对氨基苯酚在石墨烯-离子液体复合物修饰电极上的电化学行为研究

使用石墨烯(Graphene,GR)和离子液体1-丁基-3-甲基咪唑六氟磷酸盐([BMIM] PF6)作修饰剂,通过壳聚糖(CHIT)成膜,制备了石墨烯-离子液体复合物修饰电极([BMIM] PF6 - GR - CHIT/GCE).在0.1 mol/L磷酸盐缓冲液中,采用循环伏安和微分脉冲伏安法研究了对氨基苯酚在[...     

双酚A在纳米金-离子液体复合修饰电极上的电化学行为及测定

该文制备了纳米金-离子液体修饰电极(GNP-[BMIM]PF6/GCE),用红外光谱对GNP和[BMIM]PF6进行了表征.采用交流阻抗法研究了GNP-[BMIM]PF6/GCE的表面电化学特性,同时研究了双酚A(BPA)在该修饰电极上的循环伏安行为.结果表明,BPA在该修饰电极上出现1个氧化峰,无还原峰,为不可逆电化...     

磷钨酸改性蒙脱土-离子液体修饰电极上百草枯的电化学行为及测定

该文制备了磷钨酸改性蒙脱土-离子液体修饰电极(PTA-MMT-[BMIM]PF6/GCE),用红外光谱对PTA-MMT和[BMIM]PF6进行了表征.通过对比改性前后电极的交流阻抗图,发现PQ在PTA-MMT-[BMIM]PF6/GCE上电荷转移的电阻最小.研究了百草枯(PQ)在该修饰电极上的循环伏安行为.结果表明,在...     

乙炔黑-离子液体复合修饰电极上阿昔洛韦的电化学行为研究

采用乙炔黑(Acetylene Black,AB)和离子液体(1-丁基-3-甲基咪唑六氟磷酸盐[BMIM]PF6)作为复合修饰材料,制备乙炔黑-离子液体复合修饰电极(AB-[BMIM]PF6/GCE)。用红外光谱法对AB-[BMIM]PF6/GCE进行表征,用循环伏安法(CV)研究阿昔洛韦(ACV)在该修饰电极上的电化学行为。实验结果表明,在pH=4.70的磷酸盐缓冲液(PBS)中,ACV在该修饰电极上出现一氧化峰。在20~280mV/s扫速范围内,氧化峰电流与扫速平方根呈线性关系,表明该电极过程是受扩散控制。电极过程的部分动力学参数分别为:电极有效面积0.076cm2,转移电子数2,扩散系数1.817×10-4 cm2/s。用方波伏安法(SWV)测定一系列不同浓度的ACV溶液,结果表明其氧化峰电流与ACV浓度在7.0×10-7~1.0×10-4 mol/L范围内呈良好线性关系,相关系数为0.993,检出限(S/N=3)为2.30×10-7 mol/L,加标回收率为95.0%~105.6%。     

离子液体BMIMPF6修饰碳糊电极电化学测定维生素E

用疏水性离子液体1-丁基-3-甲基咪唑六氟磷酸([BMIM]PF6)作粘合剂制备了离子液体修饰碳糊电极(IL/CPE)。采用循环伏安法(CV)研究了维生素E(vitamin E,VE)的氧化产物生育酚红在IL/CPE和未修饰碳糊电极(CPE)上的电化学行为,结果表明生育酚红在IL/CPE上氧化过程更易于进行,峰电流响应ip也明显增加,表明IL/CPE对生育酚红的氧化还原反应具有良好的电催化作用。同时测定了电极过程的动力学参数:电荷转移系数α=0.8746,扩散系数D=1.65×10-3cm2/s,电极反应速率常数kf=6.64×10-2cm/s。采用方波伏安法(SWV)发现生育酚红氧化峰电流与其浓度在1.53×10-4mol/L～8.39×10-7mol/L范围内呈线性关系,检出限为1.58×10-8mol/L。该法可用于VE实际样品的分析测定。     

EuCl_3在氯化1-丁基-3-甲基咪唑中的电化学性质

应用循环伏安法研究了Eu3+在亲水性离子液体—氯化1-丁基-3-甲基咪唑([BMIM]Cl)中的电极过程.实验表明,工作电极为玻碳电极时,[BMIM]Cl的电化学窗口为-1.7～0.80V(vs.Ag/AgCl).Eu3+在[BMIM]Cl中被还原为Eu2+,此电极反应受电荷迁移和物质扩散共同控制.当体系温度从55℃升高到75℃时,Eu3+在[BMIM]Cl中的扩散系数D从3.75×10-9cm2/s变化到1.32×10-8cm2/s,该反应活化能Ea为62.6kJ/mol.     

