电化学法快速测定芹菜总黄酮含量

利用差分脉冲伏安法对芹菜总黄酮进行定量分析。选择芦丁纯品作为测定芹菜总黄酮的标准品,以纯玻碳电极为工作电极,首先采用循环伏安法优化测定条件,然后在最佳测定条件下,采用差分脉冲伏安法测定芹菜中总黄酮的含量。试验表明,芹菜总黄酮氧化峰电流与其浓度在2.0×10-6 mol/L~1.3×10~(-4) mol/L范围内呈良好的线性关系,检出限达到1.2×10~(-11) mol/L(S/N=3)。     

纳米金掺杂石墨烯修饰玻碳电极选择性测定多巴胺

构建纳米金(Au)掺杂石墨烯(GS-Nafion)修饰玻碳电极(GCE)的电化学传感器(GCE/GS/Nafion/Au),研究多巴胺(DA)和抗坏血酸(AA)在上述电极的电化学行为,并用于DA的选择性测定。将GS-Nafion溶液涂覆于GCE表面制得GCE/GS/Nafion电极,采用化学镀方法于GCE/GS/Nafion电极表面生成Au制得GCE/GS/Nafion/Au电极,采用扫描电镜(SEM)表征GS、化学镀Au和电极的制备过程,循环伏安(CV)法和示差脉冲伏安(DPV)法研究DA的电化学性质。在优化的实验条件下,DA浓度与DPV法氧化峰电流大小在1.0×10-7～1.0×10-4mol/L之间呈线性关系,线性相关系数为0.9988,检出限为4.2×10-8mol/L。该电极制备过程简单、灵敏度高、抗干扰性强,可以用于DA的测定,结果令人满意。     

Pt—Fe(Ⅲ)/MWCNTs修饰电极伏安法测定食品中的亚硝酸根

采用滴涂法和电化学沉积法构建Pt—Fe(Ⅲ)/多壁碳纳米管(MWCNTs)修饰玻碳电极(Pt—Fe(Ⅲ)/MWCNTs/GCE),研究该修饰电极对NO2-的电催化作用,并优化试验条件,在该基础上建立一种差分脉冲伏安法(DPV)测定NO2-的新方法。NO2-的氧化峰电流与其浓度在3.0×10-7~2.0×10-3 mol/L范围内呈良好的线性关系(r=0.999 3),检测限为1.0×10-7 mol/L,将该方法用于食品中NO2-的测定,效果满意。     

聚L-瓜氨酸修饰电极电化学测定食品中曲酸

为建立快速检测食品中曲酸含量的方法,通过电化学的方法将L-瓜氨酸聚合在玻碳电极表面上,制备聚L-瓜氨酸修饰电极。在最佳实验条件下,采用循环伏安法研究了曲酸在聚L-瓜氨酸修饰电极和玻碳电极上的电化学行为,与玻碳电极相比,修饰后的电极对溶液具有更好的电化学响应。曲酸的浓度在8.0×10~(-6)～2.8×10~(-4)mol/L范围内,与其氧化峰电流(i_(pa))呈良好的线性相关,相关系数为0.995 5,检出限为4.0×10~(-6)mol/L,其线性方程为i_(pa)=1.03×10~(-6)+0.060c (mol/L)。该修饰电极的灵敏度、选择性和重现性较好,适用于黄豆酱、醋和酱油中曲酸的分析。     

色氨酸在Nafion-聚半胱氨酸修饰电极上的电化学行为及分析测定

采用滴涂和电聚合的方法构筑Nafion-聚半胱氨酸修饰的玻碳电极(Nafion/L-cys/GCE),采用循环伏安法(CV)研究色氨酸在此修饰电极上的电化学行为,利用线性扫描伏安法(LSV)对色氨酸进行定量分析。结果表明,该修饰电极对色氨酸电化学氧化具有明显催化作用。色氨酸浓度在0.4×10-6~40.0×10-6mol/L范围内与氧化峰电流有良好线性关系,回归方程为I_pa(μA)=0.6997c(10-6mol/L)+5.3(R2=0.9844),检测限为1.0×10-7 mol/L。该方法用于香蕉中色氨酸的检测,回收率为95%~98%。     

