Enantioselective potential response of a human serum albumin-modified ITO electrode for tryptophan

The present study aims at extending the possibility of utilizing bulky molecules such as proteins for fabricating electrochemical chiral sensors using an indium tin oxide (ITO) electrode. Enantioselective potential response of the human serum albumin (HSA)-modified ITO electrode was observed for tryptophan (Trp) when HSA was immobilized on an ITO electrode surface modified with disuccinimidyl suberate (DSS). In this sensing system, the enantioselective interaction between HSA and Trp is detected through the chemically reactive DSS group immobilized on the ITO electrode.     

Covalent modification of a glassy carbon electrode with penicillamine for simultaneous determination of hydroquinone and catechol

A simple and highly selective electrochemical method has been developed for the simultaneous determination of hydroquinone (HQ) and catechol (CC) at a glassy carbon electrode covalently modified with penicillamine (Pen). The electrode is used for the simultaneous electrochemical determination of HQ and CC and shows an excellent electrocatalytical effect on the oxidation of HQ and CC upon cyclic voltammetry in acetate buffer solution of pH 5.0. In differential pulse voltammetric measurements, the modified electrode was able to separate the oxidation peak potentials of HQ and CC present in binary mixtures by about 103 mV although the bare electrode gave a single broad response. The determination limit of HQ in the presence of 0.1 mmol L⁻¹ CC was 1.0 × 10⁻⁶ mol L⁻¹, and the determination limit of CC in the presence of 0.1 mmol L⁻¹ HQ was 6.0 × 10⁻⁷ mol L⁻¹. The method was applied to the simultaneous determination of HQ and CC in a water sample. It is simple and highly selective.     

Phenylboronic acid self-assembled layer on glassy carbon electrode for recognition of glycoprotein peroxidase

We have successfully fabricated a phenylboronic acid self-assembled layer on glassy carbon electrodes (GCE), where 3-aminophenylboronic acid (APBA) is covalently bound to the electrochemical pretreated GCE surface with glutaraldehyde linkage. The specific binding of glycoprotein peroxidase with the self-assembled layer has been studied using horseradish peroxidase (HRP) as a model glycoprotein. Cyclic voltammetric, electrochemical impedance studies and photometric activity assays show that the affinity interaction of HRP with the APBA modified GCE surface includes specific and nonspecific bonding. The specific binding is attributed to the boronic acid–diols interaction where the boronic acid specifically binds the glycosylation sites of the HRP. This specific binding is reversible and can be split by sorbitol and glucose or released in an acidic buffer. The catalytic current of the HRP-loaded electrode, due to the catalytic oxidation of thionine in the presence of hydrogen peroxide, is proportional to HRP concentrations of the incubation solution. This work offers a new way to build novel sensors by specific binding of glycoproteins to a boronic acid self-assembled layer for determination of glycated proteins.     

电化学预处理玻炭电极上的电催化

用循环伏安法、计时电流法、计时库仑法和X射线光电子能谱法研究了恒电流法电化学预处理玻炭电极上的表面性质及其对抗坏血酸、儿茶酚和对苯二酚的电催化效应。讨论了电催化机理, 证明电极表面吸附及表面功能团的催化是发生电催化的主要原因。儿茶酚、对苯二酚和抗坏血酸的混合物的预处理电极上的波峰明显分开, 有可能应用于儿茶酚和抗坏血酸的同时测定。     

Enantioselective recognition of glutamic acid enantiomers based on poly(aniline-co-m-aminophenol) electrode column

A copolymer, poly(aniline-co-m-aminophenol), was synthesized by copolymerization of aniline and m-aminophenol in the presence of l-glutamic acid (l-Glu) as template molecules. The copolymer was filled into a porous ceramic column as the conductive stationary phase. Enantioselective recognition of Glu enantiomers was achieved on this special electrode column by applying different potentials on copolymers in the ceramic column. l-Glu anions were ejected from the ceramic column after electrochemical reduction due to the reversible redox of the copolymer while complementary cavities were left. Then a positive potential was applied to the molecularly imprinted poly(aniline-co-m-aminophenol) for re-binging Glu enantiomers in the mobile phase. The results showed good enantioselectivity.     

