Cysteamine Capped Silver Nanoparticles and Single‐walled Carbon Nanotubes Composite Coated on Glassy Carbon Electrode for Simultaneous Analysis of Hydroquinone and Catechol

A stable complex of silver nanoparticles (Ag NPs) capped by cysteamine (Cst) together with single‐walled carbon nanotube (CNTs) was used to modify a glassy carbon electrode (GCE) for simultaneous detection of hydroquinone (HQ) and catechol (CT). The resulting electrode (AgCst‐CNTs/GCE) showed excellent electrocatalysis and reversibility towards this electroactive pair. The peak separations of their oxidation‐reduction peaks decreased significantly, compared with those of the unmodified GCE. The signal responses of the AgCst‐CNTs/GCE were 5‐fold higher while its peak potential separation remained unchanged (ca. 130 mV), compared to the CNTs‐modified GCE. The oxidation peak currents obtained for HQ and CT exhibited linearly from submicromolar to hundred micromolar concentrations without any cross‐interference. The modified electrode possessed a very large active surface area with a detection limit (S/N=3) of 10 and 40 nM for HQ and CT, respectively. The sensor was demonstrated for the analysis of river water and topical cream as evinced by high accuracy and reproducibility.     

石墨烯/铁氰化钴复合膜修饰玻碳电极同时测定对苯二酚、邻苯二酚和间苯二酚

采用滴涂法和电沉积法制备了石墨烯/铁氰化钴复合膜修饰玻碳电极. 用扫描电镜对该纳米复合膜进行了表征.用循环伏安法研究了对苯二酚(HQ)、邻苯二酚(CT)和间苯二酚(RS)在修饰电极上的电化学行为. 实验结果表明, 相对于裸玻碳电极和石墨烯修饰电极, HQ, CT 和RS 在石墨烯/铁氰化钴修饰电极上的氧化峰电流显著提高. 利用差分脉冲伏安法测定, HQ, CT 和RS 分别在1.0×10^－6～1.5×10^－4 mol/L, 1.0×10^－6～2.0×10^－4 mol/L 和3.5×10^－6～2.5×10^－4 mol/L浓度范围内与氧化峰电流呈良好的线性关系, 相关系数分别为0.991, 0.993 和0.992. 信噪比为3 时, HQ, CT 和RS 检出限分别为2.0×10^－7, 2.1×10^－7 和3.5×10^－7 mol/L. 将该方法用于水样分析, 回收率为95.6%～106.1%.     

A sensor based on the carbon nanotubes-ionic liquid composite for simultaneous determination of hydroquinone and catechol

MWNTs-IL-Gel/GCE, a glassy carbon electrode modified with multiwalled carbon nanotubes (MWNTs) and ionic liquids (IL), was developed to serve as a sensor for simultaneous determination of Hydroquinone (HQ) and catechol (CC) in this paper. The modified GCE showed two well-defined redox waves for HQ and CC in both CV and DPV with a peak potential separation of ca. 0.1 V, which was large enough for simultaneous detection. The results revealed that the oxidation of HQ and CC with the enhancement of the redox peak current and the decrease of the peak-to-peak separation exhibit excellent electrocatalytic behaviors. A high sensitivity of 1.8×10(-7)M with detection limits of 6.7×10(-8)M and 6.0×10(-8)M (S/N=3) for HQ and CC were obtained. Moreover, the constants of apparent electron transfer rate of HQ and CC at MWNTs-IL-Gel/GCE were calculated as 7.402 s(-1) and 8.179 s(-1), respectively, and the adsorption quantity of HQ and CC was 1.408×10(-6) mol cm(-2) with chronocoulometry. The developed sensor can be applied to determinate directly of HQ and CC in aqueous solution.     