抗坏血酸在聚对苯二酚/铜复合膜修饰电极上电催化氧化行为的探究

利用电沉积法制备了聚对苯二酚/铜(PHQ/Cu)复合膜修饰电极,并采用循坏伏安法探究了抗坏血酸(AA)在该电极上的电催化氧化行为。结果表明,与裸电极、PHQ修饰电极相比,PHQ/Cu复合膜修饰电极对AA具有更好的催化作用,表明两种修饰剂对AA的电催化氧化有良好的协同催化作用;在0.1 mol/L磷酸盐缓冲溶液(pH=4.35)中,AA的氧化峰电流与其浓度在5×10-4~1.0×10-1 mol/L范围内呈良好的线性关系,线性方程为lgI=0.7364lgc+1.6932,R2=0.9959,检出限为2.0×10-5 mol/L。该复合膜修饰电极在冰箱内贮存9 h,其电化学信号基本保持不变,且共存物几乎不干扰AA的测定,表明电极具有良好的稳定性和较强的抗干扰能力,可以用于饮料中AA含量的测定,回收率在95.5%~109.1%之间。     

基于方波伏安法的聚多巴胺@纳米银修饰玻碳电极测定畜禽肉中氯丙嗪

基于多巴胺(dopamine,DA)的自聚反应,在纳米银(sliver nanoparticles,AgNPs)和玻碳电极(glassy carbon electrode,GCE)表面形成聚多巴胺(polydopamine,PDA)膜,使AgNPs均匀分散在GCE表面,得到PDA@AgNPs/GCE修饰电极;对DA的自聚时间、氯丙嗪的电化学测试方法及条件等进行考察和优化,构建基于方波伏安法的氯丙嗪快速检测方法;利用循环伏安法、交流阻抗法和扫描电子显微镜对修饰电极进行表征。最佳条件下,氯丙嗪在PDA@AgNPs/GCE上的氧化峰电流与其浓度在5.0×10^-8～1.0×10^-5 mol/L范围内呈良好的线性关系(R²=0.991),检出限(R_SN=3)为1.7×10^-8 mol/L。用该法测定猪肉、鸡肉和牛肉中氯丙嗪的加标回收率分别为84.9%～88.8%、79.8%～93.8%、80.6%～93.9%。该方法所用测试仪器轻巧便携,修饰电极的制备方法简便易行、成本低、便于批量制备,...     

基于碳纳米管组装电化学传感器测定金丝桃苷的含量

目的:采用单壁碳纳米管(SWCNTs)修饰玻碳电极(GCE),制作电化学传感器,研究金丝桃苷在传感器表面的电化学行为,建立一种简单的、高灵敏的金丝桃苷的电化学检测新方法。方法:将羧基化SWCNTs滴在GCE表面,采用循环伏安法(CV)研究了金丝桃苷在传感器表面的电化学行为,并对测量条件进行了优化。结果:和裸GCE电极相比较,金丝桃苷在GCE/SWCNTs电极表面的氧化峰电流和还原峰电流均急剧增加,氧化峰电流和还原峰电流与扫描速度的平方根成正比,说明金丝桃苷在修饰电极表面的反应是受扩散控制的过程。在缓冲液的pH为6.0、碳纳米管的用量为10 μL、检测电位为0.34 V的优化条件下时,金丝桃苷浓度在3.0×10-9~1.0×10-7范围内与氧化电流呈现良好的线性关系,检出限为2.41×10-9 mol/L(S/N=3)。结论:该方法灵敏度高,简单易行,具有较好的重现性及稳定性,可用于金丝桃苷的检测。     

