Amperometric sensor based on ferrocene-doped silica nanoparticles as an electron transfer mediator for the determination of glucose in rat brain coupled to in vivo microdialysis

In this paper, microdialysis sampling was combined with an enzymatic assay of glucose level in rat brain. A novel amperometric glucose biosensor based on ferrocene-doped silica (FcDS) nanoparticles conjugated with a biopolymer chitosan (CHIT) membrane was developed. These uniform FcDS nanoparticles (about 15 ± 3 nm) were prepared by a water-in-oil (W/O) microemulsion method and were characterized by TEM and electrochemical technology. The nanosilica surface exhibited high biocompatability and the ferrocene doped inside maintained its high electron-transfer efficiency as a mediator. The glucose biosensor showed a detection limit of 2.0 × 10^?6 mol L^?1 with a linear range from 5.0 × 10^?6 to 1.2 × 10^?2 mol L^?1. Coupled to microdialysis, it was used to determine the glucose concentration in rat brain. The result was in satisfactory agreement with the literature.     

Attachment of gold nanoparticles to glassy carbon electrode and its application for the voltammetric resolution of ascorbic acid and dopamine

Gold nanoparticles have been attached on glassy carbon electrode surface through sulfhydryl-terminated monolayer and the gold nanoparticles-immobilized glassy carbon electrodes have been applied to the electrocatalytic oxidation of ascorbic acid, reducing the overpotential by about 200 mV with obviously increased current response. Due to its strong electrocatalytic activity towards ascorbic acid, the gold nanoparticles modified electrode can resolve the overlapped voltammetric waves of ascorbic acid and dopamine into two well-defined voltammetric peaks with peak-to-peak separation in potentials of about 300 mV. This can be used to allow the selective determination of ascorbic acid in the presence of dopamine. The catalytic current obtained from differential pulse voltammetry is linearly dependent on ascorbic acid concentration over the range of 6.5 × 10^?6 to 1.45 × 10^?4 M with correlation coefficient of 0.998 in the presence of dopamine. The detection limit (3σ) for AA was found to be 2.8 × 10^?6 M. The simultaneous determination of ascorbic acid and dopamine in their binary mixture has also been investigated. The modified electrode shows good selectivity, stability and anti-fouling properties. The proposed methods have been used for the selective determination of ascorbic acid in the presence of dopamine and for the simultaneous determination of both them in their mixtures with satisfactory results.     

The electrochemistry and thin-layer luminescence spectroelectrochemistry of rhodamine 6G at a 4,4′-bipyridine-modified gold electrode

We report on the first direct electrochemistry and fluorescence spectroelectrochemistry of rhodamine 6G at a 4,4′-bipyridine-modified gold electrode. The value of n determined in spectropotentiostatic experiments at 1.87×10^?6 mol l^?1 of rhodamine 6G in 0.20 mol l^?1 KCl solution is 1.15, and the experimental value obtained for E⁰′ is ?0.787 V versus Ag ∣ AgCl ∣ KCl_sat, which agrees very well with the value (E⁰′=?0.791 V) obtained using cyclic voltammetry at a modified gold electrode. The values of the diffusion coefficients D_O and D_R for the oxidized and reduced forms of rhodamine 6G calculated from results of potential step and in situ fluorescence measurement experiments are 4.0×10^?6 cm² s^?1 and 4.2×10^?6 cm² s^?1, respectively. Cyclic voltammograms of rhodamine 6G show that the peak current I_p is proportional to the square root of the potential scan rate v^1/2, the ratio of the reduction to the oxidation peak height is about unity, and the separation of both reduction and reoxidation peak potentials ΔE_P is essentially constant at 135 mV at low scan rates. These results indicate that electrochemistry of rhodamine 6G at a 4,4′-bipyridine-modified gold electrode is a quasi-reversible one-electron electrode process.     