离子液体/多壁碳纳米管/壳聚糖修饰电极同时检测多巴胺、抗坏血酸及尿酸的研究

将水溶性离子液体([ BMIM] N(CN)2)、多壁碳纳米管(MWCNTs)和壳聚糖(CS)三者结合,修饰在玻碳电极上制备MWCNTs - IL - CS修饰玻碳电极,并研究了多巴胺(DA)、抗坏血酸(AA)、尿酸(UA)在该修饰电极上的电化学行为.扫描电子显微镜图显示,MWCNTs在IL - CS中能良好分散,并形...     

纳米金/单壁碳管修饰玻碳电极对黄芩苷的电催化作用及快速检测

用循环伏安法(CV)在单壁碳纳米管表面直接沉积金纳米粒子,制备了纳米金/单壁碳纳米管修饰玻碳电极(NG/SWNT/GCE),并用扫描电镜(SEM)进行表征。研究了黄芩苷在该修饰电极上的电化学行为,结果表明该修饰电极对黄芩苷具有电催化作用。用示差脉冲伏安法(DPV)对黄芩苷进行测定,其氧化峰电流与黄芩苷浓度在2.0×10-8～7.0×10-6mol/L范围内呈线性关系。检出限为5.0×10-9mol/L(S/N=3)。该修饰电极实测了中药黄芩粉中黄芩苷的含量,回收率在96.8%～102.5%。     

碳纳米管-离子液体-木质素磺酸钠复合物修饰电极同位镀铋膜测定水中铅和镉

采用涂覆法制备多壁碳纳米管(MWCNTs)-离子液体([BMIM]PF6)-木质素磺酸钠(LSS)修饰玻碳电极(GCE),然后在其表面同位镀铋膜,研究Pb(Ⅱ)和Cd(Ⅱ)在该修饰电极上的阳极溶出伏安行为。实验表明,Pb、Cd在该修饰电极上分别于-0.44V、-0.73V产生灵敏的溶出峰,Pb(Ⅱ)和Cd(Ⅱ)分别在3.0×10-8～1.0×10-6mol·L-1和2.0×10-8～8.0×10-7mol·L-1浓度范围内与其溶出峰电流呈良好的线性关系,检出限分别为4.1×10-9mol·L-1、6.9×10-9mol·L-1。该修饰电极制备简单,重现性好,用于河水中铅和镉的测定,效果良好。     

黄芩苷在Nb_2O_5-石墨烯纳米复合材料修饰电极上的电化学行为及测定

本文采用一步溶剂热法制备Nb2O5-石墨烯(Nb2O5-RGO)纳米复合材料,用于构建一种新型的黄芩苷电化学传感器。用扫描电子显微镜(SEM)对Nb2O5-RGO复合材料进行形貌表征。采用循环伏安法(CV)和线性扫描伏安法(LSV)研究了黄芩苷在Nb2O5-RGO修饰电极上的电化学行为。结果发现,Nb2O5-RGO修饰电极对黄芩苷具有显著的电催化活性。用差分脉冲伏安法(DPV)对黄芩苷进行测定,其氧化峰电流与浓度在1.0×10-5~1.5×10-6 mol·L-1和1.0×10-6~5.0×10-8 mol·L-1范围内呈良好的线性关系,检出限(S/N=3)为1.5×10-8 mol·L-1。该修饰电极的选择性高、重复性和稳定性较好。用于测定黄芩颗粒中黄芩苷的含量,加标回收率为93.0%~95.1%。     

盐酸吡哆辛在聚烟酸修饰电极上的电化学行为及测定

采用电聚合方法制备了聚烟酸修饰玻碳电极(PNA/GCE),并利用循环伏安法(CV)和差分脉冲伏安法(DPV)考察了盐酸吡哆辛(VB6)在该修饰电极上的电化学行为。结果表明,VB6在PNA/GCE上的氧化峰电流显著提高,电极反应为扩散控制的一电子两质子反应。利用差分脉冲伏安法对VB6进行测定,线性范围为0.08~400μmol/L,VB6的检出限为0.02μmol/L,测定结果的相对标准偏差为3.1%(n=8),加标回收率为95.8%~103.7%。该方法可用于VB6片中VB6含量的测定。     

Electrochemical study of the hetero-bimetallic complex [MeNC(CO)2Mn(dppm)2Pt(H)(CNMe)]+PF 6 − at a glassy carbon electrode

