Electro-oxidation and determination of trazodone at multi-walled carbon nanotube-modified glassy carbon electrode

A simple and rapid electrochemical method was developed for the determination of trace-level trazodone, based on the excellent properties of multi-walled carbon nanotubes (MWCNTs). The MWCNT-modified glassy carbon electrode was constructed and the electrochemical behavior of trazodone was investigated in detail. The cyclic voltammetric results indicate that MWCNT-modified glassy carbon electrode can remarkably enhance electrocatalytic activity towards the oxidation of trazodone in neutral solutions. It leads to a considerable improvement of the anodic peak current for trazodone, and allows the development of a highly sensitive voltammetric sensor for the determination of trazodone. Trazodone could effectively accumulate at this electrode and produce two anodic peaks at about 0.73 V and 1.00 V. The electrocatalytic behavior was further exploited as a sensitive detection scheme for the trazodone determination by differential-pulse voltammetry. Under optimized conditions, the concentration range and detection limit are 0.2-10 μM and 24 nM, respectively for trazodone. The proposed method was successfully applied to trazodone determination in pharmaceutical samples. The analytical performance of this sensor has been evaluated for detection of analyte in urine as a real sample.     

Electrochemical behavior and voltammetric determination of norfloxacin at glassy carbon electrode modified with multi walled carbon nanotubes/Nafion

A simple and rapid electrochemical method is developed for the determination of trace-level norfloxacin, based on the excellent properties of multi-walled carbon nanotubes (MWCNTs). The MWCNTs/Nafion film-coated glassy carbon electrode (GCE) is constructed and the electrochemical behavior of norfloxacin at the electrode is investigated in detail. The results indicate that MWCNTs modified glassy carbon electrode exhibited efficiently electrocatalytic oxidation for norfloxacin (NFX) with relatively high sensitivity, stability and life time. Under conditions of cyclic voltammetry, the current for oxidation of selected analyte is enhanced significantly in comparison to the bare GCE. The electrocatalytic behavior is further exploited as a sensitive detection scheme for the analyte determinations by linear sweep voltammetry (LSV). Under optimized condition in voltammetric method the concentration calibration range and detection limit (S/N=3) are 0.1-100 micromol/L and 5 x 10(-8)mol/L for NFX. The proposed method was successfully applied to NFX determination in tablets. The analytical performance of this sensor has been evaluated for detection of the analyte in urine as a real sample.     

Voltammetric determination of quercetin at a multi-walled carbon nanotubes paste electrode

Quercetin can effectively accumulate at multi-walled carbon nanotubes-paraffin oil paste electrodes (CNTPE) and cause a sensitive anodic peak at around 0.32 V (vs. SCE) in a 0.10 M phosphate buffer solution (pH = 4.0). Under optimized conditions, the anodic peak current is linear to quercetin concentration in the ranges of 2.0 × 10^− 9−1.0 × 10^− 7 M and 1.0 × 10^− 7−2.0 × 10^− 5 M, and the regression equations are i_p (μA) = 0.0017 + 0.928c (μM, r = 0.999) and i_p (μA) = 0.183 + 0.0731c (μM, r = 0.995), respectively. This paste electrode can be regenerated by repetitively cycling in a blank solution for about 2 min. A 1.0 × 10^− 6 M quercetin solution is measured for 10 times using the same electrode regenerated after every determination, and the relative standard deviation of the peak current is 1.7%. The method has been applied to the determination of quercetin in hydrolysate product of rutin and the recovery is 99.2–102.6%. In comparison with graphite paste electrode, carbon nanotubes-nujol paste electrode and carbon nanotubes casting film modified glassy carbon electrode, the CNTPE gives higher ratio of signal to background current and better defined voltammetric peak.     

