Oxidation chemistry of 2'-deoxyadenosine at pyrolytic graphite electrode

The electrochemical oxidation of 2'-deoxyadenosine has been investigated in phosphate containing supporting electrolytes in pH range 2-10 at a pyrolytic graphite electrode by cyclic sweep voltammetry, spectral studies, controlled potential electrolysis and related techniques. The oxidation of 2'-deoxyadenosine occurred in a single well-defined oxidation peak (I(a)), over the entire pH range. The electrooxidation occurred by the loss of 6.0+/-0.5 e(-) per mole over the entire pH range. The kinetics of the decay of the UV-absorbing intermediates has been studied and found to follow pseudo first order kinetics having rate constant (k) in the range (5.7-7.7)x10(-4) s(-1). The major products of electrooxidation were separated by HPLC and characterized by GC-MS/MS, (1)H NMR and a tentative mechanism for electrooxidation of 2'-deoxyadenosine has been suggested.     

Electrochemical oxidation of 2-thiouracil at pyrolytic graphite electrode

2-Thiouracil has been studied in phosphate buffers of pH 1.95-11.08 using linear and cyclic sweep voltammetry, coulometry, controlled potential electrolysis and spectral studies. One well-defined oxidation peak I(a) in the pH range 1.95-11.08 was noticed. The number of electrons involved in peak I(a) was found to be four in a thin layer cell whereas under exhaustive electrolysis condition oxidation was found to involve six electrons. A reduction peak II(c) (2e, 2H(+)) is noticed in the reverse sweep. Spectral studies during oxidation were carried out at different pH. Kinetic studies indicated that the decay of the UV-absorbing intermediate is a first order reaction. The products of the electrooxidation have been characterized and a tentative EC mechanism has been suggested for the oxidation of 2-thiouracil.     

Electrochemical oxidation of sulphapyridine at a pyrolytic graphite electrode

The electrochemical oxidation of sulphapyridine at a pyrolytic graphite electrode was studied over a wide pH range. Sulphapyridine is oxidized in an irreversible reaction involving two electrons and two protons to give an electroactive product. On the basis of voltammetric, spectral and coulometric studies and product identification, a tentative mechanism is suggested.     

Electrochemical reduction of tartrazine at multi-walled carbon nanotube-modified pyrolytic graphite electrode

Electrochemical reduction of tartrazine on multi-walled carbon nanotube-modied pyrolytic graphite electrode is investigated. A simple, sensitive and inexpensive method for determination of tartrazine in drinks is proposed. The accuracy and reproducibility of the determination method for various known amounts of tartrazine were evaluated. This method was satisfactorily applied for the determination of tartrazine in drinks. The reduction peak currents were proportional to tartrazine concentrations over two intervals in the range from 2.0 to 70.0 mg l⁻¹ and from 70.0 to 230.0 mg l⁻¹, and the detection limit for tartrazine is 0.5 mg l⁻¹.     

血红蛋白在纳米羟基磷灰石修饰的热解石墨电极上的直接电化学

采用超声辅助沉淀法合成羟基磷灰石纳米晶体,制作了以纳米羟基磷灰石(HAp)修饰的热解石墨电极(EPG)。并研究了血红蛋白在该修饰电极上的直接电化学行为。在pH6.9的磷酸盐(PBS)缓冲溶液中,得到一对可逆的血红蛋白辅基血红素Fe(Ⅲ)/Fe(Ⅱ)电对的循环伏安氧化还原特征峰,式量电位E0p′=-0.356V(vs.SCE,pH6.9),几乎不随扫速的改变而变化,电子转移数为1.041,近似一个辅基发生一个电子转移。Hb在HAp/EPG电极表面直接电子转移的速率常数为0.6074。在该纳米HAp微环境中,Hb与EPG电极之间的电子传递得到极大促进,并显示了较好的稳定性。式量电势pH3.6~9.0范围内与溶液的pH成线性关系,直线斜率为-56.0mV/pH,说明Hb的电子传递过程伴随质子的转移。探讨了Hb-HAp修饰电极对H2O2的电催经性质,为制作生物传感器打下基础。     

Cyclic voltammetric studies of a thionine coated pyrolytic graphite electrode

Cyclic voltammetry has been used to study the spontaneous adsorption and oxidative coating of thionine onto basal plane pyrolytic graphite electodes. Spontaneous adsorption leads to a monolayer of flat lying molecules together with some weakly attached upper layers. Oxidation of an adsorbed thionine monolayer results in several products which appear to include polymeric species and the sulphoxide of thionine. Similar products are obtained by an oxidative coating procedure.     