Summary Cyclic voltammetry (CV), convolution-deconvolution transformation of current, chronopotentiometry (CP), and digital simulation studies were used to evaluate the kinetic parameters of the electrode reaction of the hetero-bimetallic complex [MeNC(CO)₂Mn(dppm)₂Pt(H)(CNMe)]⁺PF ₆ ^– in dichloromethane at a glassy carbon electrode (GCE). It was found that the complex undergoes a reduction step at –0.895±0.01 V and two anodic steps at +0.903±0.01 V and 1.370±0.01 V. The reduction and oxidation steps are followed by a rapid chemical process. On the basis of the electrochemical results, an overall oxidation process was found to proceed as EEC, while the reduction process proceeds according to an ECEC scheme.

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Elektrochemische Untersuchung des hetero-bimetallischen Komplexes [MeNC(CO)₂Mn(dppm)₂Pt(H)(CNMe)]⁺PF ₆ ^– mit einer Glaskohlenstoffelektrode

Zusammenfassung Cyclische Voltammetrie (CV), Strom-Konvolution-Dekonvolution, Chronopotentiometrie und digitale Simulation wurden zur Bestimmung der kinetischen Parameter der Reaktion des hetero-bimetallischen Komplexes [MeNC(CO)₂Mn(dppm)₂Pt(H)(CNMe)]⁺PF ₆ ^– an einer Glaskohlenstoffelektrode (GCE) in Dichlormethan eingesetzt. Der Komplex zeigt eine Reduktionsstufe bei –0.895±0.01 V und zwei anodische Stufen bei 0.903±0.01 V und 1.370±0.01 V. Auf die Reduktions-und Oxidationsschritte folgt unmittelbar ein schneller chemischer Prozeß. Aus den elektrochemischen Ergebnissen läßt sich ein Gesamtoxidationsprozeß nach einem EEC — Schema ableiten, während die Reduktion nach einem ECEC — Schema verläuft.

     

Electrochemical Behaviors of Baicalin at an Electrochemically Activated Glassy Carbon Electrode and Its Determination in Human Blood Serum

Electrochemical behavior of baicalin (BA) at an electrochemically activated glassy carbon electrode (GCE) had been investigated in Britton‐Robinson (B‐R) buffer solution (pH = 2.87) by cyclic voltammetry (CV) and square wave voltammetry (SWV). The experimental results suggested that the electrode exhibited an electrocatalytic activity toward the redox of BA. The electron transfer coefficient (α) and the standard rate constant (k_s) of BA at the electrochemically activated glassy carbon electrode were calculated. The reaction mechanism was proposed and discussed in this work. Under the selected conditions, the reduction peak current was linearly dependent on the concentration of BA in the range of 5.0 × 10^?8 to 3.0 × 10^?6 mol L^?1 (r = 0.9990), with a detection limit of 2.0 × 10^?8 mol L^?1. The relative standard deviation (R.S.D.) for five times successful determination of 1.0 × 10^?6 mol L^?1 baicalin were 2.9%. The proposed method was also successfully applied for the determination of BA in human blood serum.     

2-氨基酚在离子液体-壳聚糖复合修饰电极上的电化学行为及其测定

本文采用离子液体1-丁基-3-甲基咪唑六氟磷酸盐(BMIMPF6)和壳聚糖(Chi)作为修饰剂,制备了新型修饰电极BMIMPF6-Chi/GCE,采用该修饰电极研究了2-氨基酚(OAP)的电化学行为,并对其进行了分析检测。实验结果表明,在pH=6.5的PBS缓冲液中,OAP于0.197V处出现一个明显的氧化峰,逆向扫描无还原峰,说明OAP在该电极上的电化学行为是不可逆的。OAP氧化峰电流与扫速的1/2次方在40～280 mV.s-1的范围内呈良好的线性关系,表明该电极过程受扩散控制。在最佳实验条件下,OAP峰电流与其浓度在4.0×10-7～2.0×10-4mol.L-1范围内呈良好的线性关系,Ipa(μA)=-0.534-18.424c(10-4mol.L-1),R=0.999,检出限1.4×10-7mol.L-1(S/N=3),回收率为96.8～103.7%。     

Development of a Molecularly Imprinted Poly(Acrylic Acid)‐MWCNT Nanocomposite Electrochemical Sensor for Tramadol Determination in Pharmaceutical Samples

