The Electrochemical Behavior of Nitrazepam at a Screen‐Printed Carbon Electrode and Its Determination in Beverages by Adsorptive Stripping Voltammetry

The cyclic voltammetric behavior of nitrazepam was investigated at screen‐printed carbon electrodes over the range ?1.5 V to +1.5 V. Two reduction peaks were observable on the negative scan, at ?0.7 V, and ?1.2 V using pH 6 buffer. On the return scan a single oxidation peak was obtained at ?0.05 V. For quantitative analysis of beverages, we developed an anodic adsorptive stripping voltammetric method which required only dilution with buffer. The identification of nitrazepam and flunitrazepam could be achieved using cyclic voltammetry.     

Adsorptive Stripping Voltammetric Detection of Tea Polyphenols at Multiwalled Carbon Nanotubes‐Chitosan Composite Electrode

This study reports the catalytic oxidation and detection of tea polyphenols (TPs) at glassy‐carbon electrode modified with multiwalled carbon nanotubes‐chitosan (MWCNTs‐CS) film. The adsorption of TPs at the surface of the MWCNTs through π–π conjugation prevents the aggregation of nanotubes and induces a stable MWCNTs suspension in water over 30 days. Based on the adsorptive accumulation of polyphenols at MWCNTs, TPs is sensitively and selectively detected by adsorptive stripping voltammetry. The accumulation conditions and pH effect on the adsorptive stripping detection were examined. The linear range was found to be 100 to 1000 mg L^?1 with a detection limit of 10 mg L^?1 (S/N=3) for 2.5 min accumulation. Additionally, the MWCNTs‐CS electrode is easily renewed by applying positive potential to remove the adsorbed TPs. This method was successfully applied to determine TPs in commercially available teas with satisfied result compared with that of conventional spectrometric analysis.     

Determination of Folic Acid at a Bismuth Film Electrode by Adsorptive Stripping Voltammetry

This article reports a new simple and sensitive method for the determination of folic acid by adsorptive stripping voltammetry. The method is based on the accumulation of folic acid at a bismuth film plated in situ on a glassy carbon substrate. In order to stabilize bismuth ions, sodium potassium tartrate was added to the supporting electrolyte. The bismuth film formation and folic acid accumulation conditions were optimized and measurements were carried without solution deaeration. The calibration graph was linear from 5 × 10^?10 to 2 × 10^?8 mole per liter with an accumulation time of 180 seconds with a limit of detection of 2 × 10^?10 mole per liter. The relative standard deviation for 5 × 10^?9 mole per liter of folic acid was 3.1 percent (n = 5). The method was successfully applied for determination of folic acid in pharmaceutical preparations.     

固态汞合金电极吸附伏安法测定酪氨酸

采用白合金粉与汞混合制成汞合金糊,涂布在固体石蜡碳糊电极表面,固化后制得固态汞合金电极,并首先应用于酪氨酸的测定。在含Co2 的pH 9.2的硼砂-NaOH底液中,用线性扫描伏安法在-0.80~-1.30V范围内进行扫描,酪氨酸于-1.05 V出现灵敏的还原峰,酪氨酸的浓度与峰电流在1.0×10-7~1.0×10-5mol/L范围内呈线性关系。该法已用于复方氨基酸注射液中酪氨酸含量的测定,加标回收率达96%~102%。该电极既保留了汞电极的优点,又避免了汞电极有毒、使用不方便的缺点。     

Indirect Determination of Trace Copper(II) by Adsorptive Stripping Voltammetry with Zincon at a Carbon Paste Electrode

Traces of copper(II) can be determined by adsorptive stripping voltammetry using 2‐carboxy‐2′‐hydroxy‐5′‐sulfoformazyl benzene (Zincon) as complex forming reagent. First in phosphate buffer pH 6.4, copper(II)‐Zincon complex was adsorbed on carbon paste electrode (CPE) with an accumulation potential of 0.6 V. Following this, adsorbed complex was oxidized and detected by differential pulse voltammetric (DPV) scan from 0.6 to 1.0 V. The effective parameters in sensor response were examined. The detection limit (DL) of copper(II) was 1.1 μg/L and relative standard deviations (RSDs) for 10 and 200 μg/L Cu(II) were 1.81 and 1.03%, respectively. The calibration curve was linear for 2–220 μg/L copper(II). The resulting CPE does not use mercury and therefore, has a positive environmental benefit. The method, which is reasonably sensitive and selective, has been successfully applied to the determination of trace amount of copper in water and human hair samples.     

