邻苯二酚和对苯二酚在钴氢氧化物膜修饰玻碳电极上的选择性测定

通过镀膜/循环伏安法制备了钴氢氧化物膜修饰的玻碳电极。该修饰电极对邻苯二酚(CA)和对苯二酚(HQ)具有较强的电催化活性。考察了支持电解质酸度对邻苯二酚和对苯二酚电化学响应的影响,选用0.1 mol/LPBS(pH 10.0)作为支持电解质。利用差示脉冲伏安法(DPV)对邻苯二酚和对苯二酚进行选择性检测,当两者浓度同时改变时,邻苯二酚和对苯二酚在6～100μmol/L范围内氧化峰电流与其浓度呈良好的线性关系,检出限分别为2×10–7,5×10–7mol/L(S/N=3)。钴氢氧化物膜电极具有较好的稳定性、重现性及较强的抗干扰能力,将此修饰电极应用于模拟水样中邻苯二酚和对苯二酚的测定,回收率为95.4%～100.4%。     

Platinum Nanoparticles/Poly(isoleucine) Modified Glassy Carbon Electrode for the Simultaneous Determination of Hydroquinone and Catechol

A new electrochemical sensor based on Poly(Isoleucine) modified glassy carbon electrode decorated with platinum nanoparticles (Pt/Poly(Isoleucine)/GCE) was developed for sensitive individual and simultaneous determination of hydroquinone (HQ) and catechol (CC). Scanning electron microscopy (SEM), Electrochemical impedance spectroscopy (EIS), Cyclic voltammetry (CV) and Differential pulse voltammetry (DPV) were performed in order to characterize the Pt/Poly(Isoleucine)/GCE nanocomposite. For simultaneous determination of HQ and CC, Pt/Poly(Isoleucine)/GCE showed wide linear range between the 0.01–100.0 μM. The detection limits were 0.006 μM for HQ and 0.005 μM for CC. The Pt/Poly(Isoleucine)/GC electrode exhibited good sensitivity and reliability in the simultaneous electroanalysis of two isomers in PBS of pH 7.5. The modified electrode was used to detect the isomers in naturel samples.     

Sensitive and Facile Determination of Catechol and Hydroquinone Simultaneously Under Coexistence of Resorcinol with a Zn/Al Layered Double Hydroxide Film Modified Glassy Carbon Electrode

A stable dihydroxybenzene sensor was fabricated by electrochemical deposition of Zn/Al layered double hydroxide film on glassy carbon electrode (LDHf/GCE). The sensitive and facile electrochemical method for the simultaneous determination of catechol (CA) and hydroquinone (HQ) under coexistence of resorcinol (RE) has been achieved at the LDHf/GCE in phosphate buffer solution (pH 6.5). Under the optimized conditions, the differential pulse voltammetry response of the modified electrode to CA (or HQ) shows a linear concentration range of 0.6 μM to 6.0 mM (or 3.2 μM to 2.4 mM) with a correlation coefficient of 0.9987 (or 0.9992) and the calculated limit of detection is 0.1 μM (or 1.0 μM) at a signal‐to‐noise ratio of 3. In the presence of 50 μM isomer, the linear concentration ranges for CA and HQ are 3.0 μM to 1.5 mM and 12.0 μM to 0.8 mM, respectively. The detection limits are 1.2 μM and 9.0 μM. Further, the proposed method has been performed to successfully detect dihydroxybenzene isomers in analysis of real samples, such as water and tea.     

Simultaneous Determination of Catechol and Hydroquinone on Nano-Co/L-Cysteine Modified Glassy Carbon Electrode

In this study, a novel and highly sensitive electrochemical method for simultaneous determination of catechol (CC) and hydroquinone (HQ) was developed, which worked at GCE modified with Nano cobalt (Nano-Co) by electrodeposition and L-Cysteine by electrochemical polymerization. The Nano-Co/L-Cysteine GCE was investigated by cyclic voltammetry (CV), SEM and EIS. The excellent conditions have been selected including supporting electrolyte, pH, accumulation time and scan rate. The calibration curves of were obtained that the linear regression equation was I=0.0734c+6×10⁻⁶ in the range of 5.8 μM to 103 μM (R²=0.9942) for CC and the linear regression equation was I=0.0566c+5×10⁻⁶ in the range of 5.8 μM to 100 μM (R²=0.9967) for HQ. The obtained detection limits of CC and HQ both were 6×10⁻⁷ M. The modified electrode was successfully applied to the simultaneous determination of CC and HQ in water samples.     

