Electrochemical Investigation of Oligonucleotide-DNA Hybridization on Poly(4-Methoxyphenethylamine)

This work describes the immobilization of purine and pyrimidine bases and immobilization/hybridization of synthetic oligonucleotides on graphite electrodes modified with poly(4-methoxyphenethylamine) produced in acid medium. The immobilization of adenine, guanine, cytosine and thymine on these modified electrodes was efficient, producing characteristic peaks. Another relevant observation is that, according to the literature, pyrimidine bases, cytosine and thymine are more difficult to detect. However, when immobilized onto the poly(4-methoxyphenethylamine), a significant increase in the magnitude of the current was obtained. The observation of the hybridization between the poly(GA) probe and its complementary, poly(CT) target, was possible by monitoring the guanosine and adenosine peaks or through methylene blue indicator, using differential pulse voltammetry. Hybridization results in a decrease of the peak current of guanosine and adenosine or the signal of methylene blue accumulated on the modified electrode surface. The hybridization with the complementary target was also investigated by electrochemical impedance spectroscopy. The results showed a significant modification in the Nyquist plot, after addition of the complementary target, with increase of the charge transference resistance

Chlorine evolution reaction at Ti/(RuO2+Co3O4) electrodes

A systematic investigation of the mechanistic and electrocatalytic properties of the chlorine evolution reaction, ClER, on mixed rutile/spinel oxides of nominal composition Ti/[RuO2(x)+Co3O4(1-x)] was done. Electrodes were prepared using the thermal decomposition procedure (Tcalc. = 470ºC; t calc. = 1h), with x varied between 0 and 1, changed in 0.1 steps. Kinetics were studied recording quasi-stationary current-potential curves and reaction order determined with respect to H+ and Cl-. A constant Tafel slope of about 33 mV was found for the 0 - 80 mol% RuO2 concentration interval, increasing to 40 mV for higher RuO2 contents. Experimental data support the mechanism originally proposed by Erenburg et al. for the ClER. The edge effect exerts an influence on the electronic transfer coefficient values. Analysis of the electrocatalytic activity reveals an increase in the apparent electrocatalytic activity for the mixed oxides

Electrochemistry and green chemical processes: electrochemical ozone production

After an introductory discussion emphasising the importance of electrochemistry for the so-called Green Chemical Processes, the article presents a short discussion of the classical ozone generation technologies. Next a revision of the electrochemical ozone production technology focusing on such aspects as: fundamentals, latest advances, advantages and limitations of this technology is presented. Recent results about fundamentals of electrochemical ozone production obtained in our laboratory, using different electrode materials (e.g. boron doped diamond electrodes, lead dioxide and DSAÒ-based electrodes) also are presented. Different chemical processes of interest to the solution of environmental problems involving ozone are discussed

Chlorine Evolution Reaction at Ti/(RuO 2 +Co 3 O 4 ) Electrodes

A investigação do mecanismo eletródico e das propriedades eletrocatalíticas da reação de desprendimento de cloro, RDCl, foi executada em eletrodos mistos de óxido do tipo rutila e espinélio de composição nominal Ti/[RuO 2 (x)+Co 3 O 4 (1-x)]. Os eletrodos foram preparados por decomposição térmica (T calc. = 470 o C; t calc. = 1h), com x variando entre 0 e 1 mudado em intervalos de 0,1. O estudo cinético foi executado registrando-se curvas corrente-potencial e pela determinação da ordem de reação com respeito aos íons H + e Cl -. Um valor constante do coeficiente de Tafel de 33 mV foi obtido para concentrações de RuO 2 entre 0-80% mol, aumentando para 40 mV para concentrações superiores de RuO 2 . Os dados experimentais apoiam o mecanismo de Erenburg e cols. para a RDCl. Um único mecanismo explica os resultados experimentais assumindo que o efeito "edge" influencie os valores do coeficiente de transferência eletrônica. A análise da atividade eletrocatalítica mostra que misturas de óxidos aumentam a atividade eletrocatalítica aparente. A systematic investigation of the mechanistic and electrocatalytic properties of the chlorine evolution reaction, ClER, on mixed rutile/spinel oxides of nominal composition Ti/ [RuO 2 (x)+Co 3 O 4 (1-x)] was done. Electrodes were prepared using the thermal decomposition procedure (T calc. = 470 o C; t calc. = 1h), with x varied between 0 and 1, changed in 0.1 steps. Kinetics were studied recording quasi-stationary current-potential curves and reaction order determined with respect to H + and Cl -. A constant Tafel slope of about 33 mV was found for the 0 -80 mol% RuO 2 concentration interval, increasing to 40 mV for higher RuO 2 contents. Experimental data support the mechanism originally proposed by Erenburg et al. for the ClER. The edge effect exerts an influence on the electronic transfer coefficient values. Analysis of the electrocatalytic activity reveals an increase in the apparent electrocatalytic activity for the mixed oxides

Influence of the electrolyte composition on the kinetics of the oxygen evolution reaction and ozone production processes

The influence of electrolyte composition (pure sulphuric or perchloric acid and their mixtures) on the kinetics of the oxygen evolution reaction (OER) and the electrochemical ozone production (EOP) on beta-PbO2 electrodes was investigated by electrochemical impedance spectroscopy and quasi-stationary polarisation curves. Analysis of the impedance spectra revealed a dependency of the electric double layer capacity and the adsorption pseudocapacitance, due to reaction intermediates, on electrolyte composition. The pseudocapacitance is a function of electrode potential and electrolyte composition, indicating the surface coverage by the reaction intermediates depends on these parameters. Tafel slope data support primary water discharge as rate determining step of the OER and EOP electrode processes. EOP current efficiency data (phiEOP) show pure electrolytes lead to maximum O3 production when compared to mixed electrolytes. According to the theoretical analysis of the electrode mechanism, this behaviour is a consequence of the reduction in surface concentration of the active centres leading to EOP caused by anion adsorption.A influência da composição do eletrólito (ácido sulfúrico, ácido perclórico e suas misturas) sobre a cinética eletródica da reação de desprendimento de oxigênio (RDO) e a produção eletroquímica de ozônio (PEO) em eletrodo de beta-PbO2, foi investigada empregando-se a espectroscopia de impedância eletroquímica e curvas de polarização quase-estacionárias. A análise dos espectros de impedância revelou uma dependência da capacitância da dupla camada elétrica e da pseudo-capacitância de adsorsão dos intermediários da reação com a composição do eletrólito. A pseudo-capacitância é função do potencial do eletrodo e da composição do eletrólito, indicando que a cobertura superficial pelos intermediários da reação depende destes parâmetros. Os valores do coeficiente de Tafel apoiam a descarga primária da água como sendo a etapa determinante da velocidade do mecanismo eletródico descrevendo a RDO e a PEO. Os valores da eficiência da corrente para a PEO (fiPEO) mostram que os eletrólitos puros resultam numa produção máxima de ozônio quando comparados aos eletrólitos mistos. Baseada na análise teórica do mecanismo eletródico, este comportamento é conseqüente da redução na concentração superficial dos centros ativos responsáveis pela PEO ocasionada pela adsorsão de ânions.446757Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES