Phenol and para-substituted phenols electrochemical oxidation pathways

The electrochemical behaviour of phenol, catechol, hydroquinone, resorcinol, dopamine, and para-substituted phenolic compounds, 4-ethylphenol, tyrosine, and tyramine, was studied over a wide pH range using a glassy carbon electrode. The oxidation of phenol is pH dependent and irreversible, occurring in one step, and followed by hydrolyse in ortho- and para-positions, leading to two oxidation products, catechol and hydroquinone. The oxidation of phenol oxidation products, ortho-phenol and para-phenol, is reversible and pH dependent. The oxidation potential of para-substituted phenols varies slightly due to their substituent group in position C4, and occurs in one oxidation step corresponding to the oxidation of phenol. The oxidation products of this group of para-substituted phenols are reversibly oxidised and adsorb on the electrode surface.     

Investigations of a novel ferrocene-containing lipid by cyclic voltammetry and cryogenic transmission electron microscopy

A novel chiral redox-active ferrocene compound (FcVI) with amphiphilic properties has been synthesized. Cryogenic Transmission Electron Microscopy (cryo-TEM) has been used to estimate the shape and size of the FcVI aggregates in solution. Uni- and multi-lamellar vesicles (between 40 and 300 nm in diameter) were observed in water. Large particles (of more than 1 μm in diameter) with a hexagonal fine structure were found in 50 mM aqueous Na₂SO₄ solution. Sonication transformed the latter into ‘rosette’-like structures. Cyclic voltammetry has been employed to investigate the electrochemical properties of FcVI. The amphiphile adsorbed on graphite electrodes and a reversible electrochemical behaviour, characteristic of ferrocene, was observed with redox potentials between 330 and 350 mV.     

Voltammetry and surface analysis of AISI 316 stainless steel in chloride-containing simulated concrete pore environment

The study of passive layers grown on AISI 316 stainless steel in solutions that simulate concrete pore environments contaminated with Cl^? is presented. Model solutions of saturated Ca(OH)₂ and cement extract (CE) with and without the addition of 5 g/L of NaCl are compared. Cyclic voltammetry (CV) shows different electrochemical responses of passive layers grown on samples immersed in these solutions under open circuit potential (ocp). A more resistive passive film was found on the samples exposed to the CE solution. The different voltammetric responses suggest differences in composition of the passive layers formed on each solution. XPS spectra confirm the dissimilarity in atomic composition. Optical microscope images and AFM images of the pits formed on the samples illustrate the differences of AISI 316 surface topography after exposure to model solutions. Because of these differences, it is recommended to use CE solution as a model solution and ocp passivation to simulate concrete environments.     

Asenapine, a novel psychopharmacologic agent: preclinical evidence for clinical effects in schizophrenia

Rationale Asenapine is a novel psychopharmacologic agent being developed for the treatment of schizophrenia and bipolar disorder. Materials and methods The present study was undertaken to investigate the effects of asenapine using animal models predictive of antipsychotic efficacy (conditioned avoidance response [CAR]) and extrapyramidal side effects (EPS; catalepsy). In parallel, the effects of asenapine on regional dopamine output using in vivo microdialysis in freely moving rats, dopamine output in the core and shell subregions of nucleus accumbens (NAc) using in vivo voltammetry in anesthetized rats, and N-methyl-d-aspartate (NMDA)-induced currents in pyramidal neurons of the medial prefrontal cortex (mPFC) using the electrophysiological technique intracellular recording in vitro were assessed. Results Asenapine (0.05–0.2 mg/kg, subcutaneous [s.c.]) induced a dose-dependent suppression of CAR (no escape failures recorded) and did not induce catalepsy. Asenapine (0.05–0.2 mg/kg, s.c.) increased dopamine efflux in both the mPFC and the NAc. Low-dose asenapine (0.01 mg/kg, intravenous [i.v.]) increased dopamine efflux preferentially in the shell compared to the core of NAc, whereas at a higher dose (0.05 mg/kg, i.v.), the difference disappeared. Finally, like clozapine (100 nM), but at a considerably lower concentration (5 nM), asenapine significantly potentiated the NMDA-induced responses in pyramidal cells of the mPFC. Conclusions These preclinical data suggest that asenapine may exhibit highly potent antipsychotic activity with very low EPS liability. Its ability to increase both dopaminergic and glutamatergic activity in rat mPFC suggests that asenapine may possess an advantageous effect not only on positive symptoms in patients with schizophrenia, but also on negative and cognitive symptoms.     