Simultaneous detection of hydroquinone and catechol on electrochemical-activated glassy carbon electrode by simple anodic and cathodic polarization

Herein, we report a simple method of simultaneous detection of hydroquinone (HQ) and catechol (CC) by cyclic voltammetry (CV) using activated glassy carbon electrodes (GCE). It was found that the two isomers can be completely separated by CV method on cathode polarized GCE (PGCE) after its anodic oxidation. This facile processing method solves the difficulty of electrode surface regenerating which disturb most modified electrodes for the complex composition ease of being contaminated by the analytes in measurement. Morphology and composition of the PGCE were characterized by scanning electron microscope (SEM), Fourier transform infrared (FTIR) spectra, and X-ray photoelectron spectroscopy. In addition, the reaction kinetic of HQ and CC reaction on the PGCE was investigated. It was found that the reaction kinetics of HQ and CC is a surface adsorption-controlled process at low concentration and a diffusion-controlled process at high concentration.     

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.     

The Cu-MOF-199/single-walled carbon nanotubes modified electrode for simultaneous determination of hydroquinone and catechol with extended linear ranges and lower detection limits

A novel electrochemical sensor based on Cu-MOF-199 [Cu-MOF-199 = Cu₃(BTC)₂ (BTC = 1,3,5-benzenetricarboxylicacid)] and SWCNTs (single-walled carbon nanotubes) was fabricated for the simultaneous determination of hydroquinone (HQ) and catechol (CT). The modification procedure was carried out through casting SWCNTs on the bare glassy carbon electrode (GCE) and followed by the electrodeposition of Cu-MOF-199 on the SWCNTs modified electrode. Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) were performed to characterize the electrochemical performance and surface characteristics of the as-prepared sensor. The composite electrode exhibited an excellent electrocatalytic activity with increased electrochemical signals towards the oxidation of HQ and CT, owing to the synergistic effect of SWCNTs and Cu-MOF-199. Under the optimized condition, the linear response range were from 0.1 to 1453 μmol L⁻¹ (R_HQ = 0.9999) for HQ and 0.1–1150 μmol L⁻¹ (R_CT = 0.9990) for CT. The detection limits for HQ and CT were as low as 0.08 and 0.1 μmol L⁻¹, respectively. Moreover, the modified electrode presented the good reproducibility and the excellent anti-interference performance. The analytical performance of the developed sensor for the simultaneous detection of HQ and CT had been evaluated in practical samples with satisfying results.     

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.     

Enhanced Electrochemical Determination of Catechol and Hydroquinone Based on Pd Nanoparticles/Poly(Taurine) Modified Glassy Carbon Electrode

Here, Pd nanoparticles and poly(taurine) film was prepared on the glassy carbon electrode surface (Pd/Poly(TAU)/GCE) by the rapid electrochemical technique. The proposed composite surface was characterized by scanning electron microscopy(SEM), X‐ray photoelectron spectroscopy(XPS) and electrochemical impedance spectroscopy(EIS). Enhanced electron transfer ability and higher electroactive surface area were achieved at Pd/Poly(TAU)/GCE as compared to the bare GCE and polymer film electrode. The new and highly stable Pd/Poly(TAU)/GCE was employed for the individual and simultaneous determination of hydroquinone and catechol which were environmentally toxic. Under the optimized conditions, HQ and CC were individually determined by using the differantial pulse voltammetry in the linear ranges of 0.008–100 μM and 0.001–100 μM with the detection limits of (LOD) 2.1 nM and 0.68 nM, respectively. In case of simultaneous determination, LODs were found as 10 nM and 0.88 nM for HQ and CC, respectively. The content of both analytes in the real sample analysis was evaluated in the river water and tap water successfully.     

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.     

石墨烯的制备及石墨烯修饰电极对p-苯二酚的催化氧化

采用氨水还原氧化石墨烯(GO)制备石墨烯(GN), 并考察石墨烯修饰玻碳电极(GN/GCE)电催化氧化p-苯二酚(HQ)的性能. 利用傅里叶红外光谱(FTIR)、拉曼光谱(Raman)、X射线衍射(XRD)、扫描电子显微镜(SEM)、原子力显微镜(AFM)、比表面分析(BET)和电分析化学测试等技术对GN结构、表面形貌和电化学行为进行了表征. 采用循环伏安法(CV)和差分脉冲溶出伏安法(DPV)研究GN/GCE对HQ的电催化氧化性能. 结果表明, 与裸玻碳电极(GCE)相比, [Fe(CN)₆]^3-/4-在GN/GCE上电荷转移电阻为75.0 Ω·cm², 减小约9倍, 说明GN具有良好导电性; 同时HQ在GN/GCE上氧化峰电位负移, 还原峰电位正移, 峰电位差ΔE_p减小165 mV, 且氧化还原峰电流(I_pa和I_pc)均增大, HQ电化学氧化可逆性明显改善, 表明GN/GCE对HQ氧化具有显著电催化作用.     

