多巴胺在聚亚甲基蓝/石墨烯修饰电极上的电化学行为研究

利用电聚合方法在石墨烯修饰的玻碳电极表面制备了聚亚甲基蓝/石墨烯修饰电极(PMB/GH/GCE)。采用循环伏安法(CV)和差分脉冲伏安法(DPV)研究了多巴胺(DA)和抗坏血酸(AA)在该修饰电极上的电化学行为。在pH 6.9的磷酸盐缓冲溶液中,DA和AA分别在0.208 V和-0.108 V处产生灵敏的氧化峰,与其在聚亚甲基蓝和石墨烯单层修饰电极上的电化学行为相比,两者的峰电流明显增加,峰电位差达316 mV。研究表明,电聚合方法使亚甲基蓝牢固地非共价修饰到石墨烯上,并产生协同增效作用,较好地提高了电极的灵敏度和分子识别性能,有利于在大量AA存在下实现对DA的选择性测定。在1.00×10-3mol/L AA的存在下,DA的差分脉冲伏安法峰电流与其浓度在1.00×10-7～5.00×10-3mol/L范围内呈良好的线性关系,检出限达1.00×10-8mol/L。将该方法用于盐酸多巴胺注射液的测定,结果满意。     

Gas chromatographic retention behaviour of dibenzothiophene derivatives on a smectic liquid crystalline polysiloxane stationary phase

The gas chromatographic retention behaviour, on a smectic liquid crystalline polysiloxane stationary phase, of methyldibenzothiophenes and eighteen C₂-dibenzothiophenes (sixteen dimethyldibenzothiophenes and two ethyldibenzothiophenes), out of twenty possible compounds, was investigated. The retention, in addition to vapour pressure and polarity, was greatly influenced by the molecular geometry of the solutes. The major factor affecting this behaviour was the length to breadth ratio (L/B). The elution order of the dimethyldibenzothiophenes was fairly well correlated with L/B values: Roughly, the lower the L/B values, the earlier the dimethyldibenzothiophenes were eluted. However, the solute molecular shape, although of less importance, was also a significant retention-affecting factor, having the contrary effect to L/B values on the elution order. Arc-like molecules (dibenzothiophenes) with groups attached to the outer curved side (i.e., in positions 3 and 4) were retained longer than predicted by L/B values. In contrast, isomers conforming to the arc-like arrangement (i.e., with substituents in positions 1 and 2) were less retained than predicted. The application of these identifications to a crude oil sample is described.     

在抗坏血酸存在下用L-赖氨酸修饰玻碳电极测定多巴胺

采用电化学氧化法制备了L-广赖氮酸单分子层修饰玻碳电极,研究了多巴胺（DA）和抗坏血酸（AA）在该电极上的电化学行为。结果表明,L-广赖氨酸单分子层修饰玻碳电极不仅能改善多巴胺和抗坏血酸的电化学行为,而且能将多巴胺和抗坏血酸二者在裸电极上的完全重叠的单氧化峰分开成为两个完全独立的氧化峰,循环伏安（CV）图上峰间距为507mV,差分脉冲伏安（DPV）图上峰间距为460mV,由此可实现在AA的共存下对样品中的DA进行选择性测定。     

Ga-C3N4单原子催化剂高效光驱动CO2环加成

通过配位锚定策略制备了一种高Ga单原子负载量(质量分数8.42%)的C₃N₄纳米片(Ga-C₃N₄), 用于高效光驱动CO₂环加成反应. 研究结果表明, Ga-C₃N₄中Ga单原子和均匀分布的N位点可分别作为Lewis酸/碱位点来活化环氧化合物和CO₂. 此外, Ga-C₃N₄具有优异的半导体特性, 在光照下产生的光生电子可以显著加快环氧化合物的开环速率, 即提升决速步骤的反应效率. 通过多功能协同, Ga-C₃N₄在光照下实现了CO₂到环状碳酸酯的高效催化转化.     