Catechin antioxidant action at various pH studied by cyclic voltammetry and PM3 semi-empirical calculations

The mechanism of catechin electro-oxidation at various pH was studied using cyclic voltammetry (CV) on the glassy carbon (GC) electrode and PM3 semi-empirical calculations. The influence of activation of the surface of the GC electrode on CV results has been discussed. Mixed adsorption–diffusion control has been observed by applying mechanistic criteria of CV to the results obtained at the activated electrode. The calculated catechin diffusion coefficient D = 2.78 × 10^?6 cm² s^?1. A linear increase of the current peak has been observed with the increase of substrate concentration up to 40 μmol dm^?3 (surface coverage Γ ～ 10^?11 mol cm^?2). In the whole investigated pH range, the dE/dpH value is very close to the anticipated Nernstian dependence of ?59 mV/pH indicating that the slope is not affected by the different sequences of e^? and H⁺ transfer. Molecular modeling results show a decrease of ≈5 kcal mol^?1 in ΔHoF (between radical and parent molecule) and a decrease of ≈6 eV in IP (of the parent molecule) when the parent molecule is changed from neutral to monoanionic form of catechin showing that both processes – hydrogen and electron abstraction are facilitated by deprotonation. Electrochemical oxidation of catechin is known to proceed as a two step one-electron oxidation of the B-ring of o-phenolic groups. Upon an increase in the pH, the mechanistic pathway of catechin electro-oxidation in both oxidation steps changes from an eH to the He process. In the reaction with a free radical, this may induce the change from hydrogen to electron donation.     

Electrocatalytic oxidation of nitrite on a carbon paste electrode modified with Co(II) porphyrin adsorbed on SiO2/SnO2/Phosphate prepared by the sol–gel method

This paper describes the immobilization of 5,10,15,20-tetrakis(1-methyl-4-pyridyl)-21H,23H-porphyrin ion on SiO₂/SnO₂/Phosphate obtained by the sol–gel processing method. The porphyrin was adsorbed on the surface of the modified material and furthermore metallized in situ with Co(II) ion. The porphyrin metallation process was followed using UV–Vis spectroscopy by inspecting the Q bands of the free and metallated porphyrin. A carbon paste electrode modified with material containing metallated porphyrin was used to study the electro-catalytic oxidation of nitrite ions by means of cyclic voltammetry, chronoamperometry and RDE voltammetry. The modified electrode was very stable and exhibited the electro-catalytic oxidation of nitrite ions at 0.72 V vs. SCE by a two electron mechanism producing nitrate ions at pH 5.4. The kinetic parameters of the electrode reaction process were calculated; (1 ? α)n_a was 0.479, D was (5.3 ± 0.11) × 10^?5 cm s^?1, and k⁰ could be determined as (5.4 ± 0.14) × 10^?3 cm s^?1.     

Novel solid-state cadmium ion-selective electrodes based on its tetraiodo- and tetrabromo-ion pairs with cetylpyridinium

Two novel cadmium solid-state ion-selective electrodes have been prepared by coating the surface of a graphite rod electrode directly with tetrahydrofuran solution containing PVC, cetylpyridinium–tetraiodocadmate (I) or cetylpyridinium–tetrabromocadmate (II), dioctyl phthalate and sodium tetraphenyl borate. The two sensors exhibit near-Nernstian anionic slopes of ?29.8 and ?25.1 mV/concentration decade, independently of pH over a wide range, with very fast response times of 3 and 7 s, respectively. The tetraiodocadmate (TIC) and tetrabromocadmate (TBC) electrodes posses linear ranges of 1.5 × 10^?6–1 × 10^?1 and 1.0 × 10^?6–1 × 10^?1 M and lower detection limits (LDL) of 6 × 10^?7 and 8 × 10^?7 M, respectively. The effects of membrane composition, type of plasticizer and pH of the sample solution were investigated thoroughly. The TBC electrode is shown to be free of all interference that is common for most of the reported cadmium ISEs except for that of Hg²⁺ ion. The two electrodes were applied for the determination of cadmium in some alloys and polluted water.     

Reactions of the nitro radical anion of metronidazole in aqueous and mixed solvent: a cyclic voltammetric study

Cyclic voltammetry was used to investigate the electrochemical reduction of metronidazole (2-methyl-5-nitro-1H-imidazole-1-ethanol) at glassy carbon and gold electrodes at different pHs in aqueous solution as well as in mixed solvent viz., aqueous dimethyl formamide. The electrogenerated nitro radical anion undergoes a disproportionation reaction, the rate constant of which is dependent on the pH, solvent composition and electrode material. The interactions of the nitro radical anion with thymine and cytosine were also investigated using a cyclic voltammetric technique. Both the bases were found to react with metronidazole nitro radical anion. The rate constants for such reactions in aqueous solutions were 3.5 × 10³ and 3.0 × 10³ dm³ mol^?1 s^?1 for thymine and cytosine, respectively.     

