核黄素在电化学还原石墨烯/Nafion修饰电极上的电化学行为及分析检测

本文采用电化学还原石墨烯(ECGO)/Nafion修饰玻碳电极对核黄素的循环伏安特性进行了研究。结果显示,ECGO/Nafion修饰薄膜对核黄素显示出良好的催化效果。实验考察了氧化石墨烯(GO)/Nafion的用量、扫描圈数、pH值、电位等对核黄素电化学行为的影响。在最优条件下,采用差分脉冲伏安法测定了核黄素检测的线性范围,结果显示,氧化峰电流与核黄素的浓度在7.5×10~(-8)~1.0×10~(-5) mol·L~(-1)范围内呈现良好的线性关系,检测限可达2.5×10~(-8) mol·L~(-1)。用该方法测定实际样品中的核黄素含量,效果较好。     

Electrochemical Behavior and Determination of Hyoscine‐N‐Butylbromide from Pharmaceutical Preparations

The electrooxidation of hyoscine N‐butylbromide (HBB) was investigated by rotating disk electrode voltammetry, cyclic voltammetry and controlled potential coulometry in 0.1 M HNO₃ and in 0.1 M tetrabutylammonium perchlorate (TBAP) solutions of acetonitrile at a platinum (Pt) electrode. Based on the results obtained, it is suggested that a bromide ion of HBB was oxidized in one reversible step in aqueous solutions and in two reversible steps in acetonitrile. A differential pulse voltammetric (DPV) method at a Pt electrode was developed for the determination of HBB in the concentration range of 1.0 × 10^?6‐1.0 × 10^?3 M. The procedure was applied to the determination of HBB in its formulations as well as its recovery from blood serum and urine samples.     

Electrochemical Behavior of Herbal Antitumor Drug Aloe‐Emodin at Carbon‐Coated Nickel Magnetic Nanoparticles Modified Glassy Carbon Electrode

The electrochemical behavior of aloe‐emodin (AE), an important herbal antitumor drug, was investigated at a carbon‐coated nickel magnetic nanoparticles modified glassy carbon electrode (CNN/GCE). A couple of well‐defined redox peaks was obtained. Some electrochemical parameters of AE at a CNN/GCE, such as the charge number, exchange current density, standard heterogeneous rate constant, were measured. The square wave voltammetry (SWV) response of AE was linear with the concentration over two concentration intervals viz. 6.24×10^?9?1.13×10^?6 M and 1.13×10^?6?1.23×10^?5 M, with a detection limit of 2.08 nM. A fast, simple and sensitive detection and analysis of AE was developed.     

Study of the Electrochemical Behavior of Biodiesel Microemulsion

Microemulsions have become a widely employed technique for the control of biodiesel quality but are still poorly understood as regard to their electrochemical behavior. In this work, we report the fundamental importance associated with the knowledge of electrochemical behavior of microemulsions composed of water in the presence of a supporting electrolyte, soybean biodiesel and propan‐1‐ol as consolute, along with the ferrocyanide–ferricyanide redox system applied as probe. The voltammetric results showed that for different compositions of microemulsions, variation in peak currents and change in system reversibility as well as in the electron transfer process were clearly noted. Furthermore, through the study of the diffusion coefficient, three different types of microemulsions including Oil/Water, Bicontinuous, and Water/Oil were successfully identified. Electrochemical impedance spectroscopy studies were also carried out aiming at obtaining more information regarding the electrode/solution interface. All the studies performed demonstrated that different types of microemulsions were formed upon exerting a direct influence on the electrochemical behavior of the redox probe. These results, in essence, point to the possibility of choosing a more suitable and advantageous microemulsion type for the development of an analytical method, as in the case, for example, of the microemulsions ME‐2 and ME‐3 which presented high voltammetric response in redox probe oxidation.     

Electrochemical sensitive determination of acetaminophen in pharmaceutical formulations at iron oxide/graphene composite modified electrode

Acetaminophen (AC) is one of the most commonly prescribed analgesic and antipyretic drug, which is considered to be safe as well as effective. Rational use of AC does not pose any toxicity or adverse effects, however, an overdose or prolonged use could lead to nephrotoxicity and severe hepatoxicity. Thus, monitoring of AC is essential for drug safety. In this work, a facile Fe₂O₃/reduced graphene oxide (Fe₂O₃/RGO) nanocomposite was synthesized for improved electrochemical detection of AC. The material was synthesized through a simple one-step process. For characterization of synthesized Fe₂O₃/RGO composite, energy-dispersive X-ray spectroscopy (EDX), field emission-scanning electron microscopy (FE-SEM) and electrochemical impedance spectroscopy (EIS) were employed. To verify the electrochemical performance of Fe₂O₃/RGO nanocomposite, GCE was modified with this nanocomposite and utilized for quantification of AC. The detection limit of AC was 21 nM in a linear range from 1.0 × 10⁻⁷ to 74 × 10⁻⁶ M. Furthermore, the sensor also unveiled good stability, promising sensitivity and selectivity. Hence, Fe₂O₃/RGO could be applied as a sensing material for electrochemical detection of AC. Finally, the analytical utility of the method was also verified in human urine and drug samples with some preliminary treatments.     

Electrochemical Overoxidation of Polyindole and Its Cation‐Permselective Behavior

Polyindole films prepared by potentiostatic growth in dichloromethane solution were subjected to overoxidation studies in aqueous media. Overoxidation at potentials greater than 1.1 V (vs. SCE) in 0.1 M KNO₃ or 0.1 M H₂SO₄ was possible. Overoxidation in 0.1 M NaOH resulted in mechanically unstable films which were not adherent to the electrode surface. The overoxidation process in 0.1 M KNO₃ involved removal of one electron per four indole monomer moieties in the polymer film. Nucleophilic attack led to introduction of carboxylate functionality and to cation permselective behavior, as tested by cyclic voltammetry and hydrodynamic voltammetry of hexamminoruthenium(III) and hexacyanoferrate(III). Such films may be useful in various electrochemical sensor applications.     

香兰素在玻碳电极上的电化学行为及其循环伏安测定

在pH 7.5的Tris-HCl缓冲介质的底液中,在循环伏安图上在峰电位+0.54 V处可见到香兰素的灵敏的氧化峰.其峰电流Ip与香兰素的浓度在3.286×10-6～3.944×10-4mol·L-1范围内呈线性关系,检出限(3S/N)为1.643×10-6mol·L-1.据此提出了循环伏安测定香兰素的方法,并应用于测定巧克力中香兰素的含量.在巧克力试样中加入不同浓度的香兰素标准,按方法测定以求测定方法的回收率,研究了香兰素在玻碳电极上的电化学行为,结果表明:香兰素的电极过程具有吸附性和不可逆性.     

芦丁在离子液体[bmim]BF4中的电化学行为及其影响因素

采用线性扫描伏安法和循环伏安法研究了芦丁在亲水性离子液体1-丁基-3-甲基四氟硼酸盐([bmim]BF4)中的电化学行为, 讨论了扫描速度、富集时间及温度等因素对其电化学行为的影响. 结果表明, 芦丁在[bmim]BF4中的电极过程是一个受吸附控制的准可逆过程, 电子转移数为2, 标准速率常数ks=0.126 s-1. 同时, 分别考察了水及乙醇对芦丁氧化还原特性的影响, 结果发现, 随着水或乙醇含量的增加, 芦丁的峰电位负移, 峰电流增加, 且水的影响比乙醇的影响明显. 在离子液体-水体系中, 芦丁的峰电流与浓度在4.0×10-5～1.4×10-4 mol/L范围内呈良好的线性关系, 检出限为1.0×10-5 mol/L, 有望用于芦丁含量的分析测定.     

Aspects of Electrochemical Behavior of Aldehydes and Ketones in Protic Media

Reduction of carbonyl group in aldehydes and ketones, as well as oxidation of numerous aldehydes is discussed, as well as those reductions of organic compounds where the C?O group activates cleavage of an adjacent C? X bond where X is a good leaving group like halogen, OH, NH₂ or SR or activates hydrogenation of an adjacent C?C group. Survey involves aliphatic and aromatic aldehydes, aryl alkyl and diaryl ketones, as well as α‐ketoacids, 1,2‐diketones and compounds where the carbonyl group is a part of a ring. The role of acid–base, hydration–dehydration and in some cases keto–enol equilibria on electrochemical behavior is pointed out, as well as the role of buffer kind and concentration and the nature of the cation of supporting electrolyte. Better understanding of these factors promises finding of best conditions for electroanalytical procedures.     