多壁碳纳米管-Nafion化学修饰电极在高浓度抗坏血酸和尿酸体系中选择性测定多巴胺

多巴胺是人体内一种重要的神经传递物质 ,它参与许多生命过程[1] .因此 ,测定体内多巴胺的浓度十分重要 .多巴胺的电化学分析方法已有不少报道 [2 ,3 ] .然而 ,共存的抗坏血酸和尿酸的电化学性质与多巴胺相似 ,对多巴胺的测定会产生严重干扰 .因此建立一种选择性测定多巴胺的高灵敏度的分析方法就显得尤为重要 .碳纳米管是一种新型的纳米材料 [4 ] ,它的出现引起了广泛的研究兴趣 [5,6] .由于其性质稳定 ,不溶于水及一般的有机溶剂 ,因此限制了其在电分析方面的应用 .本文将多壁碳纳米管分散在 Nafion的无水乙醇中 ,得到了一种均匀的多壁碳…     

聚对氨基苯磺酸/石墨烯复合修饰电极对尿酸的选择性灵敏测定

采用电聚合方法在石墨烯纳米片(GN)的表面聚合一层聚对氨基苯磺酸(PABSA),制备了聚对氨基苯磺酸/石墨烯复合修饰玻碳电极(PABSA/GN/GCE)。研究了尿酸(UA)和抗坏血酸(AA)在该修饰电极上的电化学行为。与聚对氨基苯磺酸修饰电极(PABSA/GCE)及石墨烯单层膜修饰电极(GN/GCE)相比,复合修饰电极PABSA/GN/GCE显著提高了对UA和AA的检测灵敏度和分离度。在0.1 mol/L磷酸盐缓冲溶液(pH7.0)中,UA和AA的峰电位差达344 mV,表明PABSA/GN/GCE能实现对UA的选择性测定。UA的峰电流与其浓度呈良好的线性关系,线性范围为1.0×10-7～8.0×10-4mol/L,检出限为4.5×10-8mol/L。该复合修饰电极用于尿样中尿酸的测定,结果满意。     

Ascorbic acid amperometric sensor using a graphene-wrapped hierarchical TiO<Subscript>2</Subscript> nanocomposite

An ascorbic acid (AA) amperometric sensor was fabricated based on a glassy carbon electrode (GCE) modified with a reduced graphene oxide-wrapped hierarchical TiO₂ (RGO—TiO₂) nanocomposite. The RGO—TiO₂ nanocomposite was synthesized via the facial wet chemical method and characterized by scanning electron microscopy and X-ray diffraction. Cyclic voltammetry and amperometric techniques were employed to investigate its electrocatalytic performance towards the AA oxidation. The combined advantages of RGO and TiO₂ provide the electrode with higher current response and lower oxidation potential compared with those of bare GCE and TiO₂ modified GCE. The proposed electrode can be used for the determination of AA in the wide concentration range from 1 to 1500 µM with the detection limit of 0.5 µM. The proposed electrode was successfully used to determine AA in vitamin C tablets and spiked fruit juice.     

抗坏血酸在聚对羟基苯甲酸(poly-PHB)修饰玻碳上的电催化

过循环伏安制备了聚对羟基苯甲酸修饰的玻碳电极。考察了该电极对抗坏血酸的电催化性能。结果显示,聚对羟基苯甲酸修饰玻碳电极对抗坏血酸有很好的电催化作用。在修饰后的电极上产生的峰电流比修饰前的电极产生的峰电流大4倍,氧化峰电位负移189 mV。其氧化峰电流与抗坏血酸浓度在2.6×10-5~3.68 ×10-4mol/L范围内呈线性关系,相关性系数为0.9984,检测限为5×10-6 mol/L(S /N = 3)。在AA与UA共存的体系中,能排除多巴胺对抗坏血酸测定的干扰。     

Enhanced sensing of dopamine in the present of ascorbic acid based on graphene/poly(p-aminobenzoic acid) composite film