Improvement of alternariol monomethyl ether detection at gold electrodes modified with a dodecanethiol self-assembled monolayer

The electro-oxidation of alternariol monomethyl ether (AME), one of the main metabolites of the Alternaria genus mycotoxins, is studied at 1-dodecanethiol (DDT)-modified gold electrodes, in acetonitrile (ACN) – aqueous phosphate buffer solutions of different pH values, by using cyclic (CV) and square-wave (SWV) voltammetries. The AME voltammetric response at the bare electrode suffers from two drawbacks: it appears at potentials close to the onset of gold oxide formation, and it is hampered by a fouling of the electrode surface due to the accumulation of oxidized products. These shortcomings are circumvented by the use of DDT-coated electrodes, since the intervening monolayer inhibits gold oxide formation and surface passivation by the electrochemical products, without affecting the oxidation kinetics of AME significantly. Diagnostic criteria based on the voltammetric peak parameters show that the electrochemical behavior of AME at the modified electrode is mainly controlled by reactant diffusion from solution, with a weak adsorption of both the mycotoxin and its oxidation products at monolayer defects. Calibration curves were constructed from the AME square-wave voltammetric response and a detection limit of 9.1 × 10^?8 mol dm^?3 was determined, which is about three times smaller than a previous estimate at platinum and glassy carbon electrodes, and about fifty times smaller than the limit derived from measurements carried out at a polyphenol oxidase-modified carbon paste electrode.     

Electrochemical behavior of quercetin: Experimental and theoretical studies

Electrochemical oxidation of quercetin, as important biological molecule, has been studied in 0.1 M phosphate buffer solution, using cyclic voltammetry, chronoamperometry, rotating disk electrode voltammetry as well as quantum mechanical calculations. The heterogeneous charge transfer rate constant, k′, transfer coefficient, α, and exchange current density, j₀, for oxidation of quercetin at the glassy carbon electrode are determined as 4.84 × 10^?2 cm s^?1, 0.65 ± 0.01 and (1.17 ± 0.39) × 10^?7 A cm^?2, respectively. The formal potential, E^0′, of quercetin is pH dependent with a slope of ?60.1 mV per unit of pH which is close to the anticipated Nernstian value of ?59 mV for a two electrons and two protons process. The standard formal potential, E⁰, of quercetin was found to be equal with 558 mV versus saturated calomel electrode (SCE). The mechanism of oxidation was deduced from voltammetric data in various pHs and also in different concentrations of quercetin. The diffusion coefficient of quercetin was calculated as 3.18 × 10^?6 cm² s^?1 for the experimental condition, using chronoamperometric results. The results of density functional theory (DFT) calculations for the oxidation of quercetin in aqueous solution, are also presented. The theoretical standard electrode potential of quercetin is obtained to be 568 mV versus SCE, which is in good agreement with the experimental value. The discrepancy between theoretical and experimental values is only 10 mV. The agreement verifies the accuracy of experimental method and the validity of mathematical model.     

A voltammetric sensor based on graphene-modified electrode for simultaneous determination of catechol and hydroquinone

In this report, a voltammetric sensor for simultaneous determination of hydroquinone (HQ) and catechol (CC) was developed at a glassy carbon electrode modified with graphene (GR/GCE). The separation of oxidation and reduction peak (ΔE) is decreased from 281 to 31 mV for HQ and from 250 to 26 mV for CC at GR/GCE, respectively. Separation of the oxidation peak potentials for HQ and CC was about 112 mV in 0.10 M acetate buffer solution (pH 4.5), and the anodic currents for the oxidation of both HQ and CC are greatly increased at GR/GCE, which makes it suitable for simultaneous determination of these compounds. Under the optimized condition, the anodic peak current of HQ is linear with the concentration of HQ from 1 × 10^?6 to 5 × 10^?5 M in the presence of 5 × 10^?5 M CC. A detection limit of 1.5 × 10^?8 M (S/N = 3) can be achieved. At the same time, the anodic current of CC is linear with the concentration of CC from 1 × 10^?6 to 5 × 10^?5 M with a detection limit of 1.0 × 10^?8 M (S/N = 3) in the presence of 5 × 10^?5 M HQ. The proposed sensor was successfully applied to the simultaneous determination of HQ and CC in tap water, and the results are satisfactory.     

