5 0倍四甲基卤化铵、10倍四乙基卤化铵不干扰测定。     

过氧化氢存在下平行催化氢波法测定奥沙普秦

在0.2mol/LKH2PO4-Na2HPO4(pH5.5±0.1)支持电解质中,奥沙普秦产生一催化氢波,峰电位Ep=-1.25V(vs.SCE)。当1×10-2mol/LH2O2存在时,该催化氢波的峰电流增加12倍,峰电位基本不变,产生一较灵敏的平行催化氢波。其二阶导数峰峰电流ip″与奥沙普秦浓度在1.0×10-7~2.6×10-5mol/L范围内呈线性关系(r=0.9995,n=10),检出限为5.0×10-8mol/L。该方法可用于药物制剂中奥沙普秦含量的测定。     

双氧水存在下钙-萘酚绿B体系的极谱波及分析应用

研究了在双氧水存在下钙-萘酚绿B体系的极谱波行为及其应用。在pH11.8的氢氧化钠溶液中,钙-萘酚绿B络合物于-0.67V可产生灵敏的极谱波,加入双氧水后极谱波移至-0.72V,且波高明显增大。导数波高与钙离子浓度在0.01-3.5mg/L范围内呈线性关系。研究了该波的性质及电极反应机理。证明为配位还原的络合吸附催化波。利用拟定的方法测定了水样、生物样品中的微量钙含量。     

槲皮素伏安行为及其稀土络合物极谱催化氢波研究

在乙醇量小于5％的水溶液中，于pH1.5至4.5，4.2至9.5分别得到槲皮素的两个还原波，均为羰基两电子还原．前者为其分子的强吸附波，后者为一价阴离子的波．在pH6.1附近的醋酸盐缓冲底液中，可获得槲皮素与Tb（Ⅲ）、Dy（Ⅲ）、Ho（Ⅲ）、Er（Ⅲ）、Tm（Ⅲ）、Yb（Ⅲ）、Lu（Ⅲ）和Y（Ⅲ）等重稀土离子络合物的双重表面催化氢波．络合物被诱导吸附，组成为（REL_2）L_吸．Sc（Ⅲ）与槲皮素形成单一表面催化氢波，其组成为（ScL）L_吸．     

Polarographic Determination of Bismuth Sensitization in the Presence of Nioxime

Abstract

Nioxime sensitizes the differential pulse polarographic determination of B1(III) in alkaline medium and in the presence of tart rate and citrate; detection limits of 8 and 12 ppb are obtained. Characterization of the electroactive process included an examination of the degree of reversibility and the effect on the peak current of pH, buffer composition, nioxime and bismuth concentrations and the presence of other metal ions.     

Polarographic Catalytic Wave of Prednisone in the Presence of Persulfate and its Application

 A polarographic catalytic wave of prednisone in the presence of K₂S₂O₈ was observed. The polarographic catalytic wave of prednisone as catalyst was attributed to such chemical reaction parallel to electrode reaction as oxidized the free radical from one electron reduction of the Δ^1,4-3 keto group of prednisone to regenerate the original keto group. The catalytic wave can be used for the determination of prednisone with the help of conventional polarographic equipment, such as linear-potential scan polarograph. In 0.12 mol l⁻¹ HAc-0.08 mol l⁻¹ NaAc-0.014 mol l⁻¹ K₂S₂O₈ (pH 4.6) supporting electrolyte, the second-order derivative peak current of the catalytic wave was rectilinear to prednisone concentration in the range of 3.2 × 10⁻⁷∼1.6 × 10⁻⁵ mol l⁻¹. The detection limit was 8.0 × 10⁻⁸ mol l⁻¹. Received August 6, 2001; accepted April 17, 2002; published online July 22, 2002     

薯蓣皂甙元的极谱催化波及其应用

采用线性扫描极谱技术,研究了薯蓣皂甙元(C27H42O3,简称皂素)的极谱催化波及应用。结果表明,在pH=5.3±0.5的BR缓冲溶液、0.1mol/LKCl和8×10-3mol/LH2O2的底液中,皂素产生极谱催化波,其一阶导数波的峰电位在-1.05V(vs.SCE)处,峰电流与皂素浓度在1.0×10-8～8.0×10-8mol/L范围内有良好的线性关系,线性回归方程:i′P=7.322×108c+3.919(μA/s),相关系数r=0.9984,检出限为1.0×10-8mol/L;该波为不可逆吸附、平行催化波。建立了测定皂素的新分析方法,并测定了黄姜中皂素的含量。     

Study and Application on Polarographic Catalytic Wave of Human Serum Albumin in the Presence of Kio3

ABSTRACT

A polarographic catalytic wave of human serum albumin (HSA) in the presence of KIO³ was reported. In 0.1 M NaAc～HAc buffer (pH4.7) solution, a reduction wave of HSA with peak potential ?0.60 V (vs., Ag/AgCl) resulted from the reduction of five disulfide linkages to sulfhydryl group. In the presence of KIO³, HSA yielded a polarographic catalytic wave at the original potential due to reduction and regeneration of these disulfide linkages. The catalytic wave can be used to determine trace of HSA. In the 0.1 M HAc～NaAc (pH4.7±0.2) ～1×10^?3 M KIO³ solution, the peak current was linearly proportional to HSA concentration in the range of 1.5×10^?7～7.5×10^?7 M. The catalytic wave improved two orders of magnitude in sensitivity compared with corresponding reduction wave.     

Anodic Polarographic Determination of Nilvadipine in Dosage Forms and Spiked Human Urine

 The anodic polarographic behaviour of nilvadipine was studied by using direct-current (DC), polarography and differential-pulse polarography (DPP). Nilvadipine, being a dihydropyridine derivative, exhibits well-defined anodic waves over the whole pH range of the Britton-Robinson buffers (BRb). In BRb of pH = 4, the diffusion-current constant was 6.45 ± 0.07 μA · mM⁻¹. The current-concentration plots are rectilinear over the ranges 1.6–12.8 and 0.2–12.8 μg/ml for DC polarography and DPP, respectively, with minimum detectability of 0.05 μg/ml (1.3 × 10⁻⁷ M) in case of the latter technique. The proposed method was successfully applied for determination of the drug in commercial capsules containing the drug, the percentage recoveries being in good agreement with the label claim. Furthermore, the method was applied for the determination of the drug in spiked human urine, the percentage recovery being 96.84 ± 2.83. Received January 25, 2001 Revision June 18, 2001