Electrochemical and spectroscopic study of vitamin D2 by in situ thin layer CD spectroelectrochemistry

The electrooxidation of vitamin D₂ (VD₂) was studied by cyclic voltammetry and in situ circular dichroic (CD) spectroelectrochemistry for the first time. The mechanism of electrooxidation and some useful kinetic and adsorption parameters were obtained. The results showed that the oxidation of VD₂ in ethanol solution is an irreversible diffusion controlled process following a weak adsorption of the electroinactive product at a glassy carbon electrode, which blocks the electrochemical reaction. The electrooxidation occurs mainly at the triene moieties of the VD₂ molecule. The CD spectroelectrochemical data were treated by the double logarithm method together with nonlinear regression, from which the formal potential E⁰=1.08 V, αn=0.245, the standard electrochemical rate constant k⁰=4.30(±0.58)×10⁻⁴ cm s⁻¹, and the adsorption constant β=1.77(±0.25) were obtained.     

Electrocatalytic Oxidation and Voltammetric Determination of L‐Cysteic Acid at the Surface of p‐Bromanil Modified Carbon Paste Electrode

The electrochemical properties of L ‐cysteic acid studied at the surface of p‐bromanil (tetrabromo‐p‐benzoquinone) modified carbon paste electrode (BMCPE) in aqueous media by cyclic voltammetry (CV) and double step potential chronoamperometry. It has been found that under optimum condition (pH 7.00) in cyclic voltammetry, the oxidation of L ‐cysteic acid at the surface of BMCPE occurs at a half‐wave potential of p‐bromanil redox system (e.g., 100 mV vs. Ag|AgCl|KCl_sat), whereas, L ‐cysteic acid was electroinactive in the testing potential ranges at the surface of bare carbon paste electrode. The apparent diffusion coefficient of spiked p‐bromanil in paraffin oil was also determined by using the Cottrell equation. The electrocatalytic oxidation peak current of L ‐cysteic acid exhibits a linear dependency to its concentration in the ranges of 8.00×10^?6 M–6.00×10^?3 M and 5.2×10^?7 M–1.0×10^?5 M using CV and differential pulse voltammetry (DPV) methods, respectively. The detection limits (2σ) were determined as 5.00×10^?6 M and 4.00×10^?7 M by CV and DPV methods. This method was used as a new, selective, rapid, simple, precise and suitable voltammetric method for determination of L ‐cysteic acid in serum of patient's blood with migraine disease.     

间苯二胺的电化学及紫外-可见薄层光谱电化学研究

研究了间苯二胺(MPD)在金电极和SnO₂;F膜电极上的循环伏安行为及在SnO₂;F膜电极上的紫外-可见薄层光谱电化学性质.获得了间苯二胺在SnO₂;F膜电极上电氧化的薄层恒电势电解-吸收光谱图,采用双对数法对紫外-可见薄层光谱电化学数据进行了处理.研究了间苯二胺的光谱及电化学性质,求得了间苯二胺的动力学修饰式量电位E⁰和αn等热力学参数.     

循环伏安和现场红外光谱电化学研究镉(Ⅱ)在普鲁士蓝/铂修饰电极上的反应

报道了普鲁士蓝(PB)膜修饰Pt电极在CdCl_2溶液中进行循环伏安(CV)扫描,衍生为含有部分六氰亚铁酸镉(CdHCF)混合修饰膜的电化学反应,并对其反应机理进行了电化学和现场红外光谱电化学(FTIRs)的研究.实验结果表明,这一混合膜中PB和CdHCF两种成分之间的相互影响并不大,两种物质基本上保持了各自为纯物质时的电化学特性.     