聚酸性铬蓝K修饰电极测定对乙酰氨基酚

研究对乙酰氨基酚(ACOP)在聚酸性铬蓝K(PACBK)修饰石墨电极上的电化学行为,并利用该电极建立测定对乙酰氨基酚的电化学方法。采用循环伏安法制备了聚酸性铬蓝修饰石墨电极,利用脉冲伏安法对对乙酰氨基酚的含量进行测定。对乙酰氨基酚的浓度在0.8~100μmol/L范围与脉冲峰电流呈现良好的线性关系(r~2=0.998 2),检出限为0.1μmol/L(S/N=3),实际样品的平均加标回收率为96.5%~101.7%,测定结果的相对标准偏差为1.2%(n=6)。该方法可用于药物对乙酰氨基酚片的质量控制。     

Influence of micelles on the electrochemical behaviors of catechol and hydroquinone and their simultaneous determination

A simple and highly selective electrochemical method for the simultaneous determination of CAT and HQ at a glassy carbon electrode in micellar solutions has been developed. The electrochemical behaviors of CAT and HQ in aqueous CPB and SDBS micellar solutions have been studied by cyclic voltammetry. The oxidation peak potentials shift negatively, the reduction peak potentials shift positively, and the peak currents increase in the presence of CPB for both CAT and HQ. However, the oxidation peak potentials shift positively, the reduction peak potentials shift negatively, and the peak currents decrease in the presence of SDBS for both CAT and HQ. The electrochemical kinetic parameters for CAT and HQ in aqueous CPB and SDBS micellar solutions were also determined by chronocoulometry (CC) and chronoamperometry (CA). The cyclic and pulse differential voltammetric behaviors of the system consisting of CAT coexisting with HQ were also investigated in this work. It was found that the oxidation peak potential waves of CAT and HQ were separated by 100 mV in the presence of CPB in 0.10 M PBS (pH 6.8). Therefore, CAT and HQ can be determined simultaneously in such a system. This simple method was applied to the simultaneous determination of HQ and CAT in a household tap water sample and it exhibited high selectivity.     

Rapid and Selective Determination of Vanillin in the Presence of Caffeine,its Electrochemical Behavior on an Au Electrode Electropolymerized with 3‐Amino‐1,2,4‐triazole‐5‐thiol

Electrochemical oxidation of vanillin (VAN) in the presence of caffeine (CAF) was studied on a gold (Au) electrode modified with 3‐amino‐1,2,4‐triazole‐5‐thiol (ATT) film by using differential pulse voltammetry (DPV) and cyclic voltammetry (CV) method. The formation of the ATT film on the Au electrode surface was characterized by the CV, fourier transform infrared spectroscopy (FTIR) and impedance spectroscopy (EIS) methods. A single irreversible oxidation peak of the VAN was obtained by using the CV method. The determination of VAN in the presence of CAF was carried out at pH 4 in Britton Robinson buffer (BR) by the DPV method. Under the optimal conditions, the oxidation peak current was proportional to the concentration of VAN in the range of 1.1 μM to 76.4 μM in the presence of CAF with the correlation coefficient of 0.997 and the detection limit of 0.19 μM (S/N=3). The selective determination of VAN in a commercial coffee sample was carried out with satisfactory results on the ATT‐Au modified electrode.     

Electrochemistry and Adsorptive Stripping Voltammetric Determination of Amoxicillin on a Multiwalled Carbon Nanotubes Modified Glassy Carbon Electrode

The study of electrochemical behavior of amoxicillin (AMX), a β‐lactam antibiotic, is described on a multiwalled carbon nanotubes (MWCNTs) modified electrode by electrochemical impedance spectroscopy (EIS) and adsorptive stripping voltammetry for sensitive determination of AMX in pharmaceutical and human urine samples within a wide pH range from 2.0 to 10.0. Also, studies by Fe₂O₃ nanoparticles modified carbon paste electrode show that iron oxide impurities in the MWCNTs are not active sites for sensing of amoxicillin. Under optimized conditions, the oxidation peak has two linear dynamic ranges of 0.6–8.0 and 10.0–80.0 μM with a detection limit of 0.2 μM and a precision of <4%.     