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.     

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%。     

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.     

A graphene-based electrochemical sensor for sensitive and selective determination of hydroquinone

Graphene was prepared by electrochemical reduction of exfoliated graphite oxide at cathodic potentials, and used to fabricate a graphene-modified glassy carbon electrode (GCE) which was applied in a sensor for highly sensitive and selective voltammetric determination of hydroquinone (HQ). Compared to a bare (conventional) GCE, the redox peak current for HQ in pH 5.7 acetate buffer solution is significantly increased, indicating that graphene possesses electrocatalytic activity towards HQ. In addition, the peak-to-peak separation is significantly improved. The modified electrode enables sensing of HQ without interference by catechol or resorcinol. Under optimal conditions, the sensor exhibits excellent performance for detecting HQ with a detection limit of 0.8?μM, a reproducibility of 2.5% (expressed as the RSD), and a recoveries from 98.4 to 101.2%.

Simultaneous determination of hydroquinone and catechol using a glassy carbon electrode modified with gold nanoparticles,ZnS/NiS@ZnS quantum dots and L-cysteine

We describe an electrochemical sensor for simultaneous determination of hydroquinone (HQ) and catechol (CC). A glassy carbon electrode (GCE) was modified with gold nanoparticles, L-cysteine, and ZnS/NiS@ZnS quantum dots using a layer-by-layer technique. The materials were characterized by X-ray diffractometry, field emission scanning electron microscopy, and electrochemical impedance and Fourier transform infrared spectroscopy. Cyclic voltammetry and differential pulse voltammetry revealed this modified GCE to represent a highly sensitive sensor for the simultaneous determination of HQ and CC. The anodic peak current for HQ at a working voltage of 80 mV (vs. Ag/AgCl) is related to its concentration in the 0.1 to 300 μM range (even in the presence of 0.1 mM of CC). The anodic peak current for CC at a working voltage of 184 mV is related to its concentration in the 0.5 to 400 μM range (even in the presence of 0.1 mM of HQ). The detection limits (at an S/N ratio of 3) are 24 and 71 nM for HQ and CC, respectively. The modified GCE was successfully applied to the determination of HQ and CC in aqueous solutions and gave satisfactory results.

A glassy carbon electrode was modified with gold nanoparticles, ZnS/NiS@ZnS quantum dots and L-cysteine and used for simultaneous determination of hydroquinone and catechol.

     

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.     

Selective Determination of Catechol in the Presence of Hydroquinone at Bare Indium Tin Oxide Electrodes via Peak‐Potential Separation and Redox Cycling by Hydrazine

The electrochemical, selective determination of catechol (CT) in the presence of hydroquinone (HQ) is not readily achieved, because the formal potentials of two phenolic compounds are very close. Here, we have developed a simple electrochemical method for the selective determination of CT by using bare indium tin oxide electrodes and employing CT redox cycling by hydrazine. The cyclic voltammetry of CT and HQ was investigated in Tris buffer (pH 9.0), phosphate buffered saline buffer (pH 7.4), and acetate buffer (pH 4.5). Especially in Tris buffer, the anodic peak potential of CT is much lower than that of HQ, resulting in a large difference between two peak potentials (ca. 0.4 V). The difference allows the selective determination of CT in the presence of excess HQ. The anodic current of CT is amplified using CT redox cycling by hydrazine, which also helps to stabilize CT and HQ in Tris buffer for several hours. The detection limits of CT in Tris buffer containing 0.1 mM HQ are 1 μM and 10 μM in the presence and absence of hydrazine, respectively.     