聚三聚氰胺修饰玻碳电极测定食品中叔丁基对苯二酚

采用电化学聚合方法制备了聚三聚氰胺膜修饰玻碳电极(poly melamine film modified glassy carbon electrode,PMel/GCE),并采用循环伏安法研究了抗氧化剂叔丁基对苯二酚(tert-butylhydroquinone,TBHQ)在修饰电极上的电化学行为,发现其氧化还原峰电流较在玻碳电极(glassy carbon electrode,GCE)上明显增强,提高了检测的灵敏度。对三聚氰胺电化学聚合时间、扫描速率、电压、段数以及测定TBHQ溶液的pH值等实验条件进行了优化。在最佳的条件下,TBHQ在4.00×10-7~1.00×10-4mol/L内与其氧化峰电流呈线性关系,相关系数:R=0.997 5,检出限为2.00×10-9mol/L。将修饰电极用于食品中TBHQ的检测,回收率在96.9%~102.2%之间。     

聚中性红修饰电极测定维生素C的方法研究

对聚中性红修饰电极的制备方法进行了研究,通过循环伏安法(CV)找到了制备电极的最佳实验条件.研究了VC在聚中性红修饰电极的电化学行为,发现聚中性修饰电极对Vc有良好的伏安响应,在100mV/s的扫速下,VC在该修饰电极上产生一对准可逆氧化还原峰,峰电流与VC浓度在1.0×10-5～1.0×10-2mol/L范围内有良好的线性关系,检出限可达到1.0×10-6mol/L.与紫外光谱法作比较,该实验方法具有可行性.     

基于不同化学还原法制备的Au/XC-72及其对L-CySH的催化氧化反应研究

本文采用乙二醇还原法、抗坏血酸还原法、柠檬酸三钠还原法及硼氢化钠还原法合成胶体金溶液,并将其负载于XC-72上制备Au/XC-72催化剂。X射线衍射(XRD)表明四种方法制备的催化剂均具有明显的Au特征衍射峰,且硼氢化钠还原法制备的Au衍射峰最平缓。透射电子显微镜(TEM)表明硼氢化钠还原法制备的金纳米颗粒(Au NPs)粒径最小,在XC-72表面分布均匀,其他三种方法制备的AuNPs粒径较大,且发生不同程度的团聚。利用制备的催化剂(Au/XC-72)修饰玻碳电极(GCE)并用于L-半胱氨酸(L-CySH)的电催化氧化机制研究,结果显示硼氢化钠还原法制备的Au/XC-72在pH为2时对L-CySH的催化氧化较其它三种方法制备的材料表现出最优的活性,且在1m M～10m M的范围内呈现线性关系,表明L-CySH在Au/XC-72上的氧化反应的速率是受扩散过程控制的。电催化活性高粒径小的Au/XC-72修饰GCE构建的传感器具有广泛的实际应用价值。     

金纳米粒子修饰电极循环伏安法测定食品中的碘

为寻求一种快速、简便、灵敏的食品中碘的测定方法,利用循环伏安法（CV）构建金纳米粒子修饰电极检测碘离子（I-）体系。利用甲烷氧化菌素（Mb）原位还原纳米金（Mb@AuNPs）,电沉积法制备自组装修饰电极。通过透射电子显微镜对Mb@AuNPs表征,CV考察碘离子的电化学行为。确定碘离子检测的优化条件为:电沉积扫描速率0.11 V/s、扫描圈数30圈、缓冲溶液浓度0.05 mol/L、缓冲溶液pH6.5。氧化峰电流与I-浓度在0.01~10.00 μmol/L范围内有良好的线性关系,R2为0.9992,检出限为2.88 nmol/L（S/N）,定量限为9.60 nmol/L,该方法检测不同食品中碘含量的加标回收率为96.22%~103.57%。结果表明该修饰电极对I-的测定具有良好的精密度、稳定性和重现性,以及较好的抗干扰能力,符合测定方法要求,可用于实际样品中碘的测定。     

电化学方法快速测定牛奶中的三聚氰胺

建立一种快速测定牛奶中三聚氰胺的电化学方法。先用三氯乙酸溶解牛奶样品,通过固相萃取提取其中的三聚氰胺。将玻碳电极在含三聚氰胺的牛奶样品提取液中进行循环伏安法扫描,在0.7V左右会出现一对氧化还原峰,此峰电流与三聚氰胺含量在15～345mg/kg的范围内呈线性关系,该方法检测三聚氰胺的检测限为5mg/kg,测定方法的回收率和相对标准偏差分别为97.3%～101.2%和3.5%～4.5%。相对于其他测定方法,此方法的样品预处理过程简单、测定速度快、成本低、不需要复杂的仪器设备。     

Determination of Ge(IV) in rice in a mercury-coated glassy carbon electrode in the presence of catechol

Electrochemical adsorptive cathodic stripping voltammetry determination of Ge(IV) using the catechol complex on a mercury-coated (MC) electrode was prepared using a glassy carbon electrode (GCE), the peak potential of which was −0.5 V vs. Ag/AgCl on MCGCE. The various parameters of the catechol concentration, its pH, and others were optimized. The linear working ranges were obtained in the concentration of 2–700 μg L⁻¹ Ge(IV). The relative standard deviation at the Ge(IV) concentration of 50 μg L⁻¹ was 1.37% (n = 15) using the optimum condition, and the detection limit was found to be 0.6 μg L⁻¹ (8.26 × 10⁻⁹ M) (S/N = 3), with an adsorption time of 180 s. The Ge(IV) response was highly linear. This developed method was applied to Ge(IV) to determine the presence of rice grains.     

Identification of monofloral honey using voltammetric electronic tongue

Quality assessment of honey is often related to its floral origin which is a complex task to evaluate. Traditional technique of floral assessment is made by melissopalynological method. However, this method is quite time consuming and also often operator dependent. Thus, the fallout is a large range of error in interpretation of the result and hence there is considerable demand for instrumental methods to assess the identification of pollen in honey. In this pursuit, an electronic tongue based on cyclic voltammetry is developed to discriminate honey samples based on their floral types and is described in this paper. The technique has been investigated using platinum as the working electrode and the resultant current from the potentiostat has been considered for data analysis. The use of principal component analysis (PCA) and linear discriminate analysis (LDA) proves to be useful in clustering honey samples. Finally, classification performances are investigated using back-propagation multilayer perceptron (BP-MLP) and radial basis function (RBF) neural network models for identification of different floral origin of honey.     

Classification of black tea liquor using cyclic voltammetry

Tea quality evaluation is a complex task and is carried out qualitatively in the industry by experienced tea tasters. But, the unpredictable and inconsistent nature of human panel tasting demands instrumental methods to assess the quality of black tea in an objective manner. For discrimination between different black tea samples and instrumental evaluation of their quality, a new method employing the principle of cyclic voltammetry is proposed in this paper. The technique has been investigated using platinum and glassy carbon as working electrodes and the resultant current from the potentiostat has been considered for data analysis. First, principal component analysis (PCA) and linear discriminant analysis (LDA) has been performed for visualization of underlying clusters and finally, a neural network model has been used to classify the data. The performance of the classifier has been established using 10-fold cross-validation method.     