Graphene/p-aminobenzoic acid composite film modified glassy carbon electrode (Gr/p-ABA/GCE) was first employed for the sensitive determination of dopamine (DA). The electrochemical behavior of DA at the modified electrode was investigated by cyclic voltametry (CV), differential pulse voltametry (DPV) and amperometric curve. The oxidation peak currents of DA increased dramatically at Gr/p-ABA/GCE. The modified electrode was used to electrochemically detect dopamine (DA) in the presence of ascorbic acid (AA). The Gr/p-ABA composite film showed excellent electrocatalytic activity for the oxidation of DA in phosphate buffer solution (pH 6.5). The peak separation between DA and AA was large up to 220 mV. Using DPV technique, the calibration curve for DA determination was obtained in the range of 0.05-10 μM. The detection limit for DA was 20 nM. AA did not interfere with the determination of DA because of the very distinct attractive interaction between DA cations and the negatively Gr/p-ABA composite film. The proposed method exhibited good stability and reproducibility.     

Use of capillary electrophoresis for the determination of vitamins of the B group in pharmaceutical preparations

The separation of four water-soluble vitamins, i.e., thiamine, riboflavine, pyridoxine and nicotinamide, was investigated by capillary zone electrophoresis and micellar electrokinetic chromatography. The usefulness of the internal standard technique in order to improve the precision of peak area when either the migration time or the injection volume varied was demonstrated. Quantitative analyses of different pharmaceutical formulations were compared with the LC method of the US Pharmacopeia. A good correlation was obtained.     

Poly(pyridine‐3‐boronic acid)/Multiwalled Carbon Nanotubes Modified Glassy Carbon Electrodes for Simultaneous Determination of Ascorbic Acid, 3,4‐Dihydroxyphenylacetic Acid and Uric Acid

Poly(pyridine‐3‐boronic acid) (PPBA)/multiwalled carbon nanotubes (MWCNTs) composite modified glassy carbon electrode (GCE) was used for the simultaneous determination of ascorbic acid (AA), 3,4‐dihydroxyphenylacetic acid (DOPAC) and uric acid (UA). The anodic peaks for AA, DOPAC and UA at the PPBA/MWCNTs/GCE were well resolved in phosphate buffer solution (pH 7.4). The electrooxidation of AA, DOPAC and UA in the mixture solution was investigated. The peak currents increase with their concentrations increasing. The detection limits (S/N=3) of AA, DOPAC and UA are 5 µM, 3 µM and 0.6 µM, respectively.     

Electrochemical determination of serotonin and the competitive adsorption with dopamine at 5,5-ditetradecyl-2-(2-trimethylammonioethyl)-1,3-dioxane bromide lipid film modified by glassy carbon electrode.

A novel and effective approach to sensitively determine serotonin, known as 5-hydroxytryptamine (5-HT), has been proposed based on a 5,5-ditetradecyl-2-(2-trimethylammonioethyl)-1,3-dioxane bromide (DTDB) self-assembled lipid bilayer membrane modified glassy carbon electrode (DTDB/GCE). A DTDB/GCE shows the strong electrocatalysis for the oxidation of 5-HT, with the peak potential shifted to less positive value of 0.376 V vs. SCE, and effectively eliminates the interference from ascorbic acid (AA), even in the presence of 100-fold concentration of AA. Differential pulse voltammetry (DPV) gave a linear current for 5-HT from 2.0 x 10(-7) to 1.0 x 10(-5) M. At the DTDB/GCE, the oxidation of 5-HT was controlled by the adsorption process; for 5-HT coexisting with DA, the competitive adsorption was observed.     

电聚合烟酰胺制备电化学传感器：同时测定多巴胺、尿酸和抗坏血酸

用循环伏安法（CV）选择不同电位区间来电聚合烟酰胺（NA）得到了两种聚合物膜修饰电极：poly-niacinamide/GCE (poly-NA/GCE)和poly- nicotinic acid /GCE (poly-NC/GCE)。这两电极都具有显著电化学催化作用,能明显地降低多巴胺（DA）、尿酸（UA）和抗坏血酸(AA)的氧化过电位,并在混合溶液中使这些物质的氧化峰电位距离足够大,可进行三物质的同时测定。poly-NC/GCE的电催化性能更好一些,用差分脉冲伏安法（DPV）测定抗坏血酸,线性范围为75–3000 µmol L-1,电流灵敏度为5.6 mA•L•mol-1;测定多巴胺,线性范围为0.37 – 16 µmol L-1,电流灵敏度为1140 mA•L•mol-1; 测定尿酸,线性范围为0.74 – 230 µmol L-1,电流灵敏度为102 mA•L•mol-1。该电极具有很高的灵敏度、选择性和抗污染能力。     