Some Electrochemical Characteristics of Boron‐ and Phosphorus‐Doped Glassy Carbon Electrodes

Three glassy carbon (GC) samples: undoped and doped with boron or phosphorus, prepared at 1000 °C, were compared in respect to hydrodynamic current‐potential curves in acidic medium, cyclic voltammograms for Fe^3+/2+ and Fe(CN)₆^3?/4? and argentometric titrations of halides. Some experiments were also carried out using standard Tokai and Sigri GC and Ag electrode. It appeared that GC doped with boron and phosphorus exhibited significant increase in hydrogen evolution overpotential. As for the electrode kinetics (ΔE_p criterion), no significant difference was observed between doped and undoped electrodes. In the potentiometric titrations the phosphorus‐doped electrode was advantageous over the other GC and Ag electrodes as it enabled more precise end‐point detection.     

阿霉素在氧化铟锡电极上的电化学行为及其应用

阿霉素(ADM)在0.02 mol/L pH 7.50的NaH2PO4-Na2HPO4缓冲溶液中,用氧化铟锡(ITO)电极进行线性扫描伏安法测定,得到一良好的还原峰,其峰电位为-0.63 V。峰电流与ADM浓度在1.0×10-7~5.0×10-6mol/L范围内呈线性关系,检出限为5.0×10-8mol/L。用循环伏安法研究了体系的电化学行为及电极反应机理。实验表明,该体系属两电子还原的不可逆过程。     

Electrochemical Behavior of Graphene‐Based Sensors on the Redox Mechanism of Aspirin

The electrochemical behavior of aspirin at a graphene modified glassy carbon electrode has been investigated using cyclic and differential pulse voltammetric techniques. The dependence of the current on pH, concentration and scan rate was investigated to optimize the experimental conditions for determination of aspirin. A plausible oxidation mechanism was proposed. Under the optimum conditions, the oxidation peak current was linearly proportional to the concentration of aspirin in the range from 1.00×10^?6 to 2.00×10^?4 M with a detection limit of 20.2 nM. The proposed method was successfully applied to aspirin determination in pharmaceutical and real samples.     

Electrochemical dissolution of magnetite in acid solutions

The present paper deals with the electrochemical behavior of magnetite microcrystals in an acid medium. A voltammetric method employing a carbon-paste electroactive electrode (CPEE) with an organic binder was used. It was found that the cathodic voltammograms, which were recorded at different scan rates, formed a set bounded in the space of i–E parameters by a generalizing voltammetric curve corresponding to the effective potential scan rate _eff. In other words, all curves are situated under one enveloping curve, just as the smaller dolls sit in the largest doll of a Russian doll. Reverse currents (a cathodic current in the anodic direction of the potential scan) were observed on the cyclic voltammogram. Forward and reverse currents obey the same laws and have one and the same generalizing curve, which could be taken as the magnetite characteristic.     

褪黑素的电化学氧化行为及伏安法测定

采用电化学方法研究了褪黑素在金电极上的不可逆氧化行为.结果表明：其伏安过程为受弱吸附和扩散共同控制的过程,氧化反应电荷转移数为2.采用伏安法对褪黑素进行测定,方法的检出限可达10^-10ml/L数量级.方法可用于脑白金胶囊中褪黑素含量的测定.     

BPA在Na-MMT-CMC/GCE修饰电极上的电化学行为与检测

用循环伏安法和方波溶出伏安法研究了双酚A(BPA)在Na-MMT-CMC/GCE修饰电极上的电化学行为,并建立了一种检测BPA的电化学方法.实验表明:在pH 11.27的B-R缓冲溶液中,在0.42 V处出现一灵敏度高、峰形好的氧化峰.在优选的实验条件下,BPA浓度在6.0 ～80 μmol/L范围内与峰电流呈良好的线性关系,方法检出限为0.24 μmol/L,运用该法用于BPA回收率的测定取得令人满意的结果.     

Electrochemical Behavior of Calcein and the Interaction Between Calcein and DNA

The electrochemical behavior of calcein (CA) has been investigated by using a conductive carbon black paste electrode (CCBPE) as working electrode. It exhibits a single well‐defined redox peak in phosphate buffered saline in the range of pH 5.5–8.0, which attributes to the irreversible oxidation with 2 electrons and 2 protons participation. Under the optimized analytical conditions, the proposed linear sweep voltammetry (LSV) method allows the determination of CA in a linear concentration range of 0.64–9.60 µM, with a limit of detection of 0.32 µM. Further, the interaction between CA and DNA were studied by voltammetric and spectrometric methods. Both studies have shown that CA can bind to DNA by the intercalation binding mode. Under the present experimental condition, the binding constant β of CA and dsDNA is 1.10×10⁷. Meanwhile, in the loop‐mediated isothermal amplification (LAMP) reaction mixture there is obvious interaction between CA and dsDNA, resulting in a nonignorable decrease of the indicating sensitivity.     