Selective electrooxidation of uric acid in presence of ascorbic acid at a room temperature ionic liquid/nickel hexacyanoferarrate nanoparticles composite electrode

A novel amperometric sensor for the determination of uric acid was fabricated using room temperature ionic liquid and nickel hexacyanoferrate nanoparticle composite which was immobilized on paraffin wax impregnated graphite electrode. The nickel hexacyanoferrate nanoparticle was characterized by UV-vis, X-ray diffraction and field emission scanning electron microscopy. The electrochemical behavior of the modified electrode was investigated in detail by electrochemical impedance spectroscopy, cyclic voltammetry and differential pulse voltammetry. Various experimental parameters influencing the electrochemical behavior of the modified electrode were optimized by varying the supporting electrolyte, scan rate and pH. The apparent electron transfer rate constant (K(s)) and charge transfer coefficient (α) of the modified electrode were found to be 1.358(± 0.02)cm/s and 0.65, respectively from cyclic voltammetry. The sensor exhibited an excellent electrocatalytic activity towards the oxidation of uric acid. The interference from ascorbic acid was easily overcome by coating the modified electrode with PEDOT layer. Under optimal condition, the determination range for uric acid is from 1.0 × 10(-6)M to 2.6 × 10(-3)M and the detection limit was 3.3 × 10(-7)M (3σ). The proposed method has been used for the determination of uric acid in human urine samples.     

Voltammetric and potentiometric study of cysteine at cobalt(II) phthalocyanine modified carbon-paste electrode

Cyclic voltammetry and potentiometry were used to investigate the electrochemical behavior of cysteine at a chemically modified electrode prepared by incorporating cobalt(II) phthalocyanine [Co(II)Pc] into carbon paste matrix. The modified electrode showed high electrocatalytic activity toward cysteine; the overpotential for the oxidation of cysteine was decreased by more than 100 mV, and the corresponding peak current increased significantly. The electrocatalytic process was highly dependent on the pH of the supporting electrolyte. The peak currents decreased when the pH was raised to 6 and totally disappeared at pH≥ 7, resulting from the autocatalytic oxidation of cysteine by Co(II)Pc at the electrode surface. Therefore, at pH values of 6 to 8, the modified electrode was used as a potentiometric sensor for quantitative measurement of cysteine in the presence of oxygen in air saturated solutions. In fact, the Co(II)Pc/Co(I)Pc couple acts as a suitable mediator for indirect oxidation of cysteine by dissolved oxygen at approximately neutral pH values. Under the optimized conditions, the potentiometric response of the modified electrode was linear against the concentration of cysteine in the range of 0.6 μM to 2 mM. The limit of detection was found to be 0.5 μM. The potentiometric response time was ≤15 s. The electrode showed long term stability; the standard deviation of the slope obtained after repeated calibration during a period of two months was 2.8% (n = 7). Application of the electrode in a recovery experiment for the determination of cysteine added to a synthetic serum sample is described.     

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.     

Simultaneous determination of hydroquinone and catechol based on three-dimensionally ordered macroporous polycysteine film modified electrode

A three-dimensionally ordered macroporous (3DOM) polycysteine (PCE) film was electropolymerized on the glassy carbon electrode (GCE) using polystyrene spheres as template. The electrochemical behaviors of hydroquinone (HQ) and catechol (CC) were studied, and two independent oxidation peaks were observed. Compared with the bare GCE and GCE modified with PCE without using template, this electrode displays larger peak currents which may be attributed to the structure of PCE and the large surface area of the nanopore array structure. As a result, a novel electrochemical method was developed for the simultaneous determination of HQ and CC. Under the optimized conditions, the peak currents were linear to concentrations in the wider ranges of 9 to 700 μM for HQ and from 3 to 700 μM for CC. The method was successfully applied to the simultaneous determination of HQ and CC in spiked water samples, and the results are satisfactory.     

Simultaneous voltammetric determination of acetaminophen and tramadol using Dowex50wx2 and gold nanoparticles modified glassy carbon paste electrode

A glassy carbon paste electrode (GCPE) modified with a cation exchanger resin, Dowex50wx2 and gold nanoparticles (D50wx2–GNP–GCPE) has been developed for individual and simultaneous determination of acetaminophen (ACOP) and tramadol (TRA). The electrochemical behavior of both the molecules has been investigated employing cyclic voltammetry (CV), chronocoulometry (CC), electrochemical impedance spectroscopy (EIS) and adsorptive stripping square wave voltammetry (AdSSWV). The studies revealed that the oxidation of ACOP and TRA is facilitated at D50wx2–GNP–GCPE. Using AdSSWV, the method allowed simultaneous determination of ACOP and TRA in the linear working range of 3.34 × 10⁻⁸ to 4.22 × 10⁻⁵ M with detection limits of 4.71 × 10⁻⁹ and 1.12 × 10⁻⁸ M (S/N = 3) for ACOP and TRA respectively. The prepared modified electrode shows several advantages such as simple preparation method, long-time stability, ease of preparation and regeneration of the electrode surface by simple polishing and excellent reproducibility. The high sensitivity and selectivity of D50wx2–GNP–GCPE were demonstrated by its practical application in the determination of both ACOP and TRA in pharmaceutical formulations, urine and blood serum samples.     