Amperometric ascorbic acid biosensor based on carbon nanoplatelets derived from ground cherry husks

In this work, a novel amperometric biosensor based on carbon nanoplatelets derived from ground cherry (Physalis peruviana) husks (GCHs-CNPTs) is reported for the sensitive and selective detection of ascorbic acid (AA). The structure of the nanoplatelets, the oxygen-containing groups and edge-plane-like defective sites (EPDSs) on the GCHs-CNPTs were characterized by scanning electron microscopy, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The presence of GCHs-CNPTs with a high density of EPDSs effectively enhances the electron transfer between AA and the glassy carbon electrode (GCE), and thus induces a substantial decrease in the overvoltage for AA oxidation compared with both a bare GCE and a GCE modified with carbon nanotubes (CNTs/GCE). In particular, an amperometric biosensor based on GCHs-CNPTs exhibited a wider linear range (0.01–3.57 mM), higher sensitivity (208.63 μA mM^− 1 cm^− 2), a lower detection limit (1.09 μM, S/N = 3) and better resistance to fouling for AA determination compared to a CNTs/GCE. The great potential of the GCHs-CNPTs/GCE for practical and reliable AA analysis was demonstrated by the successful determination of AA in samples taken from a medical injection dose and a soft drink.     

石墨烯修饰玻碳电极用于循环伏安法测定抗坏血酸

采用Hummers法制备了纳米石墨烯,并将该纳米材料分散在蒸馏水中得到悬浮液,取5μL的悬浮液滴涂在玻碳电极表面,制备石墨烯修饰电极。用循环伏安法研究了在pH 4.0磷酸盐电解质中,在-0.4～0.8V(vs.Ag/AgCl)电位范围内,抗坏血酸在修饰电极上的电化学行为。结果表明:抗坏血酸在修饰电极上在0.173V处可见明显的氧化峰,且氧化峰电流显著高于在裸玻碳电极上的氧化峰电流;并可有效排除肾上腺素、尿酸、多巴胺等物质的干扰。据此提出了用循环伏安法测定抗坏血酸的方法。抗坏血酸的线性范围为8.00×10-6～1.0×10-3 mol.L-1,检出限(3S/N)为1.0×10-7 mol.L-1。方法用于维生素C片的分析,回收率在96.3%～104.4%之间。     

抗坏血酸和尿酸在甘氨酸-壳聚糖修饰玻碳电极上的电化学行为及测定

制备了甘氨酸-壳聚糖复合膜修饰玻碳电极(Gly-CTS/GCE),研究了抗坏血酸(AA)和尿酸(UA)在该修饰电极上的电化学行为。结果表明在pH=5.59的磷酸盐缓冲溶液中,AA、UA在Gly-CTS/GCE上均产生灵敏的不可逆氧化峰,其峰电流与浓度在一定范围内呈良好的线性关系。对AA和UA混合溶液平行测定7次,相对标准偏差分别为4.6%、2.9%,表明该电极重现性和稳定性良好。AA、UA在Gly-CTS/GCE电极上的氧化峰峰电位相差340mV,据此可实现对二者的同时检测,并可应用于实际样品测定。     

聚对氨基苯磺酸/石墨烯电化学修饰电极检测药物中氧氟沙星

基于石墨烯纳米材料和循环伏安法技术制备了聚对氨基苯磺酸/石墨烯修饰电极并研究了氧氟沙星(OFL)在该修饰电极上的电化学行为,建立了一种简单快速灵敏测定氧氟沙星的电化学分析方法。 结果表明,与玻碳电极相比,对氨基苯磺酸/石墨烯电化学修饰电极能显著提高氧氟沙星的峰电流。 在优化条件下,其检测线性范围为1~600 μmol/L,最低检测限为(S/N=3)0.33μmol/L。 该修饰电极具有较好的重现性和稳定性,用于实际样品氧氟沙星滴眼液的测定,效果良好。     