Electrochemical behaviour of human adrenodoxin on a pyrolytic graphite electrode

Adrenodoxin (Adx) functions as a redox protein in the delivery of electrons to all mitochondrial cytochromes P450. In order to further characterize the human form of this protein, direct electrochemistry of human adrenodoxin (Hadx) has been observed for the first time on a pyrolytic graphite electrode (PGE) modified with poly-L-lysine. A single well-defined redox wave was observed with a midpoint potential of -448+/-3 mV vs. Ag/AgCl (sat. KCl) at scan rates of 10 mV/s and over the pH range 4.0-8.0. At slow scan rates, the reduction process was close to being electrochemically reversible whereas, at faster scan rates, only quasi-reversibility was observed. A correlation was observed between the peak separation (DeltaE) for the cyclic voltammograms and pH over a wide range of scan rates. The variation of DeltaE with pH was at a minimum (optimum reversibility) at pH 7.0 for all scan rates tested. This correlation may suggest that the direct electrochemistry method could possibly provide a means for determining protein or enzyme activity. The electron transfer rate constant, k(s), was determined to be 0.28 s(-1) at pH 7.0 and a small pH dependence was observed. The results obtained in this study demonstrate the facile nature of direct electron transfer for human adrenodoxin, and provide an estimate of the midpoint reduction potential at a pyrolytic graphite electrode via electrostatic immobilisation.     

Voltammetric oxidation of some biologically important xanthines at the pyrolytic graphite electrode

Linear and cyclic sweep voltammetry of some biologically important N-methylxanthines has been carried out. The principal and potential determining reaction for oxidation of xanthines is a 2 electron attack at the -N₉C_8⁻ double bond to give the appropriate uric acid, which is then immediately further oxidized to an intermediate 4,5-diol species. In many instances this 4,5-diol is sufficiently stable to be detected by fast sweep cyclic voltammetry as a small cathodic peak formed as a result of reduction of part of the 4,5-diol to the corresponding uric acid. The uric acid so formed can be reoxidized upon subsequent cycles at a potential close to that observed for reduction fo the 4,5-diol, so that most xanthines (and uric acids) show evidence for a reversible redox couple at about 0.4–0.55 V. Methylation at position N₇ decreases somewhat the stability of the intermediate 4,5-diol and dimethylation at N₃ and N₇ results in such a marked decreased in the stability of the diol that it cannot be observed by cyclic voltammetry.     

Anodic reactions of the halides in dimethyl sulfoxide at the pyrolytic graphite electrode

The anodic reactions of the halide ions in dimethyl sulfoxide at the pyrolytic graphite electrode have been studied. The iodide ion demonstrates a 3-step oxidation; the bromide, a 2-step oxidation and chloride, a 1-step oxidation. The electrode reaction (X^-→$\text{1}\text{2}$ X₂ + e^-) is complicated by a catalytic reaction occurring after the electrode reaction. The catalytic reaction is important for only bromide and chloride causing a considerable diffusion current enhancement. The αn_a value for all 3 primary reactions is of the order of 0.5.     

The adsorption of corypalline and related compounds on a pyrolytic graphite electrode

Anodic current-time curves have been used to study the adsorption, from TEAP-acetonitrile solution, of corypalline (7-hydroxy-6-methoxy-N-methyl-1,2,3,4-tetrahydroisoquinoline), isocorypalline (6-hydroxy-7-methoxy-N-methyl-1,2,3,4-tetrahydroisoquinoline), and 1-methyl-corypalline. A comparison with analogous cathodic current-time curves obtained with methylene blue leads to the conclusion that, on a pyrolytic graphite electrode, these isoquinoline compounds are adsorbed in a “flat-on” configuration. This conclusion is in harmony with the postulation that the known steroselective, stereospecific oxidative coupling of 1-methylcorypal-line occurs through the adsorption of the reacting molecules on the electrode surface.     

On reproducibility of preparation of basal plane pyrolytic graphite electrode surface

The basal plane pyrolytic graphite (BPPG) electrode is widely used as a “standard” electrode for studies of electrochemical activity of graphite, graphene and carbon nanotubes. We compared here different methods for preparation of the surface of BPPG using statistical analysis of the data. We showed that including/omitting of polishing step or including/omitting of acetone washing step in the preparation procedure exhibits statistically significant difference. However, using acetone of different purities does not lead into statistically significant results. In addition, all methods with BPPG provided RSD < 10% and did not produce any outlying results.     