Redox behavior of biofilm on glassy carbon electrode

Marine and freshwater biofilm usually shift the open circuit potential (OCP) of stainless steel towards the electropositive direction by + 450 mV vs SCE. The nature of oxide film and bacterial metabolism were also correlated with ennoblement process by various investigators. Glassy carbon electrode (GCE) was used in the present study and a shifting of potential in the positive side (+ 450 mV) was noticed. It indicates that biofilm contributes to the ennoblement process without any n/p-type semiconducting oxide film. The nature of the cathodic curve for the biofilm covered GCE is compared with the previous literature on the electrochemical behavior of stainless steel. The present study explains the oxidation and reduction peaks of biofilm covered GCE by cyclic voltammetry. Electrochemical impedance result reveals the diffusion process within the manganese biofilm. The present study confirms the previous investigations that the manganese biofilm rules the electrochemical behavior of materials and suggests that oxide film is not necessary to assist the ennoblement process.     

Amperometric detection of indapamide on glassy carbon electrode

This work describes the development of a fast, precise and reliable voltammetric method for the quantification of indapamide, an orally active diuretic sulfonamide used for hypertensive treatment. This compound acts inhibiting sodium reabsorption and increasing the elimination of water. This characteristic was responsible for its banishment by the International Olympic Committee since 1999. The study begins by finding an adequate potential range (−0.20 to 0.30 V) to avoid poisoning the working glassy carbon electrode (GCE) in phosphate buffer 0.10 mol L⁻¹ (pH=12.0). Utilizing flow injection analysis, linear responses between 2.0 × 10⁻⁶ mol L⁻¹ to 2.5 × 10⁻⁵ mol L⁻¹ of indapamide (R²=0.995), and detection limit (LOD) 3.0 × 10⁻⁷ mol L⁻¹ were obtained. This method was applied for the quantification of indapamide in tablets and in synthetic urine. The same flow system was used for the analysis of commercial drugs and the response obtained corresponded to 98 % of the concentration indicated on the drug label. These tablets were also analyzed by high performance liquid chromatography (HPLC), obtaining a recovery of 103 % and LOD 4.0 × 10⁻⁷ mol L⁻¹. The velocity of analysis using flow methods compares advantageously to the classical chromatographic methods. For synthetic urine, linear responses were obtained in samples spiked in the region from 5.0 × 10⁻⁶ mol L⁻¹ to 30 × 10⁻⁶ mol L⁻¹ (R²=0.991) and LOD 3.0 × 10⁻⁷ mol L⁻¹.     

邻仲丁基苯酚在玻碳电极上的电化学行为

通过循环伏安法(CV)研究了玻碳电极上邻仲丁基苯酚(OSBP)的电化学行为.结果显示:在pH=8.0的磷酸盐缓冲液中,OSBP在玻碳电极上发生的氧化反应是受扩散控制的不可逆等电子、质子转移过程,且氧化产物部分被还原.氧化峰电流与浓度在5.0×10~(-6)～2.0×10~(-4)mol·L~(-1)之间呈良好的线性关系,检出限(S/N=3)为6.60×10~7mol·L~(-1).重复测定的相对标准偏差(RSD)为4.48%(n=7),加标回收率为86.2%～100.5%.结果令人满意.     

Enhanced electron transfer by bovine serum albumin covalently attached to glassy carbon electrode and its application to determination of hydroquinone

Bovine serum albumin (BSA) was covalently attached to glassy carbon electrode (GCE) surface by the electrochemical method. An enhancement for the redox of hydroquinone (HQ) on BSA/GCE was confirmed by cyclic voltammetry and electrochemical impedance spectroscopy measurement. The electron transfer rate constant (k _s) on the BSA/GCE electrode is almost three orders of magnitude higher than that on bare GCE. The enhancing effect can be attributed to the electrostatic force between the positively charged HQ and negatively charged BSA. It is found that the enhanced redox process of HQ can be used to determine HQ sensitively. The oxidation current can reach 95% of its steady-state value within 30 s. The linear range for HQ determination is from 2.5 × 10^?8 M to 1.325 × 10^?6 M with a detection limit of 8.6 × 10^?9 M at a signal-to-noise ratio of 3. The study may provide a simple, rapid and sensitive method for determination of HQ which is present in the natural environment and in chemical industry effluent.     