Covalent modification of glassy carbon electrode with aspartic acid for simultaneous determination of hydroquinone and catechol

Glassy carbon electrode (GCE) is covalently modified with aspartic acid (Asp). The modified electrode is used for the simultaneous electrochemical determination of hydroquinone (HQ) and catechol (CC) and shows an excellent electrocatalytical effect on the oxidation of HQ and CC by cyclic voltammetry (CV) in 0.1 mol/L acetate buffer solution (pH 4.5). In differential pulse voltammetric (DPV) measurements, the modified electrode could separate the oxidation peak potentials of HQ and CC present in binary mixtures by about 101 mV though the bare electrode gave a single broad response. A successful elimination of the fouling effect by the oxidized product of HQ on the response of CC has been achieved at the modified electrode. The determination limit of HQ in the presence of 0.1 mmol/L CC was 9.0 x 10(-7) mol/L and the determination limit of CC in the presence of 0.1 mmol/L HQ was 5.0 x 10(-7) mol/L. The proposed method has been applied to the simultaneous determination of HQ and CC in a water sample with simplicity and high selectivity.     

Sensitive determination of diuron on zinc oxide nanoparticles modified carbon paste electrode in soil and water samples

An electrochemical sensor based on Zinc oxide nanoparticles (ZnONPs) modified carbon paste electrode was designed for the toxic diuron pesticide detection. The ZnONPs were synthesized through the hydrothermal route and their structural properties were investigated via scanning electron microscopy (SEM) and X-ray diffraction powder (XRD). The designed ZnONPs-modified carbon paste electrode (ZnONPs-CPE) was characterized using cyclic voltammetry and electrochemical impedance spectroscopy. The sensor showed significantly enhanced sensitivity on the diuron oxidation peak current, compared to the bare carbon paste electrode. Qualitative and quantitative analysis were performed using cyclic voltammetry (CV) and square wave voltammetry (SWV). Experimental parameters such as pH, amount of ZnONPs and frequency were evaluated and the optimized conditions were obtained with 0.1 M phosphate buffer solution at pH=8, a frequency of 50 Hz and a quantity of 5 mg of ZnONPs. Under these conditions, linear responses ranging from 1.3 to 7.7 μM and 8.6 to 30 μM of diuron were obtained, with correlation coefficients of R²=0.994 and 0.996 respectively. Detection and quantification limits of 0.22 μM and 0.84 μM (S/N=3) were respectively achieved based on the 3σ method. The interference of some ions on the oxidation peak of diuron on ZnONPs-CPE was also evaluated and no interference was observed, therefore demonstrating the selectivity of the sensor. The proposed sensor, designed with ecofriendly materials, is sensitive, selective and was effectively used for diuron determination in soils and water samples with recoveries ranging from 98 % to 101.5 %.     

A Sensitive Electrochemical Sensor for Voltammetric Determination of Ganciclovir Based on Au‐ZnS Nanocomposite

An electrode modified with ZnS and gold nanoparticles (Au‐ZnS NPs) is introduced for highly sensitive voltammetric determination of ganciclovir (GCV). Surface structure and topography of the modified electrode was studied by SEM, EDX and XRD techniques. Electrochemical oxidation of GCV was investigated by cyclic (CV) and square wave voltammetry (SWV) in Briton‐Robinson buffer solution (pH 1.5). The results showed that electrochemical oxidation of GCV at the Au‐ZnS modified glassy carbon electrode (GCE) is irreversible and exhibited diffusion controlled electrode process over the pH range from 1.0 to 6.0. The oxidation potential peak and pH relationship showed that electrons and protons were transferred simultaneously over the electrochemical oxidation process. Using the proposed sensor, the linear calibration curves were obtained in the ranges of 0.04–1.50 μM and 1.5–70.0 μM with detection limit of 0.01 μM GCV by SWV technique. The modified electrode was successfully applied as a sensitive, reproducible and repeatable sensor for determination of the trace amount of GCV in human serum, urine and cymevene vials. Reasonable results were obtained from comparing the measurements of the real samples by the new sensor to high performance liquid chromatography (HPLC) as a standard method.     