Voltammetric Determination of L‐Dopa on Poly(3,4‐ethylenedioxythiophene)‐Single‐Walled Carbon Nanotube Composite Modified Microelectrodes

In the present communication, it is shown that platinum microelectrodes electrochemically coated with a composite of poly(3,4‐)ethylenedioxythiophene and single‐walled carbon nanotubes (PEDOT/SWNT) enable determinations of 3,4‐dihydroxy‐L ‐phenylalaines (L ‐dopa) in neutral phosphate buffer solutions containing an excess of ascorbic acid. The interpenetrated networked nanostructure of the composite was characterized by scanning electron microscope (SEM) and Raman spectroscopy. It is shown that the presence of the composite gives rise to an increase in the electroactive area of an order of magnitude in compared to the area for the bare microelectrodes. The composite film‐coated microelectrode, which yielded reversible cyclic voltammograms for the ferro/ferricyanide redox couple for scan rates between 0.01 and 0.10 V s^?1, also gave rise to two well‐resolved oxidation peaks for L ‐dopa and ascorbic acid (AA). The latter effect, which was not seen in the absence of the composite, enabled differential pulse voltammetric determinations of L ‐dopa in the concentration range between 0.1 to 20 μM with a detection limit of 100 nM.     

Modification of Glassy Carbon Electrodes with a Poly‐L‐Lysine/Glutaraldehyde Film

A film of poly‐L ‐lysine (PLL) adheres better to the surface of a glassy carbon electrode when the PLL is partially cross‐linked by means of glutaraldehyde. A film composition of 97.5% PLL/2.5% glutaraldehyde gives good adhesion and retains the anionic exchange capability of the PLL. The performance of the film was tested with hexacyanoferrate(III) using electrochemical and nonelectrochemical accumulation.     

L‐Cysteine Voltammetry at a Carbon Paste Electrode Bulk‐Modified with Ferrocenedicarboxylic Acid

The electrochemical behavior of L ‐cysteine studied at the surface of ferrocenedicarboxylic acid modified carbon paste electrode (FDCMCPE) in aqueous media using cyclic voltammetry, differential pulse voltammetry and double potential step chronoamperometry. It has been found that under optimum condition (pH 8.00) in cyclic voltammetry, the oxidation of L ‐cysteine occurs at a potential about 200 mV less positive than that of an unmodified carbon paste electrode. The kinetic parameters such as electron transfer coefficient, α, and catalytic reaction rate constant, k_h were also determined using electrochemical approaches. The electrocatalytic oxidation peak current of L ‐cysteine showed a linear dependent on the L ‐cysteine concentration and linear analytical curves were obtained in the ranges of 3.0×10^?5 M–2.2×10^?3 M and 1.5×10^?5 M–3.2×10^?3 M of L ‐cysteine concentration with cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods respectively. The detection limits (3σ) were determined as 2.6×10^?5 M and 1.4×10^?6 M by CV and DPV methods.     

Multilayer Assemblies Consisting of Tri‐Vanadium‐Substituted Heteropolyanions and Its Electrocatalytic Properties

We describe the controlled fabrication of ultrathin multilayer films consisting of tri‐vanadium‐ substituted heteropolytungstate anions (denoted as P₂W₁₅V₃) and a cationic polymer of quaternized poly (4‐vinylpyridine) partially complexed with osmium bis(2,2′‐bipyridine) (denoted as QPVP‐Os) on the 4‐aminobenzoic acid (4‐ABA) modified glassy carbon electrode (GCE) surface based on layer‐by‐layer assembly. Cyclic voltammetry and UV‐vis absorption spectrometry have been used to easily monitor the thickness and uniformity of thus‐formed multilayer films. The V‐centered redox reaction of P₂W₁₅V₃ in the multilayer films can effectively catalyze the reduction of BrO and NO . The resulting P₂W₁₅V₃/QPVP‐Os multilayer film modified electrode behaves as a much promising electrochemical sensor because of the low overpotential for the catalytic reduction of BrO and NO , and the catalytic oxidation of ascorbic acid.     

New hydrophobic L‐amino acid salts: maleates of L‐leucine,L‐isoleucine and L‐norvaline