Simultaneous determination of catechol and hydroquinone based on poly (diallyldimethylammonium chloride) functionalized graphene-modified glassy carbon electrode

Simultaneous determination of catechol (CC) and hydroquinone (HQ) were investigated by voltammetry based on glassy carbon electrode (GCE) modified by poly (diallyldimethylammonium chloride) (PDDA) functionalized graphene (PDDA-G). The modified electrode showed excellent sensitivity and selectivity properties for the two dihydroxybenzene isomers. In 0.1 mol/L phosphate buffer solution (PBS, pH 7.0), the oxidation peak potential difference between CC and HQ was 108 mV, and the peaks on the PDDA-G/GCE were three times as high as the ones on graphene-modified glass carbon electrode. Under optimized conditions, the PDDA-G/GCE showed wide linear behaviors in the range of 1 × 10⁻⁶−4 × 10⁻⁴ mol/L for CC and 1 × 10⁻⁶−5 × 10⁻⁴ mol/L for HQ, with the detection limits 2.0 × 10⁻⁷ mol/L for CC and 2.5 × 10⁻⁷ mol/L for HQ (S/N = 3) in mixture, respectively. Some kinetic parameters, such as the electron transfer number (n), charge transfer coefficient (α), and the apparent heterogeneous electron transfer rate constant (k _s), were calculated. The proposed method was applied to simultaneous determine CC and HQ in real water samples of Yellow River with satisfactory results.     

Electrochemical sensor for cinchonine based on a competitive host-guest complexation

An electrochemical sensor for cinchonine (CCN) using the β-cyclodextrin (β-CD) modified poly(N-acetylaniline) (PAA) electrode has been developed, in which 1,4-hydroquinone (HQ) was chosen as a probe. Complexation of HQ with β-CD modified on the glassy carbon electrode (GCE) was examined by cyclic voltammetry (CV). HQ was included in the cavity of β-CD and reversible voltammograms were observed. In the presence of CCN, a competitive inclusion equilibrium with β-CD was established between HQ and CCN, lowering the peak current of HQ. The decrease in the peak current of HQ is directly proportional to the amount of CCN. Linear calibration plot was obtained over the range from 4.0 × 10⁻⁶ to 8.0 × 10⁻⁵ M with a detection limit (S/N = 3) of 2.0 × 10⁻⁶ M. From the inhibitory effect of CCN on the inclusion of HQ by β-CD, the apparent formation constant of CCN with the immobilized β-CD was estimated. This electrochemical sensor showed excellent sensitivity, repeatability, stability and recovery for the determination of CCN. The response mechanism of the sensor was discussed in detail. The optimum steric configuration of inclusion complex was presented by molecular dynamics simulation.     

A novel electrochemical sensor for determination of hydroquinone in water using FeWO4/SnO2 nanocomposite immobilized modified glassy carbon electrode

A novel electrochemical sensor based on iron tungstate doped tin oxide nanocomposite Nafion (FeWO₄/SnO₂/Nf) immobilized modified glassy carbon electrode (GCE) is fabricated to determine hydroquinone (HQ) in this present study. The structural morphology and phase of FeWO₄/SnO₂ nanocomposite are characterized by X-ray powder diffraction (XRD), energy dispersive X-ray analysis (EDX), Fourier transform infrared spectroscopy (FT-IR), high transmission electron microscopy (HR-TEM) and Field emission scanning electron microscopy (FE-SEM), Brunauer-Emmett-Teller (BET) and X-ray photoelectron spectroscopy (XPS) respectively. Electrochemical methods such as cyclic voltammetry (CV), difference pulse voltammetry (DPV) and amperometric (i-t curve) are used to describe the electrochemical performance of the surface modified electrode for HQ sensing studies. The FeWO₄/SnO₂/Nf immobilized GCE is exhibited excellent catalytic activity with the increasing current signal during HQ sensing. The linear range of response is obtained between 0.01 µM and 50 µM for HQ detection under optimized conditions and the low detection limit (LOD) is found to be 0.0013 µM. Moreover, the present modified electrode shows good reproducibility and excellent anti-interference behavior. In addition, the present electrochemical sensor is applied to the real samples of collected waters from various sources and the obtained experimental results are quite satisfactory.