A high-performance and simple method for rapid and simultaneous determination of dihydroxybenzene isomers

A novel idea on the basis of 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin (THPP) functionalized carbon nanotubes (CNTs) film was developed to simulate the chromatographic separation, which was able to rapidly and simultaneously detect dihydroxybenzene isomers based on their different oxidation potentials and corresponding currents. The mechanism involved in the recognition and isolation of the dihydroxybenzene isomers was explored and confirmed by UV spectra and density functional theory. It was proven that the current method for simultaneously detecting and isolating dihydroxybenzene isomers was ascribed to the priority of porphyrin film to induce oxidation of the three kinds of isomers, and the priority depends to a large extent on the different tendencies of dihydroxybenzene to interact with the peripheral hydroxyl group and with the extended π-conjugated ring of porphyrin. Most important of all, porphyrin functionalized CNTs film allows for the formation of well-defined interface and provides an advantageous and high-performance platform for the simultaneous determination and isolation of dihydroxybenzene isomers.     

Electrochemical behavior of dihydroxybenzene isomers at MWCNTs modified electrode and simultaneous determination in neutral condition

Simultaneous determination of dihydroxybenzene isomers in neutral condition was successfully realized by a simple and easy prepared modified electrode without previous chemical or physical separations. The multi-walled carbon nanotubes modified glassy carbon electrode (MWCNTs/GCE), which was prepared by the drop-coating method, was characterized by FE-SEM and TEM. Then, the electrochemical behavior of dihydroxybenzene isomers at MWCNTs/GCE was systematically studied at different temperature and pH conditions. The oxidation peak potentials were separated in neutral condition with 105 mV to hydroquinone (HQ) and catechol (CC) and 390 mV to CC and resorcinol (RS). And in neutral condition, the amperometric current were found to be linear with concentration of HQ, CC, and RS (20–140 μM) with the presence of 100 μM other isomers. Furthermore, excellent anti-interference, stability, and reproducibility were also presented by this modified electrode.     

Simultaneous determination of dihydroxybenzene isomers utilizing a thiadiazole film electrode

The present study reports a sensitive electro-analytical method for the simultaneous determination of dihydroxybenzene isomers by using a thiadiazole film electrode, which was readily prepared by electropolymerization of 2,5-dimercapto-1,3,4-thiadiazole on a glassy carbon electrode with cyclic voltammetry. The functionalized electrode has a distinguishable and sensitive response to dihydroxybenzene isomers. Under the optimized conditions, the linear stripping peak currents showed good linear relationships with hydroquinone, catechol and resorcinol at concentration ranges 0.50-120, 0.50-110 and 1.00-110 μmol/L, and the detection limits are 0.1, 0.1 and 0.3 μmol/L, respectively. The proposed method is applicable to the simultaneous determination of dihydroxybenzene isomers in real samples with the relative standard deviations of less than 5.7% and the recovery rates of 95.6%-106%. The constructed electrode is characterized by simple preparation, good selectivity, and high sensitivity advantages.     

Review on applications of carbon nanomaterials for simultaneous electrochemical sensing of environmental contaminant dihydroxybenzene isomers

Carbonaceous nanostructures stand out as an excellent electrode material to enhance the electrocatalytic, electroconductivity, and long-term stability of the electrochemical sensor in recent years. This review article focus on the important advancement in developing carbonaceous nanomaterials-based electrochemical sensors for simultaneous electrochemical sensing (binary and ternary mixtures) of environmental contaminants dihydroxybenzene isomers. The fabrication of electrochemical sensors such as graphene/carbon nanotubes hybrid composite, graphene/ carbon nanotubes supported nanomaterials, mesoporous carbon, carbon nanofiber, carbon nano-fragment and biochar modified electrode was presented coupled with suitable applications. This review discussed the selective reports on the application of dihydroxybenzene sensors during the period from 2015 to 2020.     