Glucose sensing by a carbon-paste electrode containing chitin modified with glucose oxidase

As one application for chitin, the development of a glucose sensor was attempted at a carbon paste electrode containing platinum powder and chitin powder with glucose oxidase. Immobilization of the enzyme is based on an electrostatic interaction between the protonated acetylamide group of the chitin and functional groups having a negative charge on the enzyme. Glucose oxidase was simply immobilized on the chitin in 0.1 M acetate buffer (pH 5.0). An oxidation peak of H₂O₂ produced from the enzyme reaction was observed at about +0.60 V (vs. Ag ∣ AgCl) in 0.1 M acetate buffer (pH 6.2). The calibration curve of glucose was linear in the range from 3×10^?6 to 4×10^?4 M. This method was applied to determination of glucose in a sports drink.     

Electrochemical behavior of iodide at a nickel pentacyanonitrosylferrate film modified aluminum electrode prepared by an electroless procedure

The surface of an aluminum disk electrode was modified by a thin film of nickel pentacyanonitrosylferrate and used for electrocatalytic oxidation of iodide. The cyclic voltammogram of the modified Al electrode showed surface redox behavior due to the [Ni^IIFe^III/II(CN)₅NO]^0/1? redox couple. The modifying layer shows excellent catalytic activity toward the oxidation of iodide. Different supporting electrolytes containing different alkali metal cations affected the apparent formal potential of the redox films and thus, changed the thermodynamic tendency and kinetics of the modifying film toward the catalytic oxidation of iodide. This was explained by including the concept of a surface coverage normalized-catalytic current. The kinetics of the catalytic reaction were investigated by cyclic voltammetry and rotating disk electrode voltammetry in a suitable supporting electrolyte. The results were explained using the theory of electrocatalytic reactions at chemically modified electrodes. The heterogeneous rate constant for the catalytic reaction, k, diffusion coefficient of iodide in solution, D, and transfer coefficient, α, were found to be 5.8 × 10² M^?1 s^?1, 1.3 × 10^?5 cm² s^?1 and 0.66, respectively. In addition the effect of electrode surface coverage on the dynamic range of a calibration curve was investigated. Under optimum conditions a linear calibration graph was obtained over an iodide concentration range of 2–100 mM.     

Voltammetric determination of stability constants of iron(III)–glycine complexes in water solution

Determination of the stability constants of dissolved iron(III)–glycine system in water solution (I = 0.6 mol L^?1 in NaClO₄ at 25 ± 1 °C) using differential pulse cathodic voltammetry (DPCV) was performed on a static mercury drop electrode (SMDE). Iron(III) concentration of 2.5 × 10^?5 mol L^?1 and the pH range from 9.05 to 6.36 ensured the formation of enough concentration of iron(III)–glycine higher coordination complexes (1:2 and 1:3) to be measured by the applied method. The concentrations of total glycine varied from 0.1 to 0.5 mol L^?1. Cyclic voltammetry (CV) measurements were used to investigate reversibility of the iron(III)–glycine complexes which showed one-electron reversible character. The stability constants of iron(III) [Fe(Gly)₂]⁺ and Fe(Gly)₃ complexes, which had not been reported in the literature so far, were found to be log β₂ = 16.83 ± 0.47 and log β₃ = 18.64 ± 0.70, respectively. The model that best fitted the data gave two iron(II)–glycine stability constants for [FeGly]⁺ log K₁ = 3.69 ± 0.19 and for Fe(Gly)₂ log β₂ = 5.08 ± 0.60. According to the constants found, chemical distribution of iron(III) in glycine water solution, as a function of pH, was calculated and proposed.     

