Determination of trace amounts of morphine in human plasma by anodic adsorptive stripping differential pulse voltammetry

New adsorptive anodic differential pulse stripping voltammetry method for the direct determination of morphine at trace levels in human plasma of addicts is proposed.The procedure involves an adsorptive accumulation of morphine on a HMDE,followed by oxidation of adsorbed morphine by voltammetry scan using differential pulse modulation.The optimum conditions for the analysis of morphine are pH 10.5,Eacc of -100 mV（vs.Ag/AgCl）,and tacc of 120 s.The peak current is proportional to the concentration of morphine,and a Linear calibration graph is obtained at 0.01-3.10μg mL^-1.A relative standard deviation of 1.06%（n=5）was obtained,and the limit of detection was 3 ng mL^-1.The capabiLity of the method for the analysis of real samples was evaluated by the determination of morphine in spiked human plasma and addicts human plasma with satisfactory results.

Adsorptive stripping voltammetric methods for determination of aripiprazole

Anodic behavior of aripiprazole(ARP) was studied using electrochemical methods.Charge transfer,diffusion and surface coverage coefcients of adsorbed molecules and the number of electrons transferred in electrode mechanisms were calculated for quasi-reversible and adsorp-tion-controlled electrochemical oxidation of ARP at 1.15 V versus Ag/AgCl at pH 4.0 in Britton-Robinson buffer(BR) on glassy carbon electrode.Voltammetric methods for direct determination of ARP in pharmaceutical dosage forms and biological samples were developed.Linearity range is found as from 11.4 μM(5.11 mg/L) to 157 μM(70.41 mg/L) without stripping mode and it is found as from 0.221 μM(0.10 mg/L) to 13.6 μM(6.10 mg/L) with stripping mode.Limit of detection(LOD) was found to be 0.11 μM(0.05 mg/L) in stripping voltammetry.Methods were successfully applied to assay the drug in tablets,human serum and human urine with good recoveries between 95.0% and 104.6% with relative standard deviation less than 10%.

DETERMINATION OF HISTIDINE BY DIFFERENTIAL PULSE ADSORPTIVE STRIPPING VOLTAMMETRY OF ITS NICKEL(Ⅱ)COMPLEX

Abstract: Histidine was determined at the 5. 0 ×10-1.0×10-5mol/L level by differential pulse adsorptive cathodic etripping voltammetry at a hanging mercury drop electrode using the reduction peak of its nickel(Ⅱ) complex at -1. 16v(vs. Ag(AgCl) obtained in pH-10. 2 borate buffer solution. Other amino acid. do not interfere . This methed has been used for the direct determination of histidiue in serum.

ADSORPTIVE STRIPPING VOLTAMMETRY OF A FENTANYL DERIVATIVE DNPME AT Hg ELECTRODE

A quasi-reversible reduction peak of a fentanyl derivative DNPME is found by cyclic voltammetry at Hg electrode. E_(pc)=-1.58 V (vs. Ag/AgCl). The cathodic peak shows adsorptive characteristics. The adsorbed species is DNPME neutral molecule. The method for measuring trace amount of DNPME by adsorptive stripping voltammetry is established.

Adsorptive Stripping Voltammetry of Ultra Trace Lanthanum（Ⅲ） Using an Alizarin S as Complexing Agent and Carbon Paste as Working Electrode

Ultra trace determination of lantanum（Ⅲ） has been studied by adsorptive stripping voltammetry methods using an alizarin S as complexing agent and carbon paste electrode as working electrode. The electrode was made from mixed of carbon powder and paraffin in micropipette tip with diameter of 4 ram. This method consists of two steps. The first step is the formation and adsorptive accumulation of metal ion with chelator at the electrode surface. The second step is stripping the complex from the electrode surface into the solution. The stripping step generates current which is recorded as voltammogram. The optimum conditions of instrumental parameter obtained were accumulation potential of 600 mV, accumulation time of 120 seconds, and pH of solution of 5.5. In this research, the limit detection obtained was 2.3348 × 10^-12 M （3.24× 10^-11μg/L） with sensitivity of 16.52 （nA/10u M） and the precision of standard solution of La3＋ with concentration of 2 × 10^-12 M, 4× 10^-12 M, 6 × 10^-12 M, 8 × 10^-12 M, and 10 × 10^-12M were 3.50%, 9.88%, 7.19%, 7.48% and 1.85% respectively. The linierity of this method is very good with correlation coefficient is 0.9780. Recovery percentage from La3＋ with concentration of 6× 10^-12 M and 10 × 10^-12 M are 108.84% and 91.51%, respectively.