Multi-flow-through sensor for simultaneous cation determination

The activity of several metal ions can be detected potentiometrically using glass electrode measuring chains, which have normally a cylindrical design. To analyse different cations simultaneously, on one hand several single indicator electrodes can be integrated in a prefabricated flow-through equipment, where they can be measured versus electrochemical reference electrodes. On the other hand, by principle it is possible to construct tubular flow-through electrodes. In the present case, glass electrodes are double-walled, so that the liquid internal reference system consisting of reference solution and reference element can be placed.In the case of multi-analysis, for constructional reasons it would be necessary to combine several of such flow-through electrodes by complicated connecting elements. In this paper a multi-flow-through electrode is described, which can be fabricated in one piece by substitution of the liquid by a solid reference half cell. The contact of ion-selective glasses with semiconducting zinc oxide leads to a reversible phase interface, so that a high stability of the individual half cell potentials is achieved. Nearly all electrode properties are in a good agreement with those of traditional cation selective electrodes. The pH electrodes, for example, exhibit almost linear response in a range of pH 1–10 with a slope of 57–59 mV/pH at θ = 25 °C.     

Simultaneous determination of phenylenediamine isomers and dihydroxybenzene isomers in hair dyes by capillary zone electrophoresis coupled with amperometric detection

The simultaneous determination of three isomers of phenylenediamines (o, m, and p-phenylenediamine) and two isomers of dihydroxybenzenes (catechol and resorcinol) in hair dyes was performed by capillary zone electrophoresis coupled with amperometric detection (CZE–AD). The effects of working electrode potential, pH and concentration of running buffer, separation voltage, and injection time on CZE–AD were investigated. Under the optimum conditions the five analytes could be perfectly separated in 0.30 mol L⁻¹ borate–0.40 mol L⁻¹ phosphate buffer (pH 5.8) within 15 min. A 300 μm diameter platinum electrode had good responses at +0.85 V (versus SCE) for the five analytes. Their linear ranges were from 1.0 × 10⁻⁶ to 1.0 × 10⁻⁴ mol L⁻¹ and the detection limits were as low as 10⁻⁷ mol L⁻¹ (S/N = 3). This working electrode was successfully used to analyze eight kinds of hair dye sample with recoveries in the range 91.0–108.0% and RSDs less than 5.0%. These results demonstrated that capillary zone electrophoresis coupled with electrochemical detection using a platinum working electrode as detector was convenient, highly sensitive, highly repeatable and could be used in the rapid determination of practical samples. Figure Electropherograms obtained from 10 mg mL⁻¹ hair dye sample solutions at a platinum working electrode under optimum CZE–AD conditions: (a) natural black (I), (b) golden: (1) p-phenylenediamine, (2) m-phenylenediamine, (3) o-phenylenediamine, (4) resorcinol, and (5) catechol     

Voltammetric determination of dihydroxybenzene isomers using a disposable pencil graphite electrode modified with cobalt-phthalocyanine

Microchimica Acta - A novel voltammetric assay for the simultaneous determination of hydroquinone (HQ), catechol (CC) and resorcinol (RS) by using an electrochemically treated pencil graphite...     

聚甲苯胺蓝/碳纳米管/玻碳电极同时伏安法测定苯二酚异构体

通过电聚合甲苯胺蓝于多壁碳纳米管修饰玻碳电极上制备了聚甲苯胺蓝/碳纳米管/玻碳电极,研究了三种苯二酚异构体在该电极上的电化学行为。结果表明,修饰电极对苯二酚异构体的氧化表现出优异的电催化性能和选择性。考察了各种影响因素。在5.0×10-6～2.0×10-4mol/L的范围内,苯二酚异构体的阳极峰电流与其浓度有线性关系,建立了一种同时伏安分析3种苯二酚异构体的新方法。     

Simultaneous determination of dihydroxybenzene positional isomers by capillary electrochromatography using gold nanoparticles as stationary phase

The paper describes the enhanced separation of o-, m-, p-dihydroxybenzene by capillary electrochromatography (CEC) using gold nanoparticles (AuNPs) as stationary phase. The effect of the AuNPs concentration upon separation was investigated. The experimental parameters, including separation voltage, pH, and concentration of running buffer, were optimized. Under the optimum conditions, a good resolution of three dihydroxybenzene isomers was obtained within 15 min in a 50 cm effective length capillary modified with 0.02 nmol/L AuNPs at a separation voltage of 16 kV in a 50 mmol/L acetate buffer (pH 5.0). The linear ranges were from 10(-6) to 10(-4) mol/L and the detection limits were as low as 10(-7) mol/L. This method was successfully used to analysis two kinds of hair coloring agent sample with recoveries in the range of 90-105% and relative standard deviations (RSD) less than 5.0%.     