Electrocatalytic detection of thiols using an edge plane pyrolytic graphite electrode

The first example of using an edge plane pyrolytic graphite electrode in electroanalysis is reported as the determination of homocysteine, N-acetylcysteine, cysteine and glutathione is studied. The response of the electrode in the direct oxidation of thiol moieties is explored and found to be electrocatalytic producing a reduction in the overpotential while having enhanced signal-to-noise characteristics compared to glassy carbon and basal plane pyrolytic graphite electrodes. The effectiveness of the methodology is examined in the determination of cysteine species in a growth tissue media that contains a high number of common biological interferences. The advantageous properties of this electrode for thiol determination lie in its excellent catalytic activity, sensitivity and simplicity.     

Permselective-membrane pyrolytic graphite electrode for the study of microvolumes of [2Fe-2S] ferredoxin

A permselective-membrane pyrolytic graphite electrode was used to study the electrochemistry of [2Fe-2S] ferredoxin entrapped between the membrane and the graphite surface, in the presence of poly(l-Lysine). Factors influencing the electrode response [such as the concentration of poly(l-lysine), ionic strength and pH] were explored. The analytical performance of this permselective-membrane electrode, which allows 20 pmol of ferredoxin to be detected, was examined.     

Scanning probe microscopic imaging of guanine on a highly oriented pyrolytic graphite electrode.

Guanine adsorbed onto a highly oriented pyrolytic graphite electrode was studied by MAC-Mode Atomic Force Microscopy (AFM), and the electrochemical behaviour of the guanine layer was investigated with Electrochemical AFM. Guanine adsorbs spontaneously, without forming a well-packed structure, into nucleation spots, which are stable with time and cover the surface uniformly and almost completely. The process of guanine adsorption and nucleation can be controlled and the effect of altering the exposure time and varying the potential was investigated.     

Edge plane pyrolytic graphite electrode covalently modified with 2-anthraquinonyl groups: theory and experiment

An edge plane pyrolitic graphite (EPPG) electrode was modified by electrochemical reduction of anthraquinone-2-diazonium tetrafluoroborate (AQ2-N(2)(+)BF(4)(-)), giving an EPPG-AQ2-modified electrode of a surface coverage below a monolayer. Cyclic voltammograms simulated using Marcus-Hush theory for 2e(-) process assuming a uniform surface gave unrealistically low values of reorganisation energies, λ, for both electron transfer steps. Subsequently, two models of surface inhomogeneity based on Marcus-Hush theory were investigated: a distribution of formal potentials, E', and a distribution of electron tunneling distances, r(0). The simulation of cyclic voltammograms involving the distribution of formal potentials showed a better fit than the simulation with the distribution of tunneling distances. Importantly the reorganization energies used for the simulation of E' distribution were similar to the literature values for adsorbed species.     

Potentiometric stripping analysis at a stationary electrode

The feasibility of controlling the transport mechanism of the oxidizing species at the working electrode during the stripping step of potentiometric stripping analysis is demonstrated. When linear diffusion of the oxidizing species is the rate-determining mechanism at the working electrode/solution interface and when the physical properties of the medium are considered to lower the diffusion coefficient of the oxidizing species, the relative sensitivity of the technique is enhanced by a factor of 50 for all the common ions studied by potentiometric stripping analysis. Examples and comparison with the normal procedure are given for Cu, Cd, Zn, Pb, Bi, Tl and Ga. The “stationary electrode” procedure is compatible with the normal instrumentation without great modification; it is self-optimizing with respect to time and resolution and preserves all the inherent advantages of potentiometric stripping analysis compared to other electrochemical techniques of trace analysis. The enhancement of the relative sensitivity by this modification permits measurements in the 0.01–0.1 ppb range for metal ions; the total time required is 2–4 min for a single determination and the relative standard deviations are about 3%.     

Electrochemical determination of adenine and adenosine: adsorption of adenine and adenosine at the pyrolytic graphite electrode

Adenine and adenosine are polarographically reducible from aqueous solution at pH 4.7 at the DME at the same E(1 2 ) and are also voltammetrically oxidizable at the PGE, but at different potentials, adenosine at higher potentials. Competitive adsorption of both compounds at the PGE results in a decrease in the scanning voltammetric oxidation peak of adenine in the presence of adenosine, reaching a constant value when the concentration of the latter is above 6 mM. In mixtures, the sum of the two is obtained by polarography at the DME. Solid adenosine is then added to the solution and the adenine is determined by voltamrnetry at the PGE.