STUDY ON THE DETERMINATION OF METRONIDAZOLE IN HUMAN SERUM BY ADSORPTIVE STRIPPING VOLTAMMETRY

In Britton-Robinson buffer,metronidazole is preconcentreted on HHDE at 0.0 V(Vs.Ag- AgCI),An adsorptive stripping peak is observed at-0.62 V.Tho response is linear from 1x10^(-8)to 1×10^(-6)mol/L with 1.5 min accumulation.The method has been successfully applied to the deternation of metronidazole in human serum and formulations.

Determination of trace amount of antimony (Ⅲ) by adsorption voltammetry on carbon paste electrode

A sensitive method is described for the determination of trace antimony based on the antimony-bromopyrogallol red (BPR) adsorption at a carbon paste electrode (CPE). Three steps were involved in the overall analysis: preconcentration,reduction and stripping. Optimal conditions were found to be an electrode containing 25% paraffin oil and 75% high purity graphite powder as working electrode;a 0.10 mol/L HCl solution containing 40 μmol/L BPR as accumulation medium;a 0.20 mol/L HCl solution as reduction and stripping electrolyte;accumulation time,150 s;reduction potential and time,-0.50 V,60 s;scan range from -0.50 to 0.20 V. Interferences by other ions were studied as well. The detection limit was found to be 0.5 nmol/L for 150 s preconcentration. The linear range was from 1.0 nmol/L to 0.50 μmol/L. Application of the proposed method to the determination of antimony in water and human hair samples gave good results.

Trace Determination of Scandium Using Adsorption Voltammetry of Mix-Polynuclear Complex of Scandium-Calcium-Alizarin Red S at Carbon Paste Electrode

A novel method was described for the determination of ultra trace amount of scandium based on the cathodic adsorptive voltammetry of the mix-polynuclear complex of scandium-calcium-alizarin red S at a carbon paste electrode (CPE). The 2nd-order derivative linear scan voltammograms of the adsorbed complex were recorded by model JP-303 polarographic analyzer from 0.0 to -1.0 V (vs. SCE). The experimental conditions of the working procedure were optimized. The results show that the complex can be adsorbed on the surface of the CPE, yielding one peak at -0.61 V, corresponding to the reduction of the alizarin red S in the mix-polynuclear complex at the electrode. The detection limit of Sc^(3+) is 1.0×10^(-10) mol·L^(-1) for 3 min of accumulation time. The procedure was successfully applied to the determination of trace amount of scandium in the sample ores.

Direct Electrochemical Evidence of the Dissociation and Adsorption Behavior of Acetonitrile at Gold Electrodes by Ultrafast Voltammetry

Ultrafast cyclic voltammetry was used to study the redox behavior of a gold electrode in acetonitrile. The direct electrochemical evidence of the dissociation and adsorption behavior of acetonitrile at gold electrodes was found. It could be stated that two consecutive redox paths are involved, each with a special adsorption state acting as the reaction intermediate. The mean value, obtained of the electron-transfer rate constant of the second path, was 1.3 × 10^5 s^-1 with a standard deviation of 0.24 × 10^5 s^-1.

Study on the adsorptive catalytic voltammetry of aloe-emodin at a carbon paste electrode

A new catalytic voltammetric method for the determination of anthraqunone medi-cines at a carbon paste electrode (CPE) was described for the first time. The mechanism of the catalytic reaction was investigated by using linear sweep voltammetry, cyclic voltammetry, con-stant potential electrolysis and so on. The experiment results indicate that aloe-emodin was effi-ciently accumulated at a CPE by adsorption. In the following potential scan, aloe-emodin was reduced to homologous anthrahydroquinone compound, then the compound was immediately oxidized to aloe-emodin by the dissolved oxygen, and the aloe-emodin was again reduced at the CPE. As a result, a cyclic catalytic reaction was established. But a reversible redox reaction of aloe-emodin can only be observed at a mercury electrode, no catalytic reaction occurs there. A sensitive catalytic voltammetric peak of aloe-emodin was obtained at about ?0.60 V (vs. SCE) in 0.56 mol/L NH3-NH4Cl buffer (pH 8.9). The proposed method was applied to the determination of aloe-emodin in the Radix Rhei with satisfactory results. The determination results were in good agreement with reference values obtained by the HPLC. The adsorptive catalytic voltammetry for the determination of organic compound at CPE, chemically modified electrode and other solid electrodes could be significant in the studies on pharmacology, pharmacodynamics, toxicity of medicine, clinical medicine and biochemistry.