Crystals of maleates of three amino acids with hydrophobic side chains [L‐leucenium hydrogen maleate, C₆H₁₄NO₂⁺·C₄H₃O₄⁻, (I), L‐isoleucenium hydrogen maleate hemihydrate, C₆H₁₄NO₂⁺·C₄H₃O₄⁻·0.5H₂O, (II), and L‐norvalinium hydrogen maleate–L‐norvaline (1/1), C₅H₁₁NO₂⁺·C₄H₃O₄⁻·C₅H₁₂NO₂, (III)], were obtained. The new structures contain C₂²(12) chains, or variants thereof, that are a common feature in the crystal structures of amino acid maleates. The L‐leucenium salt is remarkable due to a large number of symmetrically non‐equivalent units (Z′ = 3). The L‐isoleucenium salt is a hydrate despite the fact that L‐isoleucine is a nonpolar hydrophobic amino acid (previously known amino acid maleates formed hydrates only with lysine and histidine, which are polar and hydrophilic). The L‐norvalinium salt provides the first example where the dimeric cation L‐Nva...L‐NvaH⁺ was observed. All three compounds have layered noncentrosymmetric structures. Preliminary tests have shown the presence of the second harmonic generation (SGH) effect for all three compounds.     

Determination of Esomeprazole on an Electropolymerized L‐arginine and β‐cyclodextrin Modified Screen Printed Carbon Electrode

The formation of an inclusion complex of the proton‐pump inhibitor (PPI) drug esomeprazole (ESO) with ß‐cyclodextrin (ß‐CD) has been investigated and proven by cyclic voltammetry (CV). The formation constant of the complex was determined. Thereafter, an electropolymerized β‐CD and L‐arginine (L‐arg) modified screen printed carbon electrode (P‐β‐CD‐L‐arg/SPCE) was developed for the determination of ESO using differential pulse adsorptive stripping voltammetry (DPAdSV). A significant enhancement of the peak current was observed when applying an accumulation step due to the effect of adsorption. Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) further indicated that the polymer of β‐CD and L‐arg efficiently improved the electron transfer kinetic between analyte and electrode surface. Under the optimized conditions, the oxidation peak current was linearly proportional to the concentration of the drug in the range of 1.0×10^?8 to 1.0×10^?5 M. The DPAdSV method was successfully used to determine the concentrations of the drug in spiked human serum samples.     

Disposable Injection‐Moulded Cell‐on‐a‐Chip Microfluidic Devices with Integrated Conducting Polymer Electrodes for On‐Line Voltammetric and Electrochemiluminescence Detection

This work reports the construction and characterization of plastic electrochemical micro‐flow‐cells with integrated injection‐moulded polymer electrodes. The three electrodes (working, auxiliary, and reference) were fabricated by injection‐moulding from a conducting grade of polystyrene loaded with carbon fibers. On‐chip reference electrodes were prepared by coating one of the conducting polymer electrodes with a Ag/AgCl layer (implemented either by e‐beam evaporation of Ag followed by electrochemical formation of AgCl or by applying a Ag/AgCl paste). Working electrodes were either polymer electrodes coated with Au by e‐beam evaporation or bare conducting polymer electrodes. The electrodes were integrated into the micro‐flow‐cells by an over‐moulding process followed by ultrasonic welding. The devices were characterized by optical and electrochemical techniques. Studies by cyclic voltammetry (CV), anodic stripping voltammetry (ASV) and electrochemiluminescence (ECL) demonstrate ‘proof–of‐principle’ of the micro‐flow‐cells as electrochemical sensors.     

Electrochemical Behaviour and Rapid Determination of L‐Dopa at Electrochemically Pretreated Screen Printed Carbon Electrode

A simple and rapid voltammetric method based on a disposable electrochemically pretreated screen‐printed carbon electrode is proposed for the determination of L ‐dopa. Under optimum differential pulse voltammetry conditions a limit of detection of 3.6×10^?7 M for L ‐dopa was obtained. The method was successfully applied to the determination of L ‐dopa in a commercial pharmaceutical formulation.     

Electrochemical impedance spectroscopy and in situ UV‐vis spectroelectrochemistry studies of Poly(N‐vinyl carbazole)/ Polydimethylsiloxane composite electrodes

Poly(N‐vinyl carbazole)/polydimethylsiloxane (PNVCz/PDMS) composite electrodes were prepared by electrochemical polymerization of NVCz monomer onto PDMS‐coated platinum (Pt) and glassy carbon (GC) electrode surfaces to investigate the influence of the insulating constituent, PDMS and process temperature on the capacitive performance of the coated layers. The electrochemical properties of the bilayer coatings were studied by electrochemical impedance spectroscopy and UV‐vis spectroelectrochemistry measurements. The low‐frequencies capacitance values of composite electrodes indicated that the capacitive behaviors of the composites decreased with increasing PDMS content (from 5.0 to 10.0; in wt/v%) in coating solutions at 25 °C, and with decreasing coating temperatures (from 25 °C to ? 15 °C) of PDMS and PNVCz and, more resist PDMS/PNVCz layers formed. Copyright © 2011 John Wiley & Sons, Ltd.     