A glassy carbon electrode modified with C-dots and silver nanoparticles for enzymatic electrochemiluminescent detection of glutamate enantiomers

This paper describes an electrochemiluminescent (ECL) based method for chiral recognition and detection of both glutamate (Glu) enantiomers. The luminophore luminol (Lum) was used as both the reductant and stabilizer of Ag nanoparticles (AgNP-Lum) which were combined with carbon quantum dots (C-dots) and placed on a glassy carbon electrode (GCE) along with the enzyme glutamate oxidase (GluOx). The use of these materials is found to result in strong amplification of ECL. The nanomaterials used were characterized by transmission electron microscopy (TEM) and Fourier transform infrared (FTIR). The stepwise fabrication of the electrode was verified by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Under optimized conditions and by applying a typical potential of 0.6 V, the ECL increases linearly in the 5.0 μM to 5.0 mM Glu concentration range, with a 1.6 μM lower detection limit and satisfactory selectivity. A Glu logic gate idea has been designed that is based on this enzymatic biosensor.

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Graphical abstract Schematic presentation of the electrochemiluminescent (ECL) biosensor. A glassy carbon electrode (GCE) was modified with C-dots and silver nanoparticles which were deoxidized by luminol (AgNP-Lum) for enzymatic specific detection.

     

A new chiral electrochemical sensor for the enantioselective recognition of penicillamine enantiomers

A new chiral electrochemical sensor has been successfully prepared through chemical linking l-methotrexate (l-Mtx) onto the gold electrode surface. Cyclic voltammetry and electrochemical impedance spectroscopy were used to investigate the enantioselective interaction between l-Mtx and Pen enantiomers. The results showed that the l-Mtx-modified gold electrode can selectively recognize penicillamine (Pen) enantiomers using Zn(II) as central ion, and larger response signal was observed from d-Pen owing to the selective formation of Zn complexes. The interaction time between the modified electrode and Pen enantiomers containing Zn(II) was considered. And the electrochemical response of the modified electrode to a series of different concentration of Pen in the presence of Zn(II) was also monitored. In addition, the enantiomeric composition of d- and l-Pen enantiomer mixtures was monitored by measuring the current responses of the sample.     

多壁碳纳米管-Nafion修饰电极测定左旋氧氟沙星

本文报道了用多壁碳纳米管-Nafion修饰玻碳电极测定痕量左旋氧氟沙星的方法。详细研究了左旋氧氟沙星在修饰电极上的电化学行为。实验表明,该电极对左旋氧氟沙星具有良好的电催化作用。在伏安图中,+1.73V处出现一灵敏氧化峰,利用该峰可进行左旋氧氟沙星的测定。在优化条件下,氧化峰电流与左旋氧氟沙星的浓度在0.001~0.5 mg.mL-1范围内成良好的线性关系。信噪比等于3时,检出限为1×10-4mg.mL-1。用于实际样品中左旋氧氟沙星的测定,加标回收率为97.32~102.82。     

邻苯二酚在活化玻碳电极上的电化学行为

邻苯二酚( QH2,儿茶酚)等有机化合物是人体内的电活性物质,直接参与人体内的各种生理过程.     

Modifiying glassy carbon electrode with ferrocene-bridged polysilsesquioxanes

Ferrocene-bridged polysilsesquioxanes film electrodes were prepared via depositing the sols formed by hydrolysis of 1,1′-bis[(2-triethoxylsilyl)ethyl]ferrocene (BTEF) or co-hydrolysis of poly(vinylalcohol) (PVA) with BTEF or tetraethoxysilane (TEOS) with BTEF onto glassy carbon electrode (GCE) surface. The electrochemical behavior of the modified electrodes were characterized by cyclic voltammogram (CV) in aqueous solution. The BTEF film, BTEF/PVA film and BTEF/TEOS film all exhibit a redox wave at E^0’ are 0.504, 0.326, 0.318 V, with the peak potential separation (ΔE) are 0.132, 0.042, 0.028 V, and the value of i_pa/i_pc are 1.8097, 1.007, 1.064 (vs. SCE), respectively. This suggests that BTEF/PVA film and BTEF/TEOS film have a good reversible redox behavior and the redox peak is corresponded to a one-electron reduction and oxidation process. After successive 50 time’s cyclic voltammetric, there is no peak potential shift, and the peak current only decreased 5.58, 4.95%, respectively. BTEF/PVA film has better hydrophilicity and shows a more perfect electrocatalytic activity in the oxidation of H₂A than that of the BTEF/TEOS film. The catalytic peak current has a linear relationship with the concentration of H₂A in the range of 1.0 × 10⁻⁵~1.0 × 10⁻³ M.     

Studies on the electrochemistry of rutin and its interaction with bovine serum albumin using a glassy carbon electrode modified with carbon-coated nickel nanoparticles

We report on a glassy carbon electrode modified with carbon-coated nickel nanoparticles (C-Ni/GCE) that can be used to study the electrochemical properties of rutin and its interaction with bovine serum albumin (BSA) via cyclic voltammetry and differential pulse voltammetry. The effects of pH value, accumulation potential, accumulation time and reaction time were optimized. A pair of reversible peaks is found in the potential range of 0 to around 0.6 V at pH?5.0. Two linear response ranges (with different slopes) are found, one in the 2 to 210 nM concentration range, the other between 0.21 and 1.72 μM. The detection limit is as low as 0.6 nM. On addition of BSA to the rutin solution, a decrease of the current is observed that is proportional to the concentration of BSA. The binding constant and stoichiometric ratio were calculated.

磺胺在碳纳米管修饰玻碳电极上的电化学行为

磺胺类抗菌药是一类允许在饲料中添加的兽用广谱抗菌药.它被广泛用于治疗家畜呼吸道、消化道细菌感染、猪萎缩性鼻炎、禽霍乱、伤寒等疾病[1].停药期用药或用药不当将导致动物食品中抗菌药残留超标.人们长期食用含磺胺类抗菌药残留超标的动物产品,将导致肝肾损伤和体内耐药菌株产生,危害到人们的身体健康和疾病治疗.     

Synthesis of chiral cyclodextrin metal-organic framework modified with platinum on glassy carbon electrodes: Electrochemical chiral recognition of methionine enantiomers

A platinum nanoparticle-modified chiral cross-linked cyclodextrin MOF (Pt-CLMOF) was synthesized. Then, a chiral electrochemical sensor was constructed using the Pt-CLMOF nanomaterials for the recognition of methionine (Met) enantiomers and the chiral recognition mechanism was revealed by density functional theory calculations. The recognition effect of Pt-CLMOF modified electrode (Pt-CLMOF/GCE) on Met was studied by differential pulse voltammetry. The enantioselectivity coefficient (IL/ID) was 1.98. There is an acceptable linear relationship between peak current and Met enantiomer concentration in the 2–200 μM range, the detection limits of L–Met and D-Met were 0.33 and 0.60 μM which were obtained by this electrochemical sensor, respectively. The synthesized materials were successfully applied to the analysis of Met enantiomers, indicating that Pt-CLMOF materials have good application potentiality.     

Glucose biosensor based on new carbon nanotube-gold-titania nano-composites modified glassy carbon electrode

In this paper, a novel biosensor was prepared by immobilizing glucose oxidase （GOx） on carbon nanotube-gold-titania nanocomposites （CNT/Au/TiO2） modified glassy carbon electrode （GCE）. SEM was initially used to investigate the surface morphology of CNT/Au/TiO2 nanocomposites modified GCE, indicating the formation of the nano-porous structure which could readily facilitate the attachment of GOx on the electrode surface. Cyclic voltammogram （CV） and electrochemical impedance spectrum （EIS） were further utilized to explore relevant electrochemical activity on CNT]Au/TiO2 nanocomposites modified GCE. The observations demonstrated that the immobilized GOx could efficiently execute its bioelectrocatalytic activity for the oxidation of glucose. The biosensor exhibited a wider linearity range from 0.1 mmol L-1 to 8 mmol L^-1 glucose with a detection limit of 0.077 mmol L^- 1.