Determination of Trace Vanadium by Adsorptive Stripping Voltammetry at a Carbon Paste Electrode

A method for the voltammetric determination of vanadium using a carbon paste electrode (CPE) was described. The new procedure is based on the adsorptive accumulation of the V(V)‐alizarin red S(ARS) complex onto the surface of the CPE, followed by the electrochemical reduction of adsorbed species. The optimal experimental conditions include the use of 0.10 mol/L acetate buffer (pH 5.1), 1.0×10^?5 mol/L ARS, an accumulation potential of ?0.10 V (versus SCE), an accumulation time of 2 min, a scan rate of 200 mV/s and a second‐order derivative linear scan mode. The reduction peak for the complex appears at ?0.52 V. The peak current is proportional to the concentration of V(V) over the range of 0.10–15.0 μg/L, and the detection limit is 0.04 μg/L for a 2 min adsorption time. The relative standard deviations(n=8) for 2.0 and 0.50 μg/L V(V) are 3.1 and 4.7%, respectively. The proposed method was applied to the determination of vanadium in water samples.     

吸附溶出伏安法测定普罗帕酮的研究

在pH 6.47的磷酸盐缓冲溶液中,可得到普罗帕酮的吸附溶出峰。峰电位为-1.38V(vs.Ag/AgCl),富集1min,溶出峰电流与普罗帕酮浓度在8.0x10~(-9)～7.0x10~(-7)mol/L范围内呈线性关系。富集4min检测下限为3.0×10(-10)mol/L。该法用于测定普罗帕酮制剂及人血清中的痕量普罗帕酮,均得到了满意的结果,并探讨了电极反应过程机理。     

杯芳烃修饰玻碳电极吸附溶出伏安法测定微量铅

研究了以杯芳烃衍生物修饰玻碳电极,以其吸附溶出伏安法测定微量铅。对富集时间、铅的浓度、支持电解质、样品溶液pH值及部分离子干扰等进行了实验。实验发现以氢氧化钠溶液处理修饰电极可提高测定灵敏度,经过优化处理后,线性范围和检出限分别为5.0×10-7～1.0×10-5mol/L和1.0×10-8mol/L。应用本法对合成水样进行了测定,结果满意。本文还对吸附溶出机理进行了讨论。     

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 ,奥美拉唑的电极过程是一个两电子两质子的准可逆过程     

Adsorptive Stripping Voltammetric Determination of Trace Level Ricin in Castor Seeds Using a Boron‐doped Diamond Electrode

Ricin, (Ricinus communis agglutinin, RCA) is one of the most poisonous of naturally occurring substances and has great potential for bioterrorism because no antidote exists. Fast detection at low concentrations is a challenge, and vital to the development of proper countermeasures. In this study, a square wave adsorptive stripping voltammetric (SWAdSV) method for determining RCA using a cathodically polarized boron‐doped diamond (BDD) electrode is presented. An irreversible electrochemical RCA oxidation peak was identified on the BDD electrode by different voltammetric techniques using both direct and adsorptive stripping modes. An adsorption‐controlled (slope log Ip vs log v of 0.80) pH‐dependent process was observed. For values of 1.0≤pH≤9.0, the numbers of protons and electrons associated with the oxidation reaction were estimated (ca. 1.0) by differential pulse voltammetry. The RCA oxidation step may correspond to the oxidation of tryptophan amino acid residues, and occurs in a complex mechanism. The excellent analytical performance of the cathodically polarized BDD electrode in combination with the stripping mode ramp was verified with RCA by using a short deposition time in an open circuit potential (120 s). Under optimized analysis conditions, a linear response in the range of (3.3–94.0)×10⁻⁹ mol L⁻¹ (r²=0.9944) and a limit of detection of 6.2×10⁻¹⁰ mol L⁻¹ were estimated. This LOD is lower than several methods found in the literature. For example, it is 168 times lower than that obtained by using square wave voltammetric with a glassy carbon electrode. Moreover, an even lower LOD might be achieved by using the SWAdSV method with a higher pre‐concentration time. In addition, trace levels of RCA were successfully determined in different castor seed cultivars with an overall average recovery from 99.2±1.6 % for the three different RCA‐A concentration levels. The high accuracy of the analytical data highlights the use of the proposed method for determining RCA in other samples.     