苦参碱在多壁碳纳米管修饰玻碳电极上的电催化氧化及其电分析方法

研究了苦参碱(Matrine, MT) 在多壁碳纳米管修饰玻碳电极(MWCNT/GCE)上的电化学行为. 与GCE相比, MT在MWCNT/GCE上峰电位负移120 mV, 峰电流增大约2.5倍, 表明MWCNT/GCE对MT的电化学氧化具有良好的催化作用. 同时测定并计算了MT在MWCNT/GCE上的电极过程动力学参数: 电子转移系数α、电极反应速率常数ks、扩散系数D. 运用差分脉冲伏安法对苦参碱样品含量进行测定, 相对标准偏差为0.12%～2.9%, 加标回收率为98.4%～99.0%. 该方法可用于MT的电化学定量测定.     

Anodic stripping voltammetric determination of mercury using multi-walled carbon nanotubes film coated glassy carbon electrode

An electrochemical method for the determination of trace levels of mercury based on a multi-walled carbon nanotubes (MWNT) film coated glassy carbon electrode (GCE) is described. In 0.1 mol L^–1 HCl solution containing 0.02 mol L^–1 KI, Hg²⁺ was firstly preconcentrated at the MWNT film and then reduced at –0.60 V. During the anodic potential sweep, reduced mercury was oxidized, and then a sensitive and well-defined stripping peak at about –0.20 V appeared. Under identical conditions, a MWNT film coated GCE greatly enhances the stripping peak current of mercury in contrast to a bare GCE. Low concentrations of I^– remarkably improve the determining sensitivity, since this increases the accumulation efficiency of Hg²⁺ at the MWNT film coated GCE. The stripping peak current is proportional to the concentration of Hg²⁺ over the range 8×10^–10–5×10^–7 mol L^–1. The lowest detectable concentration of Hg²⁺ is 2×10^–10 mol L^–1 at 5 min accumulation. The relative standard deviation (RSD) at 1×10^–8 mol L^–1 Hg²⁺ was about 6% (n=10). By using this proposed method, Hg²⁺ in some water samples was determined, and the results were compared with those obtained by atomic absorption spectrometry (AAS). The two results are similar, suggesting that the MWNT-film coated GCE has great potential in practical analysis.     

Voltammetric determination of nicotinic acid by glassy-carbon electrode modified with multiwall carbon nanotubes

A glassy-carbon electrode modified with a thin film of multiwall carbon nanotubes is used for the determination of nicotinic acid (NA). At the electrode, the latter yields a well-defined and very sensitive oxidation peak at 0.21 V (SCE). Investigation of the electrochemical behavior of NA shows that the electrode significantly enhances the NA oxidation peak current, compared with the non-modified electrode. Based on this, a very sensitive and simple electrochemical method is proposed for the NA determination after the optimization of all experimental parameters. The oxidation peak current is proportional to the NA concentration over the range 2×10⁻⁷ to 4×10⁻⁵ M, and the detection limit is 8×10⁻⁸ M after a 4-min accumulation. The relative standard deviation of 5.4% for the successive determination of 1×10⁻⁶ MNA (n=10) indicates excellent reproducibility. The analysis method is successfully demonstrated using tablet samples. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 2, pp. 190–195. The text was submitted by the author in English.     

Sensitive voltammetric determination of paracetamol by poly (4-vinylpyridine)/multiwalled carbon nanotubes modified glassy carbon electrode

A novel glassy carbon electrode (GCE) modified with a composite film of poly (4-vinylpyridine) (P4VP) and multiwalled carbon nanotubes (P4VP/MWCNT GCE) was used for the voltammetric determination of paracetamol (PCT). This novel electrode displayed a combined effect of P4VP and MWCNT on the electro-oxidation of PCT in a solution of phosphate buffer at pH 7. Hence, conducting properties of P4VP along with the remarkable physical properties of MWCNTs might have combined effects in enhancing the kinetics of PCT oxidation. The P4VP/MWCNT GCE has also demonstrated excellent electrochemical activity toward PCT oxidation compared to that with bare GCE and MWCNT GCE. The anodic peak currents of PCT on the P4VP/MWCNT GCE were about 300 fold higher than that of the non-modified electrodes. By applying differential pulse voltammetry technique under optimized experimental conditions, a good linear ratio of oxidation peak currents and concentrations of PCT over the range of 0.02–450 μM with a limit of detection of 1.69 nM were achieved. This novel electrode was stable for more than 60 days and reproducible responses were obtained at 99% of the initial current of PCT without any influence of physiologically common interferences such as ascorbic acid and uric acid. The application of this electrode to determine PCT in tablets and urine samples was proposed.     