Solubility of dihydroxybenzene isomers in supercritical carbon dioxide

The equilibrium solubilities of dihydroxybenzene isomers pyrocatechol, resorcinol and hydroquinone have been measured in supercritical carbon dioxide using a simple static method. The measurements were performed in the pressure range from 120 to 400 atm at temperatures 35, 45, 55 and 65°C for pyrocatechol and resorcinol and in the pressure range from 120 to 200 atm at temperature 35°C for hydroquinone. The solubility of the isomers in supercritical CO₂ was found to vary in the order pyrocatechol>resorcinol≫hydroquinone. The experimental data were correlated by use of the density based model proposed by Chrastil.     

Simultaneous determination of dihydroxybenzene and phenylenediamine positional isomers using capillary zone electrophoresis coupled with amperometric detection

In general capillary zone electrophoresis (CZE) separation models, o‐, m‐, and p‐phenylenediamine isomers can be separated in a weak acidic running buffer for their pK_a values being 4.52, 5.64, 6.04, respectively, while o‐, m‐, and p‐dihydroxybenzene isomers can be separated in a weak basic buffer for their pK_a values being 9.40, 9.40 and 10.04, respectively. So, it is hard to find a suitable running buffer at a fixed pH in normal CZE for simultaneous separation of these two groups of positional isomers. In this paper, a novel method based on alternately running two different pH buffers in CZE coupled with amperometric detection (CZE‐AD) was designed to simultaneously determine these two groups of positional isomers. It is found that when two different pH running buffers were employed alternately under appropriate order and time, the six analytes could be separated perfectly in less than 20 min and the detection limits were as low as 10^–7 mol/L. Furthermore, the effects of working electrode potential, pH and concentration of running buffer, separation voltage and injection time on CZE–AD were investigated. Experimental results demonstrated that the introduced method was practical to simultaneously determine two groups of positional isomers with different pK_a and had some advantages of high sensitivity, good repeatability and small sample requirement.     

Simultaneous voltammetric determination of dihydroxybenzene isomers using a poly(acid chrome blue K)/carbon nanotube composite electrode

A novel modified electrode was fabricated by electropolymerization of acid chrome blue K at a multi-walled carbon nanotubes modified glassy carbon electrode. The electrode developed was used for simultaneous determination of the isomers of dihydroxybenzene in environmental samples using first order linear sweep derivative voltammetry with background subtraction. A linear relationship between peak current and concentration of hydroquinone, catechol and resorcinol was obtained in the range of 1 × 10⁻⁶–1 × 10⁻⁴ mol L⁻¹, and the detection limits were estimated to be 1 × 10⁻⁷, 1 × 10⁻⁷ and 9 × 10⁻⁸ mol L⁻¹, respectively. The constructed electrode showed excellent reproducibility and stability. Real water samples were analyzed and satisfactory results were obtained. This method provides a new way of constructing electrodes for environmental and biological analysis.     

Spectrophotometric simultaneous determination of nitroaniline isomers by orthogonal signal correction-partial least squares

The simultaneous determination of nitroaniline isomer mixtures by using spectrophotometric methods is a difficult problem in analytical chemistry, due to spectral interferences. By multivariate calibration methods, such as partial least squares (PLS), it is possible to obtain a model adjusted to the concentration values of the mixtures used in the calibration range. Orthogonal signal correction (OSC) is a preprocessing technique used for removes the information unrelated to the target variables based on constrained principal component analysis. OSC is a suitable preprocessing method for partial least squares calibration of mixtures without loss of prediction capacity using spectrophotometric method. In this study, the calibration model is based on absorption spectra in the 200–500 nm range for 21 different mixtures of nitroaniline isomers. Calibration matrices were containing 1–21, 1–15 and 1–18 μg ml⁻¹ of m-nitroaniline, o-nitroaniline and p-nitroaniline, respectively. The RMSEP for m-nitroaniline, o-nitroaniline and p-nitroaniline with OSC and without OSC were 0.6567, 0.2692, and 0.3134, and 1.3818, 1.2181, and 0.3953, respectively. This procedure allows the simultaneous determination of nitroaniline isomers in real matrix samples and good reliability of the determination was proved.     