Spectroelectrochemical Study of N‐Substituted Phenoxazines as Electrochemical Labels of Biomolecules

The electrochemical conversion of N‐substituted phenoxazines (NSP's) bearing a CH₂CH₂? X substitute (where X?OH, COOH, CH₂NH₂, CH₂SO₃H, CH₂NHCOR) was investigated using cyclic voltammetry on a bulk gold electrode and a thin‐layer spectroelectrochemical cell. The electrochemical oxidation of NSP's on the gold electrode was quasi‐reversible and proceeded in a diffusion‐controlled regime. The formal redox potential of NSP's covered the range from 0.39 to 0.45 V vs. SCE. The electrochemical oxidation of NSP's in the thin‐layer spectroelectrochemical cell produced radical cations that showed absorbance at 385, 410 and 530 nm. Electrochemical conversion fitted the general voltammetric current‐potential equation of a reversible wave, whereas electrolysis at constant potential showed a typical Cottrell behavior. Combining of NSP's with a biologically‐relevant theophylline molecule did not change electrochemical and spectral properties of the phenoxazine core. Theophylline enlarged with NSP's demonstrated electrochemical and biocatalytic behavior similar to that of NSP's. The investigated NSP's possess electrochemical and spectral properties that are useful as biomolecular labels for electroanalysis.     

Immobilization of Tyrosinase on Chitosan — An Optimal Approach to Enhance the Productivity of L‐DOPA from L‐Tyrosine

Tyrosinase was immobilized on Chitosan (CTS) beads to produce 3,4‐dihydroxy‐L‐phenylalanine (L ‐DOPA) from L ‐tyrosine. Epichlorohydrin (ECH), ethylene glycol diglycidyl ether (EGDE), and glutaraldehyde (GLU) were used as coupling agents, respectively. Ultraviolet/visible measurements on CTS films showed that the reaction intermediate (L ‐dopaquinone) attacked the amino groups on CTS, so the amine residues on chitosan were capped by acetic acid anhydride (Ac) or formaldehyde (Fm) to avoid the deactivation of the immobilized tyrosinase. The pH and temperature of the maximal rate to produce L‐DOPA were investigated. GLU (coupling agent) and Ac (capping agent) were selected for practical utility. A 7.5% (w/v) concentration of GLU was found to attain maximal activity of the immobilized enzyme. The thermal stability of tyrosinase immobilized on CTS‐GLU‐Ac, and after treatment with sodium borohydride, was enhanced to a great extent. The L ‐DOPA converting efficiency in the environmental conditions of this study decreased from 45.1% to 39.9% (between 1^st and 30^th batch). This immobilized tyrosinase can be used practically in the production of L‐DOPA from L‐tyrosine.     

Voltammetric and Differential Pulse Stripping Study of Adenine on a Sol‐gel Derived Carbon Composite Electrode

This communication reports on the electrochemical investigation of adenine on a sol‐gel carbon composite electrode (CCE). Cyclic voltammetric (CV) technique is used to characterize the redox behavior of adenine at CCE. The peak current and peak potentials are dependent on the pH of the buffer solution. From the scan rate and peak current study, there is evidence of adsorption of adenine on the CCE. The parameters affecting the differential pulse stripping adsorption peak were systematically optimized. Under optimum conditions of E_acc=?0.10 and t_acc=60 s, a linear calibration plot was obtained, 2×10^?7–1×10^?6 M. This CCE is useful for the simultaneous analysis of adenine and guanine from denatured DNA.     