Highly Sensitive and Selective Adsorptive Stripping Voltammetric Method Employing a Lead Film Screen‐printed Electrode for Determination of Cobalt as its Nioximate Complex

A carbon screen‐printed electrode modified in‐situ with lead film (PbF‐SPCE) was applied for the adsorptive stripping voltammetric determination of Co(II) in the form of a complex with 1,2‐cyclohexanedione dioxime. Lead film was electrochemically deposited in situ on SPCE from a 0.2 M ammonia buffer solution (pH 8.7) containing 5 ? 10^?5 M Pb(NO₃)₂ and 5 ? 10^?5 M nioxime. Due to the very low LOD (0.003 µgL^?1, i.e., 0.05 nmol L^?1 Co(II); t_acc=120s), the developed procedure could be rated among the most sensitive methods employing SPEs. The Ni(II) signal was significantly lower than the Co(II) one and the separation of Ni(II) and Co(II) peaks was even better at the PbF‐SPCE than at the hanging mercury drop electrode.     

New Protocol for Determination of Rifampicine by Adsorptive Stripping Voltammetry

For determinations of organic compounds by adsorptive stripping voltammetry till now the same material of the electrode has been used for the accumulation and stripping steps. This paper describes a new protocol for extending the range of organic compounds, which can be determined by adsorptive stripping voltammetry. In the proposed procedure the accumulation step was performed on the electrode modified by a lead film, which assures adsorption of the studied species on the modified electrode and then the stripping step of the accumulated substance was performed on the support of the lead film electrode. As an example rifampicine was accumulated by adsorption at the lead film electrode while in the stripping step lead film and then the accumulated rifampicine were oxidized at a glassy carbon electrode. Using an acetate buffer as a supporting electrolyte a calibration graph for rifampicine in the range from 2.5×10^?10 to 1×10^?8 mol L^?1 was obtained. The detection limit for rifampicine following 60 s accumulation time was equal to 9×10^?11 mol L^?1. The obtained detection limit was comparable or lower than reported previously for other stripping voltammetric procedures. The proposed procedure was applied to rifampicine determination in pharmaceutical preparation.     

阴极溶出伏安法测定异烟肼的研究

报道了吸附阴极溶出伏安法测定异烟肼。探讨了电极反应机理。在０．０１ｍｇｏｌ／Ｌ硼砂底液中，峰电位为－１．４０Ｖ。峰电流与异烟肼浓度在４．０＊１０＾－７－１．５＊１０＾－５ｍｏｌ／Ｌ范围内呈良好的线性关系，相关系为０．９９１３。该方法用于异烟肼片剂的测定，获得满意结果。     

Rapid Assay of Bisphenol A Released from Baby Feeding Bottles by Adsorptive Stripping Voltammetry on a Diphenylether Carbon Paste Electrode

This work reports the determination of bisphenol A (BPA) released from baby feeding bottles by adsorptive stripping voltammetry on a diphenylether carbon paste electrode (DPE-CPE). BPA was as accumulated on the surface of the DPE-CPE by an adsorptive/extractive mechanism at ?0.20 V in B-R buffer at pH 7.0. Following pre-concentration, an anodic scan was applied in the range ?0.20 V to +1.00 V during which BPA was oxidized and the oxidation peak current was related to the BPA concentration in the sample. The parameters related to both the preconcentration and stripping step were investigated. Using the selected conditions, the limit of detection for BPA was 7.8 × 10^?9 mol L^?1 at a preconcentration time of 240 s and the % relative standard deviation was 4.2% for 6.7 × 10^?7 mol L^?1 of BPA (n = 8). The proposed method was applied to the determination of BPA leaching from polycarbonate baby feeding bottles under simulated conditions of typical use. The results compared well with those obtained with liquid chromatography-tandem mass spectrometry (LC-MS/MS).     

玻碳电极吸附伏安法测定痕量硫化物的研究

研究了利用玻碳电极吸附伏安法测定痕量硫化物的新方法。在含高铁离子的酸性溶液中,硫化物与对-氨基苯二甲基盐酸盐(p-ADAD)反应生成亚甲基蓝,采用线性扫描伏安法亚甲基蓝于-0.30 V(vs.SCE)在玻碳电极上出现灵敏的还原峰,峰电流与S2-浓度在0～25μg/mL范围内呈良好的线性关系。优化了实验条件,研究了电极反应机理。该方法具有灵敏、简便、快速、避免汞污染等特点。已成功用于多种水样中痕量硫化物的测定,回收率为98.0%～104.6%,结果令人满意。     

吸附溶出伏安法测定苯胺的研究

在酸性介质中,苯胺与亚硝酸根离子和盐酸萘乙二胺反应生成玫瑰红色偶氮染料,该染料在汞电极上具有良好的吸附性能,并且在氨性缓冲介质中可在汞电极上还原,于－０．５５Ｖ左右产生一灵敏的吸附极谱波。据此,建立了吸附溶出伏安法测定苯胺的方法。当吸附富集时间为３ｍｉｎ时,该法的检测下限为５×１０－９ｍｏｌ／Ｌ,比分光光度法降低了近两个数量级。应用本方法测定了废水中的苯胺,结果满意。     

Determination of Trace Amount of Lead(II) in Sweet Fruit‐Flavored Powder Drinks by Differential Pulse Adsorptive Stripping Voltammetry at Carbon Paste Electrode

A new method is described for the determination of lead based on the cathodic adsorptive stripping of the lead–nuclear fast red (NFR) at a carbon paste electrode (CPE). The differential pulse voltammograms of the adsorbed complex of lead–NFR are recorded from ?0.10 to ?0.60 V (versus Ag/AgCl electrode). Optimal conditions were found to be an electrode containing 25% paraffin oil and 75% high purity graphite powder, 4.0×10^?5 mol L^?1 NFR; buffer solution (pH of 3.0), accumulation potential and time, ?0.20 V, 60 and 120 s (for high and low concentration of lead), respectively. The results show that the complex can be adsorbed on the surface of the CPE, yielding one peak at ?0.34 V, corresponding to reduction of NFR in the complex at the electrode. The detection limit was found to be 0.2 ng mL^?1 with a 120s accumulation time. The linear ranges are from 0.5 to 50 (t_acc=120 s) and 50 to 200 ng mL^?1 (t_acc=60 s). Application of the procedure to the determination of lead in lake water, bottled mineral water, synthetic samples and sweet fruit‐flavored powder drinks samples gave good results.     

Voltammetric Behavior of Testosterone on Bismuth Film Electrode: Highly Sensitive Determination in Pharmaceuticals and Human Urine by Square‐Wave Adsorptive Stripping Voltammetry

In this paper, an electrochemical application of bismuth‐film electrode (BiFE) fabricated via ex‐situ electrodeposition onto a glassy carbon electrode for testosterone determination was investigated in aqueous and aqueous/surfactant solutions. In cyclic voltammetry, the compound showed one irreversible and adsorption‐controlled reduction peak. The BiFE revealed good linear response in the examined concentration range of 1 to 45 nmol L^?1 testosterone in Britton? Robinson buffer, pH 5.0 containing 3 mmol L^?1 cetyltrimethylammonium bromide. The limit of detection was 0.3 nmol L^?1 (0.09 ng mL^?1). Finally, the BiFE was satisfactorily applied for quantitation of testosterone in both pharmaceutical (oil‐based ampoule) and biological (human urine) samples.     

Stripping Voltammetric Determination of Mercury in Fish Oil Capsules Using a Screen‐printed Gold Electrode

This work presents a simple electrochemical method for Hg determination in fish oil capsules using anodic stripping voltammetry (ASV) on a screen‐printed gold electrode (SPGE). Samples were treated in an ultrasonic bath for 15 min in the presence of a 1 : 1 (v/v) concentrated HCl/H₂O₂ mixture at room temperature. The limit of detection (LOD) was estimated as 0.25 μg L⁻¹ (corresponding to 7.6 μg kg⁻¹ of oil) with a linear range between 5 and 400 μg L⁻¹ (90 s of deposition time). The analyzed fish oil samples presented Hg concentration below the LOD value. Recovery values for samples spiked with oil standard containing Hg ranged from 95 to 105 %. The method is precise (inter‐day and intra‐day RSD<4 % for n=3) as well as the SPGE sensors (RSD=4.3 %, n=3), which were used continuously (around 100 analyses without replacement) under such oxidation media. The proposed method is feasible to be applied for on‐site determinations due to the portability of sensing and sample treatment approaches.     

Uric Acid Determination by Adsorptive Stripping Voltammetry on Multiwall Carbon Nanotubes Based Screen‐Printed Electrodes

A sensitive electroanalytical methodology for the determination of uric acid in real samples using adsorptive voltammetry at a multiwalled carbon nanotubes (MWCNT) modified screen printed electrode (SPCE) is presented. Adsorption of uric acid takes place at open circuit potential at an optimized pH 5.0. Studies about the effect of accumulation time and scan rate on the analytical signal were developed and confirm the adsorption nature of the electrodic process. Quantitative analysis of uric acid by using its oxidation process at +0.18 V (vs. an Ag pseudoreference electrode) was carried out with an accumulation time of 5 min. Thus, a linear voltammetric based reproducible determination of uric acid (RSD 5 %) in the range 1–100 µM was obtained. The method was then successfully used for the determination of uric acid in real clinical samples of urine without detection of interferences. The proposed methodology only requires a dilution of the real sample and present advantages as low cost and easy handling for non specialized technicians.