Sensitive voltammetric determination of tyrosine using multi-walled carbon nanotubes/4-aminobenzeresulfonic acid film-coated glassy carbon electrode

A chemically modified electrode is constructed based on the multi-walled carbon nanotubes (MWNTs)/4-aminobenzeresulfonic acid (4-ABSA) film-coated glassy carbon electrode. The electrocatalytic oxidation of tyrosine (Tyr) is investigated on the surface of the MWNTs/4-ABSA-modified electrode using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The prepared modified electrode shows voltammetric responses with high sensitivity and selectivity for Tyr in optimal conditions, which makes it very suitable for sub-micromolar detection of Tyr. A sensitive oxidation peak at +0.64 V is employed to determine Tyr. Good linear relationship between the oxidation peak current and the Tyr concentration in the range of 1 × 10⁻⁷ to 5 × 10⁻⁵ mol/L is obtained in phosphate buffer solution with pH 7.0. By use of modified electrode, the voltammetric detection limit for Tyr in DPV measurements is 8 × 10⁻⁸ mol/L (S/N = 3). Good sensitivity, selectivity and stability of the low-cost modified electrode make it very suitable for the determination of trace amounts of Tyr in pharmaceutical and clinical preparations.     

Study on electrochemical behavior of tryptophan at a glassy carbon electrode modified with multi-walled carbon nanotubes embedded cerium hexacyanoferrate

Electrochemical behavior of cerium hexacyanoferrate (CeHCF) incorporated on multi-walled carbon nanotubes (MWNTs) modified GC electrode is investigated by scanning electron microscopy (SEM) and electrochemical techniques. The CeHCF/MWNT/GC electrode showed potent electrocatalytic activity toward the electrochemical oxidation of tryptophan in phosphate buffer solution (pH 7.0) with a diminution of the overpotential of 240 mV. The anodic peak currents increased linearly with the concentration of tryptophan in the range of 2.0 × 10⁻⁷ to 1.0 × 10⁻⁴ M with a detection limit of 2.0 × 10⁻⁸ M (at a S/N = 3). And the determination of tryptophan in pharmaceutical samples was satisfactory.     

二苯氨基碳酰肼在多壁碳纳米管修饰电极上的电催化氧化及电化学动力学研究

肼及其衍生物被广泛应用于医药,农药,水处理,军事,航天,光稳定剂以及化工生产助剂等诸多领域。因此对肼及其衍生物的研究有着极其重要的意义。二苯氨基碳酰肼(二苯氨基脲,又名二苯卡巴肼,D iphenyl Carbazide,DPC)广泛用于重金属离子的检测分析[1-4]。但是,目前关于DPC的电化学     

对硝基苯酚在多壁碳纳米管修饰玻碳电极上的电化学行为及分析测定

水中对硝基苯酚主要来源于化工、制药行业,它有致癌作用。人们已对它的测定方法进行了大量的研究,最早采用的测定方法是分光光度法,其检测限偏高;色谱法测定对硝基苯酚,操作繁琐,仪器昂贵,分析成本高。后来又发展了一种操作更方便的直接用于测定的电化学方法。本文旨在利用碳纳米管对对硝基苯酚的吸附性能,研究对硝基苯酚在多壁碳纳米管修饰电极上的电化学行为。     