A new voltammetric sensor based on molecularly imprinted poly(acrylic acid)‐MWCNT nanocomposite (MIP‐MWCNT) drop‐coated onto glassy carbon electrode (GCE) was developed and applied to tramadol (TR) determination in pharmaceutical samples. The voltammetric sensor prepared by suspension of MIP‐MWCNT at 1 : 1 (w/w) ratio show an improved performance compared to unmodified GCE. The electrochemical method is based on preconcentration of tramadol onto MIP‐MWCNT modified GCE surface at ?1.5 V vs Ag/AgCl for 180 s in 0.1 Britton‐Robinson buffer (pH 8.0) at stirred solution. Upon preconcentration, the differential anodic voltammogram was recorded under the optimized condition giving rise to an analytical curve varying from 9.0 up to 30.0 μmol L^?1 (R²=0.997) and limits of detection and quantification of 1.4 and 4.8 μmol L^?1, respectively. The method precision was assessed in terms of intraday (n=6) and interday (two consecutive days) precision, giving relative standard deviations (RSD%) values between 2.8 to 7.4 %. Excipients usually found in pharmaceutical pills (magnesium stearate, microcrystalline cellulose, starch, and silica) and paracetamol were evaluated as potential interferents, however no interference was evidenced in TR determination. The method applicability was evaluated by TR analysis in pharmaceutical samples. Moreover, the method accuracy was attested by comparison of addition and recovery assays with a reference technique (high‐performance liquid chromatography).     

Electrochemical Study and Application on Shikonin at Poly(diallyldimethylammonium chloride) Functionalized Graphene Sheets Modified Glass Carbon Electrode

The electrochemical behaviors of shikonin at a poly(diallyldimethylammonium chloride) functionalized graphene sheets modified glass carbon electrode(PDDA-GS/GCE) have been investigated. Shikonin could exhibit a pair of well-defined redox peaks at the PDDA-GS/GCE located at 0.681 V(E_pa) and 0.662 V(E_pc)[vs. saturated calomel electrode(SCE)] in 0.1 mol/L phosphate buffer solution(pH=2.0) with a peak-to-peak separation of about 20 mV, revealing a fast electron-transfer process. Moreover, the current response was remarkably increased at PDDA-GS/GCE compared with that at the bare GCE. The electrochemical behaviors of shikonin at the modified electrode were investigated. And the results indicate that the reaction involves the transfer of two electrons, accompanied by two protons and the electrochemical process is a diffusional-controlled electrode process. The electrochemical parameters of shikonin at the modified electrode, the electron-transfer coefficient(α), the electron-transfer number(n) and the electrode reaction rate constant(k_s) were calculated to be as 0.53, 2.18 and 3.6 s^-1, respectively. Under the optimal conditions, the peak current of differential pulse voltammetry(DPV) increased linearly with the shikonin concentration in a range from 9.472×10^-8 mol/L to 3.789×10^-6 mol/L with a detection limit of 3.157×10^-8 mol/L. The linear regression equation was I_p=0.7366c+0.7855(R=0.9978; I_p: 10^-7 A, c: 10^-8 mol/L). In addition, the modified glass carbon electrode also exhibited good stability, selectivity and acceptable reproducibility that could be used for the sensitive, simple and rapid determination of shikonin in real samples. Therefore, the present work offers a new way to broaden the analytical application of graphene in pharmaceutical analysis.     

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。     

A Reduced Graphene Oxide‐based Electrochemical DNA Biosensor for the Detection of Interaction between Cisplatin and DNA based on Guanine and Adenine Oxidation Signals

A glassy carbon electrode (GCE) was modified by electrochemically reduced graphene oxide (ERGO) for subsequent dsDNA immobilization. The interaction of cisplatin with dsDNA was studied at this modified electrode. Quantitative investigations were performed by adsorptive transfer stripping voltammetry (AdTSV) using differential pulse voltammetry (DPV). The morphology and structure of graphene oxide (GO) and ERGO modified GCEs (GO/GCE and ERGO/GCE, respectively) were characterized by UV‐vis, FT‐IR, Raman spectroscopy and cyclic voltammetry. Compared with the bare GCE and the GO/GCE, the ERGO/GCE exhibited excellent electrocatalytic activity towards the oxidation of dsDNA due to guanine and adenine groups, testified by high oxidation peak currents and decreased oxidation potentials. The interaction of micromolar concentrations of cisplatin with surface confined dsDNA was readily detected as inferred from the decrease of the voltammetric oxidation peaks of guanine and adenine. This trend was significantly greater at the ERGO/GCE compared to the GO/GCE. The interaction of cisplatin with dsDNA was also studied in solution phase by AdTSV with detection at the ERGO/GCE.