A chemiluminescence array sensor based on graphene-magnetite-molecularly imprinted polymers for determination of benzenediol isomers

A chemiluminescence (CL) array sensor for determination of benzenediol isomers simultaneously using the system of luminol–NaOH–H₂O₂ based on a graphene-magnetite-molecularly imprinted polymer (GM-MIP) is described. Use of graphene in the GM-MIP thus prepared is helpful to improve the adsorption capacity, while use of magnetite nanoparticles can facilitate the isolation of GM-MIP at end of their synthesis, and rendering easier the use of the polymers in the array sensor. The adsorption performance and properties were characterized. The GM-MIP was used to increase the selectivity in CL analysis. In addition, the sensor was reusable and of good selectivity and adsorption capacity. The array sensor was finally used for the determination of hydroquinone, resorcinol and catechol in waste water samples simultaneously.     

Multi-syringe flow injection solid-phase extraction system for on-line simultaneous spectrophotometric determination of nitro-substituted phenol isomers

In this paper, a time-based multi-syringe flow injection (MSFI) approach is proposed for automated disk-based sorbent extraction of three nitro-substituted phenol isomers (2-, 3-, and 4-nitrophenol) followed by on-line simultaneous determination of individual species by diode-array spectrophotometry. The method involves the on-line enrichment of the targeted analytes from an acidic medium containing 0.1 mol L⁻¹ HCl onto a co-polymeric sorbent material, and the concurrent removal of potentially interfering matrix components. The nitrophenol isomers are subsequently eluted with an alkaline solution (0.7 mol L⁻¹ NaOH), whereupon the eluate is delivered to a diode-array spectrophotometer for recording of the spectral data in the UV-vis region. Deconvolution of strongly overlapped spectra was conducted with multivariate regression models based on multiple linear regression calibration. The analytical performance of the chemometric algorithm was characterized by relative prediction errors and recoveries.The MSFI manifold was coupled to a multiposition selection valve to set a rugged analyzer that ensures minimum operational maintenance via exploitation of membrane switching protocols. As compared with earlier methods for isolation/pre-concentration of nitro-substituted phenols based on liquid-liquid extraction, the proposed flow-through disk-based system should be regarded as an environmentally friendly approach because the use of harmful organic solvents is circumvented. Under the optimized chemical and physical variables, the 3σ_blank detection limits for 2-, 3-, and 4-nitrophenol were 1.2, 3.2 and 0.3 μmol L⁻¹ for a sample loading volume of 1.5 mL, and the relative standard deviations were ≤5.0%. The flowing system, which is able to handle up to 135 samples automatically, was proven suitable for monitoring trace levels of the target isomers in mineral, tap, and seawater.     

Fabrication of a nanostructure-based electrochemical sensor for simultaneous determination of N-acetylcysteine and acetaminophen

A carbon-paste electrode modified with 2,7-bis(ferrocenyl ethyl)fluoren-9-one (2,7-BF) and carbon nanotubes (CNTs) was used for the sensitive and selective voltammetric determination of N-acetylcysteine (NAC). The mediated oxidation of NAC at the modified electrode was investigated by cyclic voltammetry (CV). Also, the values of catalytic rate constant (k), and diffusion coefficient (D) for NAC were calculated. Differential pulse voltammetry (DPV) of NAC at the modified electrode exhibited two linear dynamic ranges with a detection limit (3σ) of 52.0 nmol L⁻¹. DPV was used for simultaneous determination of NAC and acetaminophen (AC) at the modified electrode, and quantitation of NAC and AC in some real samples by the standard addition method.     

人工神经网络法同时测定苯二酚异构体

研究了人工神经网络法与紫外分光光度分析相结合，用于邻苯二酚、间苯二酚、对苯二酚异构体的含量测定。本研究采用人工神经网络法，直接对苯二酚异构体混合液的紫外吸收光谱数据进行预测，不需预先分离，即可得到各异构体的浓度。