Characterization and electrocatalytic properties of cobalt hexacyanoferrate films immobilized on Au-colloid modified gold electrodes

An electroactive cobalt hexacyanoferrate (CoHCF) film was electrodeposited from a solution containing Co²⁺ and Fe(CN)₆^3? ions on the bare gold or the Au-colloid modified electrode. The cation (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺) and the anion (F^?, Cl^? and Br^?) effects on the redox peak of the CoHCF film were investigated in detail. On the other hand, the electrocatalytic oxidations of thiosulfate at the CoHCF/gold and CoHCF/Au-colloid/gold electrodes were compared. At the CoHCF/Au-colloid/gold electrode, we obtained a response current larger by a factor of 2 and a three times lower detection limit than those at a CoHCF/gold electrode. The linear ranges were 1.0 × 10^?4 to 2.8 × 10^?3 M for the CoHCF/gold electrode and 7.5 × 10^?5 to 4.8 × 10^?3 M for the CoHCF/Au-colloid/gold electrode. These results showed that the immobilized CoHCF at the Au-colloid modified electrode exhibited a higher catalytic activity and a wider linear range toward thiosulfate. Additionally, the effects of the applied potential and the solution pH were studied.     

The reduction of l-cystine hydrochloride at lead using static and rotating disc electrodes

The reduction of the disulphide, l-cystine hydrochloride to the l-cysteine hydrochloride thiol, in 0.1 mol dm^?3 HCl at 298 K, has been studied at pre-treated, circular, 0.50 cm² lead disc electrodes using steady state linear sweep voltammetry, non-steady state voltammetry and controlled potential coulometry. The diffusion coefficient for l-cystine hydrochloride was approximately 4.8 × 10^?10 m² s^?1 from the three techniques. Reduction of the disulphide was irreversible and hydrogen evolution occurred as a competitive reaction at approximately ?1.35 V vs. SCE. Analysis of the mixed control kinetics, using a Koutecky–Levich approach, allowed the relative roles of charge transfer and mass transport to be resolved. Anomalously high Tafel slopes, of typically ?183 mV, were observed due to disulphide adsorption. The charge transfer kinetics are consistent with the first electron gain being rate determining while reaction orders are +1 with respect to both the disulphide and proton concentrations. The mechanism of l-cystine hydrochloride reduction has been critically discussed.     

Electroreduction of halogenated fumaric esters: a combined electrochemical and computational investigation

Diethyl fumarate and related halogenated derivatives have been studied by cyclic voltammetry and electrolysis, on mercury and glassy carbon electrodes, in DMF + 0.1 mol L^?1 TBAP and in acetonitrile + water (3:4) with 0.1 mol L^?1 NaCl or 0.1 mol L^?1 TEAP. For compounds with two reducible functionalities, the electron-deficient olefin and the C–X group, the grade of substitution on the halogenated carbon causes differences on the site involved in the first electron transfer thus determining the chemical reactivity. Enediester compounds with –CH₂– groups insulating the gem-trihalide groups (–CX₃, X=Br and Cl) suffer reduction, and the C–X cleavage is the reaction of choice. The reaction pathway also depends on the nature of the electrode and significant positive potentials shifts for compounds with a gem-tribromide group are evident in the cyclic voltammogram on a mercury electrode, in relation to results on a glassy carbon electrode. The formation of easily reduced organomercurials is the main reason for this intense positive shift in the first electron transfer. On a vitreous carbon electrode, factors directly related to the strength of the C–X bond play a determinant role. Concerning electrolysis, the gem-tribromo derivative furnishes H₂CCBr₂ and ethyl hydrogenfumarate, through hydrolysis produced by initial cleavage of the C–Br. For the other polyfunctional compounds (–CHX₂, –CH₂X), the olefin is reduced first to yield dimers and/or hydrogenated products depending upon the reaction conditions. Quantum chemical calculations performed on the anion radical of these compounds yield spin densities located on the –CBr₃/–CCl₃ group and on the enediester group for the –CCl₂/–CBr₂, –CH₂Br/–CH₂Cl derived compounds. Upon geometry optimisation, the C–Br bond in compounds containing –CBr₃ groups are longer, suggesting that this bond can easily be cleaved, yielding organomercurial compounds, in the case of the use of a mercury electrode or leading to bond cleavage, for inert electrodes. For the other substituents, the optimisation basically does not affect the geometry of the radical anion compared to the neutral substrate. These results have been confirmed by the calculated dissociation energy of the C–Br bond, which for the –CBr₃ group is approximately 100 kJ mol^?1 as against 240 kJ mol^?1 for the same bond in the –CH₂Br group. The coherence between the experimental and calculated data reinforces the usefulness of these computational tools in rationalising the reactivity of electrogenerated species as well as in predicting the electrochemical reaction outcome.     