ADDITIVE SQUARE WAVE VOLTAMMETRY FOR COMPLEXING ADSORPTIVE CATALYTICAL SYSTEMS

The voltammetry for complexing adsorptive catalytical systems (CACS) has high sensitivity due to the coexistence of the adsorptive reducing current and the catalytical current. However, no study has been made on the case in which square wave voltammetry is used.

Catalytic Adsorptive Stripping Voltammetry at a Carbon Paste Electrode for the Determination of Amiodarone

Voltammetry using solid electrodes usually suffers from the contamination due to the deposition of the redox products of analytes on the electrode surface. The contamination has resulted in poor reproducibility and overelaborate operation procedures. The use of the chemical catalysis of oxidant on the reduction product of analyte not only can eliminate the contamination of analyte to solid electrodes but also can improve the faradaic response of analyte. This work introduced both the catalysis of oxidant K2S2O8 and the enhancement of surfactant Triton X-100 on the faraday response of amiodarone into an adsorptive stripping voltammetry at a carbon paste electrode for the determination of amiodarone. The method exhibits high sensitivity, good reproducibility and simple operation procedure. In 0.2 mol·L^-1 HOAc-NaOAc buffer （pH=5.3） containing 2.2×10^-2 mol·L^-1 K2S2O8 and 0.002% Triton X-100, the 2.5th-order derivative stripping peak current of the catalytic wave at 0.3 V （vs. Ag/AgCl） is rectilinear to amiodarone concentration in the range of 2.0×10^-10-2.3×10^-8 mol·L^-1 with a detection limit of 1.5×10^-10 mol·L^-1 after accumulation at 0 V for 30 s.

Trace determination of zirconium using anodic adsorptive voltammetry at a carbon paste electrode modified with multi-walled carbon nanotubes

A carbon paste electrode modified with multi-walled carbon nanotubes (MWCNT) was prepared and the determination of ultra trace amount of zirconium based on the anodic adsorptive voltammetry of the zirconium-calcium-alizarin red S mix-polynuclear complex is described in this paper for the first time. The results showed that the sensitivity and the selectivity of the method are excellent. The second de-rivative linear scan voltammograms of the complex were recorded by polarographic analyzer from 200 to 1200 mV (vs. SCE) and it was found that the complex can be adsorbed on the surface of the electrode, yielding a peak at about 840 mV, corresponding to the oxidation of ARS in the complex. The peak cur-rent increases linearly with Zr (IV) concentration in the range of 6.0×10-12―6.0×10-11 mol·L-1 (accumu-lation time 120 s), 6.0×10-11―2.0×10-9 mol·L-1 (accumulation time 90 s) and 2.0×10-9―1.0×10-7 mol·L-1 (accumulation time 60 s) and the detection limit (S/N = 3) is 2.0×10-12 mol·L-1 (accumulation time 180 s). The procedure has been successfully applied to the determination of zirconium in the ore samples.

肾上腺素电氧化过程的快速扫描循环伏安研究

以快速循环伏安法为主要手段，研究了肾上腺素电化学氧化反应机理 .肾上腺素在 1 mol· dm－ 3 H2SO4中的电化学氧化反应，具有扩散控制的基本特征，并伴随着电活性质粒的弱吸附现象 .在快速电势扫描条件下，肾上腺素电氧化过程遵从 EC反应机理 .当肾上腺素浓度低于 1.00× 10－ 3 mol· dm－ 3时，吸附现象的特征趋于显现出来 ;在快速电势扫描速率下，电活性质粒吸附的特征更加明显 .结合表面伏安法分析，估算了肾上腺素电氧化过程的传递系数α =0.264.电化学反应速率常数 ks=31.81 s－ 1.