苯甲酰肼在多壁碳纳米管修饰玻碳电极上的电催化氧化及其电化学动力学性质

研究了苯甲酰肼(BH)在MWCNT/GCE上的电化学行为。实验结果表明,BH在GCE上的直接电化学氧化十分迟缓,无氧化峰出现,但在MWCNT/GCE上BH在0.20 V处出现了一个不可逆氧化峰,且峰电流大幅度增大,表明MWCNT/GCE对BH电化学氧化具有良好的催化作用。同时用计时库仑法(Chro-nocoulometry,CC)和计时电流法(Chronoamperometry,CA)测定了电极过程动力学参数:扩散系数D=8.73×10-5cm2.s-1,电子转移系数α=0.85,电极反应速率常数kf=1.45×10-3s-1。稳态电流-时间实验结果表明,电流响应信号随其浓度成比例增长,响应时间小于6 s,最低响应浓度为1×10-6mol/L。该方法可用于BH电化学定量测定。     

Cobalt hexacyanoferrate modified multi-walled carbon nanotubes/graphite composite electrode as electrochemical sensor on microfluidic chip

Nanomaterial-based electrochemical sensor has received significant interest. In this work, cobalt hexacyanoferrate modified multi-walled carbon nanotubes/graphite composite electrode was electrochemically prepared and exploited as an amperometric detector for microchip electrophoresis. The prepared sensor displayed rapid and sensitive response towards hydrazine and isoniazid oxidation, which was attributed to synergetic electrocatalytic effect of cobalt hexacyanoferrate and multi-walled carbon nanotubes. The sensitivity enhancement with nearly two orders of magnitude was gained, compared with the bare carbon paste electrode, with the detection limit of 0.91 μM (S/N = 3) for hydrazine. Acceptable repeatability of the microanalysis system was verified by consecutive eleven injections of hydrazine without chip and electrode treatments, the RSDs for peak current and migration time were 3.4% and 2.1%, respectively. Meanwhile, well-shaped electrophoretic peaks were observed, mainly due to fast electron transfer of electroactive species on the modified electrode. The developed microchip-electrochemistry setup was successfully applied to the determination of hydrazine and isoniazid in river water and pharmaceutical preparation, respectively. Several merits of the novel electrochemical sensor coupled with microfluidic platform, such as comparative stability, easy fabrication and high sensitivity, hold great potential for hydrazine compounds assay in the lab-on-a-chip system.     

亚硝酸根在纳米金修饰玻碳电极上的电催化氧化行为及其测定

采用直接电化学沉积法制备出纳米金修饰玻碳电极,研究了其对亚硝酸根的电催化氧化作用。结果表明,亚硝酸根在该修饰电极上于0.8 V处出现了一个良好的氧化峰。在最优实验条件下,亚硝酸根的峰电流与其浓度在2×10-6～2×10-3mol/L范围内呈一定的线性关系,检出限为6.0×10-7(S/N=3),提出了用循环伏安法测定亚硝酸根的方法。纳米金修饰电极用于东莞自来水水样中亚硝酸根的测定,回收率在98.1%～101.4%之间。对比本方法,用分光光度法对东莞自来水样中亚硝酸根进行了测定,结果满意。     

Determination of trace thiocyanate with nano-silver coated multi-walled carbon nanotubes modified glassy carbon electrode

Novel nano-silver coated multi-walled carbon nanotube composites were prepared and used to fabricate a modified electrode. The application of the nano-silver coated multi-walled carbon nanotube composites modified electrode for determination of trace thiocyanate is demonstrated for the first time. The influence of substrate, pH and interference of coexisting substances was investigated for response properties of the electrode. There was a linear relationship at the range 2.5 × 10⁻⁹ to 5 × 10⁻⁸ mol L⁻¹ and 5 × 10⁻⁸ to 1 × 10⁻⁶ mol L⁻¹ of thiocyanate with the decrement of anodic DPV peak currents. The limit of detection was 1 × 10⁻⁹ mol L⁻¹(S/N = 3). The constructed electrode showed excellent reproducibility and stability. Actual urine and saliva samples of smoker and non-smoker were analyzed and satisfactory results were obtained. This method provides a new way to construct any electrode for biological and environmental analysis.     