Voltammetric Sensor for Sodium Nitroprusside Determination in Biological Fluids Using Films of Poly‐L‐Lysine

Sodium nitroprusside (NP), a commercial vasodilator, can be pre‐concentrated on vitreous carbon electrode modified by films of 97.5%: 2.5% poly‐L ‐lysine (PLL): glutaraldehyde (GA). This coating gives acceptable anion exchange properties whilst giving the required improvement of adhesion to the glassy carbon electrode surface. Linear response range and detection limit on nitroprusside in B‐R buffer pH 4.0, were 1×10^?6 to 2×10^?5 mol L^?1 and 1×10^?7 mol L^?1, respectively. The repeatability of the proposed sensor, evaluated in term of relative standard deviation, was measured as 4.1% for 10 experiments. The voltammetric sensor was directly applied to determination of nitroprusside in human plasma and urine samples and the average recovery for these samples was around 95–97% without any pre treatment.     

Electrocatalytic Oxidation of NADH by Oxidized s‐Adenosyl‐L‐Methionine (SAMe): Application to NADH and SAMe Determinations

s‐Adenosyl‐L ‐methionine (SAMe) is an adenosine analogue with therapeutical activity against affective disorders and liver dysfunctions. It can be oxidized on graphite electrode yielding a strongly adsorbed electroactive oxidation product for which a quinone‐imine structure is proposed. This compound is capable of electrocatalyzing the NADH oxidation at low potentials, lowering the overvoltage by about 300 mV. An amperometric method for NADH determination at +0.1 V (Ag|AgCl|KCl_sat) is developed using an oxidized‐SAMe‐modified electrode in pH 9. Linear calibration plots were obtained with a detection limit of 2.4 nM. The electrode response time and the relative standard deviation of the slope of the calibration plot for 5 different modified electrodes were 12 s and 5.6% respectively. The catalytic scheme also provides the first method to determine SAMe itself by adsorptive differential pulse voltammetry. The linear range was found to be 42.4–424 nM with a reproducibility of 6.9%. The method was applied to SAMe determination in a pharmaceutical formulation.     

Voltammetric Reduction of a 4‐Nitroimidazole Derivative on a Multiwalled Carbon Nanotubes Modified Glassy Carbon Electrode

We report the electrochemical behavior of a 4‐nitroimidazole derivative, 1‐methyl‐4‐nitro‐2‐hydroxymethylimidazole (4‐NImMeOH), on glassy carbon electrode (GCE) modified with multiwalled carbon nanotubes (MWCNT). As dispersing agents, dimethylformamide (DMF) and water were used. The electrochemical response of the resulting electrodes was evaluated using linear sweep, cyclic and square‐wave voltammetry (LSV, CV and SWV). Several parameters such as medium pH, nature and concentration of the CNTs dispersion and accumulation time were tested. The optimal conditions determined for obtain better response were: pH 2, dispersion concentration=4 mg/mL of CNT in water, accumulation time=7 min. The MWCNT‐modified GCE exhibited attractive electrochemical properties producing enhanced currents with a significant reduction in the overpotential and good signal‐to‐noise characteristics, in comparison with the bare GCE. The modified electrode is highly repeatable for consecutive measurements, reaching a variation coefficient of 2.9% for ten consecutive runs.     

Electrochemical and Spectroelectrochemical Analysis of 4‐(4‐(5‐Phenyl‐1,3,4‐oxadiazole‐2‐yl)phenoxy)‐Substituted Cobalt(II), Lead(II) and Metal‐Free Phthalocyanines

Electrochemical and spectroelectrochemical analyses of 4‐(4‐(5‐phenyl‐1,3,4‐oxadiazole‐2‐yl)phenoxy)‐substituted metal‐free phthalocyanine ( H₂Pc ( 1 )) and metallated phthalocyanines ( PbPc ( 2 ) and CoPc ( 3 )) were performed in solution. Voltammetric characterizations of the phthalocyanine complexes were investigated by using cyclic voltammetry and square wave voltammetry techniques. CoPc ( 3 ) gave common metal and ring based electron transfer reactions; however they split due to the aggregation. Although PbPc ( 2 ) illustrated reversible reduction processes during the voltammetric measurements, it was de‐metallized and thus turned to the metal free phthalocyanine during repetitive voltammetric cycles and in situ spectroelectrochemical measurements.