Preparation of polyaniline modified electrode in novel ionic liquid and its application in ion chromatography

In this work, a promising electrochemical detector has been fabricated by immersing a glass carbon electrode (GCE) in aniline containing novel ionic liquid and scanning between -1.0 and 1.0 V for 40 cycles, and was used in ion chromatography (IC) system. The morphology of the modified electrode surface was characterized by scanning electron microscope (SEM). The polyaniline (PANI) film showed excellent electrocatalytic activity than bare GCE and provided enhanced selectivity and stability for the detection of ascorbic acid (AA). Separated by IC with phosphate buffer solution (pH = 5.2) as eluent, AA could be determined by the PANI/GCE successfully at the working potential of 0.3 V. The retention time of AA was approximately 5.75 min, and the peak shape of AA was satisfactory. The calibration curve of AA was linear (r > 0.99), in the range between 0.05 mg/L and 1000 mg/L and the detection limit was 23.41 μg/L (S/N = 3). The proposed method was successfully applied in the detection of AA in four beverage samples. The recoveries of AA in these samples were from 92.32% to 110.57%.     

Electropolymerization of Thin Film Conducting Polymer and Its Application for Simultaneous Determination of Ascorbic Acid,Dopamine and Uric Acid

In this paper electropolymerization of a thin film of para‐phenylenediamine (PPD) is studied at glassy carbon electrode (GCE) in sulfuric acid media by cyclic voltammetry. The results showed that this polymer was conducting and had a reproducible redox couple in the potential region from 0.0 to 0.4 V in phosphate buffer solution. This modified GCE (p‐PPD‐GCE) was applied for simultaneous determination of ascorbic acid (AA), dopamine (DA) and uric acid (UA) using differential pulse voltammetry (DPV). The p‐PPD‐GCE in 0.1 M phosphate buffer solution (pH 5.0) separated the DPV signals of AA, DA and UA with sufficient potential differences between AA–DA and DA–UA and also enhanced their oxidation peak currents. The oxidation currents were increased from 2.0 to 2000.0 µM for AA, 10.0 to 1250.0 µM for DA and 50.0 to 1600.0 µM for UA. The detection limits were evaluated as 0.4, 1.0 and 2.5 µM for AA, DA and UA, respectively (S/N=3).     

CuO Nanostructures Based Electrochemical Sensor for Simultaneous Determination of Hydroquinone and Ascorbic Acid

A simple, sensitive and reliable electrochemical sensor has been developed based on CuO nanostructures modified glassy carbon electrode for simultaneous determination of hydroquinone (HQ) and ascorbic acid (AA). The CuO nano material was synthesized by aqueous chemical growth method using different sources of OH. The characterization of nano material was performed by Fourier transform infrared spectroscopy, X‐ray diffraction, field emission scanning electron microscopy and energy dispersive X‐ray spectroscopy. The glassy carbon electrode was modified by CuO nano material using drop cast method and studied by cyclic voltammetry. The CuO/GCE exhibited excellent electrocatalytic activity towards the oxidations of HQ and AA in borate buffer solution (pH 8.0) and the corresponding electrochemical signals have appeared as two well resolved oxidation peaks with significant peak potential differences of (0.21V vs. Ag/AgCl). Differential pulse voltammetry was used for simultaneous determination of HQ and AA using the CuO/GCE. At the optimum conditions, for simultaneous determination by synchronous change of the analyte concentrations, the linear response ranges were between 0.0003–0.355 mM for HQ and 0.0001–0.30 mM for AA respectively. Furthermore, CuO/GCE was successfully applied for the independent determination of AA in fruit juices as well as for the simultaneous determination of HQ and AA in cosmetic samples.