普鲁士蓝/多壁碳纳米管修饰电极测定维生素C

利用电化学方法在多壁碳纳米管修饰的玻碳电极表面聚合一层普鲁士蓝,制备普鲁士蓝/多壁碳纳米管修饰玻碳电极,运用循环伏安法研究了维生素C(vc)在该修饰电极上的电化学行为.该修饰电极对Vc显示出快速的电化学响应和较好的电催化活性,在pH为4.0的磷酸盐溶液中,Ve浓度与其氧化峰电流在8.0×10-4～1.0×10-2 mol/L范围内呈现良好的线性关系,相关系数为0.9993,检测限为6.4×10-5mol/L.该电极具有较好的稳定性和重现性.     

盐酸左氧氟沙星在聚L-精氨酸/多壁碳纳米管修饰电极上的电化学行为

运用循环伏安法、线性扫描伏安法、计时电量法等研究了盐酸左氧氟沙星在聚L-精氨酸/多壁碳纳米管修饰电极上的电化学行为。实验表明:盐酸左氧氟沙星在聚L-精氨酸/多壁碳纳米管修饰电极上的电极反应过程为等电子等质子吸附控制的不可逆过程,在pH=6.0的Na2HPO4-NaH2PO4支持电解质中,其氧化峰电流与浓度在7.0×10-6~1.0×10-4mol·L-1范围内呈良好的线性关系,相关系数R为-0.9992,检出限为5.0×10-6mol·L-1,样品测定回收率为98.26%~101.70%。     

Voltammetric oxidation and determination of cinnarizine at glassy carbon electrode modified with multi-walled carbon nanotubes

We discovered a novel method to prepare a protein-based hydrogel, that is, a “Three-Dimensional Nanostructured Protein Hydrogel (3D NPH)”, which is composed of protein–polymer hybrid nanoparticles. In this study, we propose a novel protein microarray whose 3D NPH spots were prepared by dispensing a small volume of the solution of protein–polymer mixture on a substrate. The dispensed solution had a short time for cross-linking before its drying-up and the resulting 3D NPH had loosely cross-linked, thin spongy structure. Therefore, the reaction ratio between ligands and analytes was drastically improved in this system compared with the large volume system for Surface Plasmon Resonance (SPR) protein microarray.     

Electrochemical behavior of phenol at acetylene black-dihexadecyl hydrogen phosphate composite modified glassy carbon electrode in the presence of cetyltrimethylammonium bromide

The electrochemical response of phenol at acetylene black (AB)-dihexadecyl hydrogen phosphate (DHP) composite modified glassy carbon electrode in the presence of cetyltrimethylammonium bromide (CTAB) was investigated. In this system, a sensitive oxidation peak at 0.62 V (SCE) was obtained. The electrode process and the influence of CTAB on the oxidation of phenol were explored by chronocoulometry and linear sweep voltammetry (LSV). Experimental conditions for the determination of phenol were optimized. In the range of 5.0 × 10⁻⁷ to 1.2 × 10⁻⁵ M, the phenol concentration was linear with the oxidation peak current and the detection limit was found to be 1.0 × 10⁻⁷ M for 3 min accumulation. The method was applied for the determination of phenol in lake water and the results were satisfactory. Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 2, pp. 222–229. The text was submitted by the authors in English.     

Application of multi-walled carbon nanotubes modified carbon ionic liquid electrode for electrocatalytic oxidation of dopamine

A simple, sensitive, and reliable method based on a multi-walled carbon nanotubes (MWNTs) modified carbon ionic liquid electrode (CILE) has been successfully developed for determination of dopamine (DA) in the presence of ascorbic acid (AA). The acid-treated MWNTs with carboxylic acid functional groups could promote the electron-transfer reaction of DA and inhibit the voltammetric response of AA. Due to the good performance of the ionic liquid, the electrochemical response of DA on the MWNTs/CILE was better than that of other MWNTs modified electrodes. Under the optimum conditions a linear calibration plot was obtained in the range 5.0×10(-8) to 2.0×10(-4) mol L(-1) and the detection limit was 1.0×10(-8) mol L(-1).