Voltammetric and XPS investigations of nickel hydroxide electrochemically dispersed on gold surface electrodes

A chemically modified electrode composed of mixed hydroxide and oxyhydroxide nickel film (6–8 nmol cm^?2) on the gold substrate (Au ∣ Ni) was characterized by cyclic voltammetry and XPS techniques. The gold substrate electrodes were firstly electrochemically conditioned in 0.2 M NaOH by cycling the potential between ?0.25 and 0.6 V versus SCE, then modified by cathodic electrodeposition of nickel hydroxide films. These nickel films were obtained either by voltage cycling (50 mV s^?1) between 0.0 and ?0.5 V (SCE) or at constant potential of ?0.3 or ?0.5 V using non-deaerated 50 mM Ni(NO₃)₂ solutions. X-ray photoelectron spectroscopy (XPS) characterisation and voltammetric behaviour of Au ∣ Ni electrodes in alkaline solutions are described. Continuous electrochemical cycling of the Au ∣ Ni electrodes induces significant changes of the nickel films in terms of crystallographic structures and chemical composition. Combination of XPS and electrochemical methodologies have demonstrated the ability to follow the morphological and chemical changes in alkaline solutions upon cycling potentials. Angular-dependent XPS measurements have demonstrated that electrochemical treatment induces the formation of a uniform film layer with the following chemical distribution: Au ∣ Ni(OH)₂ ∣ NiOOH. The electrocatalytic activity of the Au ∣ Ni electrodes is investigated in alkaline medium using glucose as a model compound. The favourable combination of active species such as gold and nickel leads to a sensing electrode with strong catalytic activity over a wide range of applied potentials.     

Electrochemical study on Cd binding to metallothioneins isolated from the mussel, Mytilus galloprovincialis

Voltammetric studies on the binding properties of the purified metallothionein (MT) fractions isolated from mussel (Mytilus galloprovincialis) digestive gland for cadmium ions were performed. The capacity of MT to complex cadmium and the stability constants of the Cd–MT complex have been determined from the direct titration of MT with cadmium ions in 0.59 M NaCl medium at pH 7.9. Comparing cadmium binding properties of the two isoforms of mussel MT studied denoted as MT10(III) and MT10(IV), it appears that they are distinctly different. In the presence of two different MT isoforms voltammetric determination of cadmium results in specific anodic signals which are observed at E_p=?0.67 V and at E_p=?0.80 V (vs. a Ag ∣ AgCl electrode) for isoform MT10(III), and isoform MT10(IV) respectively, indicating the existence of two different Cd–MT complexes. This is in agreement with the difference in their calculated apparent stability constants (K=9×10⁹ dm³ mol^?1 for MT10(III) and K=1.4×10¹⁰ dm³ mol^?1 and K=2.0×10¹⁰ dm³ mol^?1 for MT10(IV)). The saturation of the two MT10 fractions occurs at different Cd(II) concentrations, and the capacity of MT10(IV) to bind cadmium ions is 2.5 times greater than the capacity of MT10(III). The electrochemical technique, and method for the experimental data assessment presented in this study are suitable for physico-chemical characterization of metallothioneins as the proteins responsible for binding of toxic metals on a cellular level. Using the voltammetric method time dependent changes of the three-dimensional structure of the MT molecule were observed.     

Voltammetry of sparingly soluble metal complexes: a differential pulse polarographic study of the Zn(II)+oxalate system

An extension of a voltammetric model for the complexation between metal ions and mixtures of ligands (either simple or macromolecular, labile or inert) is proposed for the study of the Zn(II)+oxalate system. The model considers the presence of species of low solubility that can be assumed to behave as soluble inert complexes. As well as the solubility problem, a loss of reversibility in the zinc reduction process occurs. This problem is overcome by increasing the effective time scale of the measurements. The application of the model to experimental data has produced reliable results, which can be used to estimate complexation constants and solubility products, as long as the irreversible processes that influence the current and potential measurement are avoided.     

Repeated treatment with ascorbate or haloperidol,but not clozapine,elevates extracellular ascorbate in the neostriatum of freely moving rats

Acute administration of neuroleptic drugs alters the extracellular level of ascorbate in the neostriatum, and increasing evidence suggests a role for this vitamin in the behavioral, and possibly therapeutic, effects of these drugs. To shed further light on this issue, extracellular ascorbate was recorded in the neostriatum and nucleus accumbens of awake, behaving rats following chronic treatment with either classical (haloperidol) or atypical (clozapine) neuroleptics or ascorbate itself. Electrochemically modified, carbon-fiber microelectrodes were lowered in place the day after the last of 21 daily injections of either haloperidol (0.5 mg/kg, SC), clozapine (20 mg/kg, IP), sodium ascorbate (500 mg/kg, IP) or vehicle. Voltammetric measurements were obtained during quiet rest and following administration ofd-amphetamine (2.5 mg/kg). Repeated treatment with either haloperidol or ascorbate elevated basal extracellular ascorbate and potentiated the amphetamine-induced increase in ascorbate release in neostriatum but not nucleus accumbens. Both treatment groups also showed a significant increase in amphetamine-induced sniffing and repetitive head movements compared to vehicle-treated animals. In contrast, repeated clozapine had no effect on extracellular ascorbate in either neostriatum or nucleus accumbens, but increased the locomotor response to an amphetamine challenge. Thus, to the extent that increases in neostriatal ascorbate exert neuroleptic-like effects, such effects are likely to parallel haloperidol rather than clozapine.