Electrochemical Behavior of Thalidomide at a Glassy Carbon Electrode

Thalidomide is an oral drug marketed in the 1950s as a sedative and an anti‐emetic during pregnancy that was removed from the market when its teratogenic side effects appeared in new born children due to inadequate tests to assess the drug's safety. Recent studies evaluating the use of thalidomide in cancer and HIV diseases have sparked renewed interest. The electrochemical behavior of thalidomide on a glassy carbon electrode has been investigated using cyclic, differential and square‐wave voltammetry in aqueous media at different pHs. The oxidation mechanism of thalidomide is an irreversible, adsorption‐controlled process, pH dependent up to values close to the pK_a and occurs in two consecutive charge transfer reactions. A mechanism of oxidation of thalidomide involving one electron and one proton to produce a cation radical, which reacts with water and yields a final hydroxylated product is proposed. The reduction of thalidomide is also a pH dependent, irreversible process and occurs in a single step, with the same number of electrons and protons transferred. The reduction mechanism involves the protonation of the nitrogen that bridges the two cyclic groups, and the product of the protonation reaction causes irreversible dissociation. Both thalidomide and the non electroactive oxidation and reduction products are strongly adsorbed on the glassy carbon electrode surface.     

Sensitive Electrochemical Determination of Trifluralin at a Disposable Pencil Graphite Electrode

A sensitive differential pulse (DP) voltammetric method has been proposed for the determination of trifluralin (TFA) based on both its reduction and oxidation at a disposable pencil graphite electrode (PGE). DP voltammograms recorded under optimized conditions show that oxidation and reduction peak currents increased linearly in the range from 1.0 to 75.0 μM and from 0.50 to 100.0 μM TFA, respectively. LOD and sensitivity values have been determined as 0.39 μM and 11170 μA mM⁻¹ cm⁻² for oxidation and as 0.20 μM and 22167 μA mM⁻¹ cm⁻² for reduction. The acceptable recovery values (95.2–104.8 %) were obtained from real water samples.     

Electrodes of Nontoxic Solid Amalgams for Electrochemical Measurements

The preparation, activation and electrochemical pretreatment of electrodes based on nontoxic solid amalgams were described. Testing of metal solid amalgam electrodes (MeSAEs) proved their broad applicability in many respects, e.g., as to the range of working potentials and the level of background currents, well comparable with those of the hanging mercury drop electrode (HMDE). A regeneration of their surfaces before each measurements could be simply automatized using a PC‐controlled system providing a reasonable repeatability of voltammetric measurements down to 3% RSD. Combination with stripping techniques at accumulation times t_ac=300 s the detection limit amounted to the concentration level of 1 ppb Cu(II), Pb(II), Cd(II), Zn(II), etc. Best electrochemical properties were exhibited by the silver solid amalgam electrode (AgSAE). For example, polished AgSAE (p‐AgSAE), completely free of liquid mercury, proved satisfactory even at more negative potentials enabling the determination of Zn(II), Mn(II), IO , etc. Moreover, even better repeatability of mercury meniscus modified AgSAE (m‐AgSAE) was due to better quality and renewability of its surface. In many cases further testing confirmed that under appropriate conditions MeSAEs represent good, often cheaper and more users‐friendly alternatives to HMDE.     

兴奋剂马钱子碱的电化学氧化及其伏安法测定

以玻碳电极为工作电极，硫酸钾为支持电解质，在合适的ｐＨ条件下，通过循环伏安法，首次观测到了马钱子碱的不可逆氧化峰。在浓度为２０×１０－４～４０×１０－３ｍｏｌ／Ｌ范围内其峰电流与浓度呈线性关系，检测限为１０×１０－５ｍｏｌ／Ｌ。在正常人体的尿样中，采用标准加入法进行回收实验，其平均回收率为１００８％。该法简便、快速，用５０×１０－４ｍｏｌ／Ｌ的马钱子碱溶液重复测定１０次，相对标准偏差为１８％。对其反应机理作了初步探讨。