硒的汞膜电极示差脉冲吸附伏安法

本文研究了在Britton-Robinson溶液(pH=2.1)中,硒(Ⅳ)-邻苯二胺体系的示差脉冲吸附伏安行为,讨论了电极过程。由硒-邻苯二胺体系产生的吸附还原峰可检测低至5.0×10^(10)mol/L的硒。硒浓度在1.0×10^(-9)～1.0×10^(-6)mol/L范围内与其峰电流呈良好的线性关系。本法可用于发样中痕量硒的测定。

奥美拉唑在碳糊电极上的吸附伏安测定法研究

研究了奥美拉唑在碳糊电极上的电化学行为及检测方法 ;在1.2mol·L -1H2SO4 底液中 ,通过富集用碳糊电极吸附伏安法测定奥美拉唑 ;阴极峰电位为0.403V(vsSCE) ,峰电流与奥美拉唑的浓度在7.8×10-8～3.7×10-5 mol·L-1 范围内呈良好的线性关系 ;该法的检出限为1.43×10-8 mol·L-1;用标准加入法测得回收率范围为94 %～102 % ;对奥美拉唑胶囊用该法进行了测定 ,获得了满意的结果 ;该法的优点是成本低 ,操作方便 ,重复性好及检出限较低 ;对电极响应机理进行了探讨 。

基于溶出伏安法的铋微阵列电极检测饮料中的铅和镉

建立了基于溶出伏安法的铋微阵列电极检测饮料中重金属的方法。该传感器采用三电极体系,铋微阵列电极为工作电极,铂薄膜电极为对电极,Ag/AgCl电极为参比电极。铋是一种低毒的重金属,采用铋作为反应物质可以使检测过程更加安全。微阵列电极具有高通量测定、便于微型化、抗干扰性等优点。实验表明,该传感器可同时检测出Pb2+和Cd2+,检出限分别为0.067和0.064 mg/L,且具有很好的重复性。此传感器用于检测橙汁中的Pb2+和Cd2+,结果令人满意。

茜素紫修饰碳糊电极阳极溶出伏安法测定痕量锡

研究了利用茜素紫修饰碳糊电极测定痕量锡的阳极溶出伏安法。在 0 1 5mol/L醋酸盐缓冲溶液 (pH 4 .8)中 ,通过开路富集 ,Sn 和茜素紫形成络合物富集于电极表面 ,然后经过介质交换至 3 0mol/L的盐酸溶液中 ,于 -0 .80V还原后再进行阳极化扫描 ,于 -0 .68V左右获得一灵敏的锡的溶出峰。二次导数峰电流与Sn 浓度在 8.4× 1 0 -9～ 1 .4× 1 0 -6mol/L范围内呈良好的线性关系。检出限达 4×1 0 -9mol/L ,同时对电极反应机理进行了讨论。

抗癌药长春新碱及其与微管蛋白相互作用的电化学研究

在 0 0 5mol/LTris,0 15mol/LNaCl溶液中 ,用吸附伏安法研究长春新碱 (VCR) ,其峰电位在 -1 68V (vs .Ag/AgCl) ,峰电流与 1 0× 10 -8～ 2 0× 10 -7mol/LVCR浓度成正比 ,检测限为 7 0× 10 -9mol/L .用常规脉冲极谱法、线性扫描和循环伏安法等研究该体系的电化学行为 .实验表明 ,电极还原过程为具有吸附特征的不可逆过程 .VCR的吸附符合Frumkin吸附等温式 .也研究了VCR与微管蛋白的相互作用 .实验表明 ,VCR与微管蛋白形成一电活性的结合物 ,这一结合物具有吸附性 。

头孢噻肟钠的降解及其产物伏安行为的研究

头孢噻肟钠在ＮａＯＨ溶液中降解后，于０．１ｍｏｌ／ＬＮａＯＨ中得一灵敏的吸附伏安还原峰，Ｅ＿ｐ＝－０．７８Ｖ（ｖｓ，Ａｇ／ＡｇＣｌ），ｉ＿ｐ与头孢噻肟钠浓度在１．０×１０￣（－９）～１．０×１０￣（－８）、１．０×１０￣（－８）～１．０×１０￣（－７）、１．０×１０￣（－７）～１．０×１０￣（－６）ｍｏｌ／Ｌ范围内呈线性关系，检出限为５．０×１０￣（－１０）ｍｏｌ／Ｌ，用多种电化学手段研究其降解产物的伏安行为，测定了电极反应的有关参数，探讨了降解反应和电极反应机理。实验表明，体系属准可逆吸附波。