基于Au/SiO2信号放大的沙门氏菌检测方法

目的：基于Au/SiO2信号放大,通过循环伏安法实现对沙门氏菌（Salmonella）的高灵敏度检测。方法：将与沙门氏菌靶基因DNA互补配对的碱基序列（捕捉DNA和显示DNA）,分别修饰于导电玻璃电极（indium tin oxide,ITO）及Au/SiO2纳米颗粒表面,构建捕获探针和显示探针,当在体系中加入沙门氏菌靶DNA后,会形成捕捉DNA-靶DNA-显示DNA构成的“三明治夹心”结构。由于Au/SiO2的含量与靶DNA浓度呈正相关,因此靶DNA浓度的变化可导致ITO峰电流值相应变化,从而达到检测目的。结果：在最优实验条件下,检测沙门氏菌靶DNA时,浓度在10－11～10－7 mol/L范围内呈现出良好的线性关系,线性回归方程为y=－0.000 3x＋0.000 1（R2=0.998 9）,最低检测限为6 pmol/L;检测沙门氏菌时,线性范围为50～7 910 CFU/mL,线性回归方程为y=－1.6×10－7x＋0.003 2（R2=0.994 0）,最低检测限为35 CFU/mL。结论：经特异性及实验加标回收实验证明本方法可用于实际样品的检测。     

Determination of trans-resveratrol in red wine by adsorptive stripping square-wave voltammetry with medium exchange

In the present paper, a method for the determination of trans-resveratrol in red wine samples, by adsorptive stripping square-wave voltammetry (Ad-SSWV) in a glassy carbon electrode, is presented. In 0.10 M perchloric medium, trans-resveratrol experiments an adsorptive–oxidative process, which promotes the appearance of a peak at 0.72 V. Calibration graph have been constructed from 5.0 to 35 ng/mL. Detection limit of 4.2 ng/mL has been calculated, according to Clayton criterion. Extraction of trans-resveratrol from red wine with diethylether and posterior clean-up with C18 cartridges is carried out. Recovery percentages close to 100% have been calculated with different red wine samples. The accumulation of analyte in the electrode is carried out at +0.60 V for 60 s, in the presence of 0.10 M HClO₄ and 10% of ethanol; the measurement stage is performed after a medium exchange, in 0.10 M HClO₄ and 30% of ethanol. The standard addition method was employed for the analysis of real samples, since a matrix effect is observed in red wine extract. The method has been applied to several commercial red wines samples, and the results have been satisfactorily validated by HPLC.     

方波伏安法检测酱油和食盐中乙二胺四乙酸铁钠

采用方波伏安法建立乙二胺四乙酸铁钠(NaFeEDTA)的检测方法。用pH值为3.0的磷酸缓冲溶液作为底液;电化学条件为扫描增量10mV、方波频率2.5kHz、方波振幅100mV,可实现对NaFeEDTA的检测。试液中NaFeEDTA的质量浓度在10～200mg/L范围内,标准曲线相关系数为0.9997,检出限为4mg/L。对铁强化酱油和食盐中的NaFeEDTA检测的回收率为(93.5±2.1)%和(96.8±2.8)%。     

Lead levels in retail samples of Spanish infant formulae and their contribution to dietary intake of infants

Lead concentrations in 82 different types of infant formulae (cow's milk and soy based) marked in Spain were analysed by acid-microwave decomposition and anodic stripping voltammetry. Dietary lead intake from infant formula and tap water used for powder formula reconstitution were estimated in comparison with the provisional tolerable weekly intake (PTWI). Additionally, the influence of physical state (powder and ready-to-use formulae), the type of container used and the impact of the industrial process from different manufacturers on lead levels were evaluated. According to the results, lead exposure from drinking water was negligible with respect to formulae investigated; where soya formulae contributed the highest intake (58-73% PTWI), non-adapted starter and specialized formulae gave an moderate intake (31-42 and 26-37% PTWI, respectively), and, finally, pre-term, adapted starter and follow-up formulae provided the lowest lead intake (22-25, 22-26 and 16-22% PTWI, respectively). Based on the current state of knowledge about lead toxicity, manufacturers are called to make an additional effort in order to keep a maximum lead level at 20 µg l^-1 for all infant formulae, although it is recommendable that these formulations supply the upper limit (5 µg l^-1) of 'normal' human milk.