Interactions between DNA and a water-soluble C60 derivative studied by surface-based electrochemical methods

A novel electrochemical micromethod for the investigation of the interactions between DNA and non-electroactive species is described. The method was developed using the system of double-stranded DNA (dsDNA) modified gold electrodes (dsDNA/Au), a synthesized water-soluble C₆₀ derivative as a model, and [Co(phen)₃]^3+/2+ (phen=1,10-phenanthroline) as an electroactive indicator. Electrochemical studies with dsDNA-modified gold electrodes suggest that the C₆₀ derivative can interact strongly with dsDNA, with binding sites of the major groove of the double helix and phosphate backbone of dsDNA, a binding constant of (1.6 ± 0.2) × 10⁵ M^?1 obtained in 5 mM NaCl in Tris–HCl buffer, and a dissociation rate constant from the dsDNA/Au surface of (1.2 ± 0.1) × 10^?2 min^?1.     

A piezoelectric gene-sensor using actinomycin D-functionalized nano-microspheres as amplifying probes

A gene-sensing system has been developed using actinomycin D-functionalized magnetic nano-microspheres, which can interact with double-stranded DNAs (dsDNAs) anchored on the gold film electrode of an electrochemical quartz crystal microbalance (EQCM). Actinomycin D acts as a guide that leads heavy microspheres onto the dsDNAs at the EQCM film. A magnetic separation shelf could separate unreacted microspheres conveniently. The modification and DNA hybridization at EQCM electrodes were examined by microgravimetric and electrochemical methods. In this way, an outstanding change in frequency decrease has been monitored owing to the mass increase on the EQCM electrodes. The limit for the determination of target DNA could be improved from 6.2×10^?8 to 2.0×10^?12 mol l^?1 by the amplifying technique.     

Evidence of self-protonation on the electrodic reduction mechanism of an anti-Helicobacter pylori metronidazole isotere

The electrochemical reduction mechanism of 1-(2-ammoniumethyl)-2-methyl-5-nitroimidazole bromide (2) in DMSO + 0.1 mol l^?1 TBAP has been investigated by cyclic voltammetry and macroscale electrolysis, on a glassy carbon electrode, in comparison with metronidazole (1). The cyclic voltammogram of 2 is represented by three reduction waves, one of them at less negative potential, when compared to the first wave of metronidazole which indicates that it undergoes easier reduction. There is evidence for a self-protonation mechanism in the electroreduction of 2, represented by the absence of the first wave in the successive cyclic voltammogram, by the disappearance of the first reduction wave upon addition of base and increase of the same wave in the presence of exogenous proton donors. The stoichiometry of the reaction, at the first reduction wave, involves 0.8 mol electron mol^?1 and yields 0.2 mol of 4e^?/4H⁺ reduced derivative (probably an unstable hydroxylamine) and 0.8 mol of the amine derivative, the conjugated base of 2. The second and third waves are typical for nitroaromatic reduction and are related to the reduction of the nitro group in this aminoderivative.     

Hall effect measurements on CdTe layers electrodeposited from acidic aqueous electrolyte

The electrical properties of CdTe layers electrodeposited from an acidic sulfate aqueous electrolyte were examined by resistivity and Hall effect measurements. It was revealed that the resistivity, conduction type, and carrier density of the as-deposited CdTe layers could be controlled by the deposition potential. The resistivity varied in the range from 2 × 10⁶ to 2 × 10⁸ Ω cm. The CdTe layers deposited at potentials slightly positive to the Cd²⁺/Cd equilibrium potential (?0.37 V vs. SHE?E??0.30 V) had n-type conductions, while those deposited at more positive potentials (?0.15 V ?E??0.05 V) were p-type. The carrier densities of the CdTe layers were on the order of 10¹⁰–10¹¹ cm^?3. As the deposition potential became more positive, the electron density decreased, and conversely, the hole density increased. The electron mobilities for the n-type CdTe layers were in the range 7–40 cm² V^?1 s^?1, while the hole mobility was about 1 cm² V^?1 s^?1.