石墨烯修饰电极的制备及其对对乙酰氨基酚的伏安测定

利用滴涂的方法制备了石墨烯修饰电极;石墨烯修饰电极对对乙酰氨基酚（ACOP）的电化学氧化具有明显的催化作用。 研究了ACOP在石墨烯修饰电极上的电化学行为,建立了测定ACOP的电化学分析新方法。 考察了磷酸盐缓冲溶液的pH值对ACOP电化学行为的影响。 结果表明,氧化还原峰电位随pH值升高发生负移;在pH=6.0磷酸盐缓冲溶液中,对乙酰氨基酚在修饰电极上呈现一对灵敏的氧化还原峰。 对乙酰氨基酚在石墨烯修饰电极上的氧化峰峰电流与其浓度在6.00×10-7~4.00×10-5 mol/L范围内呈良好的线性关系,相关系数为0.994 0;检出限为5.00×10-8 mol/L。 其回归方程为：ipa(A)=3.00c+1.21×10-5。 该修饰电极具有良好的灵敏度、选择性和稳定性,可用于对乙酰氨基酚药片分析。     

Nanodiamond Decorated with Silver Nanoparticles as a Sensitive Film Modifier in a Jeweled Electrochemical Sensor: Application to Voltammetric Determination of Thioridazine

Nanodiamond? graphite (NDG) decorated with Ag nanoparticles (AgNPs‐NDG) was prepared and used to construct a novel sensitive sensor for the voltammetric determination of thioridazine (TR). The results indicate a remarkable increase in the oxidation peak currents together with a negative shift in the oxidation peak potentials, in comparison to the bare pyrolytic graphite electrode. Remarkable enhancement in microscopic area of the electrode along with strong adsorption of TR on the surface of the modified electrode resulted in a considerable increase in the peak current of TR. The surface morphology and the nature of the composite film deposited on PGE were characterized by scanning electron microscopy, atomic force microscopy, cyclic voltammetry and electrochemical impedance spectroscopy. Experimental variables, such as the deposited amount of the modifier suspension, pH of the supporting electrolyte, the accumulation potential and time are optimized by monitoring the CV responses of TR. Under the optimal conditions, the modified electrode showed a wide linear response to the concentration of TR in the range of 0.08–100 µM with a detection limit of 0.01 µM. The prepared modified electrode showed several advantages: simple preparation method, high stability and uniformity in the composite film, high sensitivity, long‐term stability and remarkable voltammetric reproducibility in response to TR. The modified electrode can be successfully applied for accurate determination of trace amounts of TR in pharmaceutical and clinical preparations.     

Simultaneous Electrochemical Determination of Hydroquinone and Bisphenol A using a Carbon Paste Electrode Modified with Silver Nanoparticles

In this paper, a rapid and sensitive modified electrode for the simultaneous determination of hydroquinone (HQ) and bisphenol A (BPA) is proposed. The simultaneous determination of these two compounds is extremely important since they can coexist in the same sample and are very harmful to plants, animals and the environment in general. A carbon paste electrode (CPE) was modified with silver nanoparticles (nAg) and polyvinylpyrrolidone (PVP). The PVP was used as a reducing and stabilizing agent of nAg from silver nitrate in aqueous media. The nAg‐PVP composite obtained was characterized by transmission electron microscopy and UV‐vis spectroscopy. The electrochemical behavior of HQ and BPA at the nAg‐PVP/CPE was investigated in 0.1 mol L⁻¹ B−R buffer (pH 6.0) using cyclic voltammetry (CV) and square wave voltammetry (SWV). The results indicate that the electrochemical responses are improved significantly with the use of the modified electrode. The calibration curves obtained by SWV, under the optimized conditions, showed linear ranges of 0.09–2.00 μmol L⁻¹ for HQ (limit of detection 0.088 μmol L⁻¹) and 0.04–1.00 μmol L⁻¹ for BPA (limit of detection 0.025 μmol L⁻¹). The modified electrode was successfully applied in the analysis of water samples and the results were comparable to those obtained using UV‐vis spectroscopy.     

Multi-walled carbon nanotubes modified glass carbon electrode and its electrocatalytic activity towards oxidation of paracetamol

Multi-walled carbon nanotubes (MWNTs) modified glassy carbon electrode (GCE) was simply and conveniently fabricated. The electrochemical properties of paracetamol (PCT) at the prepared modified electrode were investigated by cyclic voltammetry (CV). Based on this, an ultrasensitive and rapid electrochemical method was developed for the determination of PCT. The result indicated that the oxidation of PCT was greatly improved at the MWNTs-modified GC (MWNTs/GC) electrode as compared with the bare GC electrode, with relatively high sensitivity, stability and life time. Good linear relationship between the oxidation peak current and the PCT concentration in the range of 1 × 10⁻⁷ to 1 × 10⁻³ M (r = 0.996) was obtained in phosphate buffer solution (PBS) with pH 6.5, the detection limit was 2 × 10⁻⁸ M (S/N = 3) by use of modified electrode. The proposed method was successfully applied to the PCT determination in tablets.