Interaction of brilliant cresyl blue and methylene green with DNA studied by spectrophotometric and voltammetric methods

The binding behavior of two cationic dyes, brilliant cresyl blue (BCB) and methylene green (MG) to calf thymus DNA was studied by spectrophotometric and voltammetric methods. A red shift of the adsorption spectra and hypochromism accompany the binding of BCB and MG to calf thymus DNA. In 5 x 10(-2) mol dm(-3) NaCl, 5 x 10(-3) mol dm(-3) tris-HCl pH 6.87 buffer solution, the apparent binding constants are: K-BCB+ 3.0 x 10(4)M(-1) (N = 4.13) and K-MG+ = 8.8 x 10(4)M(-1) (n = 4.44). Electrochemical studies show that the formal potentials shift negatively upon addition of DNA, indicating that the oxidized forms of the dyes have stronger affinity to DNA than the reduced ones. K-BCB+/K-BCBH and K-MG+/K-MGH are evaluated to be 10.39 and 7.04. respectively. Our investigation suggests that the two cationic dyes interact with DNA predominantly via electrostatic interaction.

Determination of the relative contribution of phenolic antioxidants in orange juice by voltammetric methods

The electrochemical oxidation of caffeic, chlorogenic, sinapic, ferulic and p-coumaric acids was investigated by cyclic voltammetry on acetate buffer pH 5.6 on glassy carbon electrode and modified glassy carbon electrode. According to their voltammetric behavior, the antioxidant activity of these phenolic acids was evaluated and the results pointed to the following sequence: caffeic acid (E-a = +0.31 V) > chlorogenic acid (+ 0.38 V) > sinapic acid (+ 0.45 V) > ferulic acid (+ 0.53 V) >p-coumaric acid (+ 0.73 V). The results were confirmed by DPPH test, which evidenced the strongest antiradical activity for compounds possessing the cathecol moiety (caffeic and chlorogenic acids). Linear calibration graphs were obtained for their determination at concentrations from 1 x 10(-4) to 1 x 10(-3) mol L-1. The method was applied to orange juice. Selectivity was illustrated by the analysis of caffeic and chlorogenic acids electrodeposited on a glassy carbon electrode previously modified by electrochemical activation in the presence of ascorbic acid. (C) 2003 Elsevier B.V. All rights reserved.

Electrochemical oxidation and voltammetric determination of the antimalaria drug primaquine

Primaquine, an antimalarial drug, presents a well-defined oxidation peak around +0.6V vs SCE at a glassy carbon electrode that can be used for its determination. Calibration graphs were obtained for primaquine in B-R buffer pH 4.0 from 3.00 x 10(-5) mol L-1 to 1.00 x 10(-2) mol L-1 using linear-scan voltammetry and 3.00 x 10(-5) mol L-1 to 1.00 x 10(-2) mol L-1 using differential pulse or square-wave voltammetry. The correspondent detection limits was 9.4 mu g mL(-1); 4.2 and 1.8 mu g mL(-1), respectively. All the voltammetric methods were applied with success in direct determination of the primaquine in commercial tablets without separation or extraction procedures.

Electrochemical reduction and voltammetric determination of diloxanide furoate in non-aqueous medium

The electrochemical reduction of diloxanide furoate (DF) in acetonitrile on glassy carbon electrode was studied in this work. It was observed that DF is reduced after a reversible one-electron transfer followed by an irreversible chemical reaction, diagnosed as C-Cl bond cleavage. Its reduction was followed by linear (LSV), differential pulse (DPV) and square wave voltammetry (SWV). Analytical curves were obtained for DF determination using all the investigated voltammetric techniques. For LSV was obtained a linear range (LR) from 5.0 × 10-4 to 1.0 × 10-2 mol L-1, with detection limit (DL) of 1.5 × 10-4 mol L-1 and sensitivity (S) of 2.1 × 104 μA mol-1 L. The analytical parameters obtained by DPV were: LR = 5.0 × 10-4 to 2.2 × 10-3 mol L-1, DL = 7.8 × 10-5 mol L-1, S = 3.7 × 104 μA mol-1 L. For SWV were obtained a LR = 7.5 × 10-6 to 1.2 × 10 -3 mol L-1, DL = 5.5 × 10-6 mol L -1 and S = 2.8 × 105 μA mol-1 L. Thus, the SWV was the most sensible technique, which can be used for DF determination at low concentration levels. Statistics methods were used to evaluate the analytical procedure, where recovery around to 100% was obtained for all voltammetric techniques. Relative standard deviations were lower than 5.0% (N=5). The obtained t values evaluating all the three voltammetric methods were less than the tabulated ones, indicating that there are no evidences of systematic error. ©2005 Sociedade Brasileira de Química.

meso-substituted octabromoporphyrins: Synthesis, spectroscopy, electrochemistry and electronic structure

The free-base, copper(II) and zinc(II) derivatives of 5,10,15,20-tetraarylporphyrin (aryl = phenyl, 4-methylphenyl or 4-chlorophenyl) and the corresponding brominated 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraarylporphyrin derivatives have been synthesized and their spectral and redox properties compared by UV/VIS, H-1 NMR, ESR and cyclic voltammetric methods. Substitution with the electron-withdrawing bromine groups at the pyrrole carbons has a profound influence on the UV/VIS and H-1 NMR spectral features and also on the redox potentials of these systems. On the other hand, electron-withdrawing chloro or electron-donating methyl groups at the para positions of the four phenyl rings have only a marginal effect on the spectra and redox potentials of both the brominated and the non-brominated derivatives. The ESR data for the copper(II) derivatives of ail these systems reveal that substitution at either the beta-pyrrole carbons and/or the para positions of the meso-phenyl groups does not significantly affect the spin-Hamiltonian parameters that describe the metal centre in each case. Collectively, these observations suggest that the highest-occupied (HOMO) and lowest-unoccupied molecular orbitals (LUMO) of the octabromoporphyrins involve the porphyrin pi-ring system as is the case with the non-brominated derivatives.-Investigations have been carried out to probe the electronic structures of these systems by three different approaches involving spectral and redox potential data as well as AMI calculations. The results obtained suggest that the electron-withdrawing beta-bromine substituents stabilize the LUMOs and, to a lesser degree, the HOMOs and that the extent of these changes can be fine-tuned, in a subtle way, by substituting at the meso-aryl rings of a given porphyrin.

Fabrication of a metalloporphyrin - Polyoxometalate hybrid film by a layer-by-layer method and its catalysis for hydrogen evolution and dioxygen reduction

Tetrakis (N-methylpyridyl) porphyrinato] cobalt (CoTMPyP) and 1:12 silicotungstic acid (SiW12) were alternately deposited on a 4-aminobenzoic acid (4-ABA)-modified glassy carbon electrode through a layer-by-layer method. The resulting organic-inorganic hybrid films were characterized by cyclic voltammetry (CV) and UV/vis absorption spectroscopy. We proved that the prepared multilayer films are uniform and stable. SiW12-containing multilayer films (SiW12 as the outermost layer) exhibit remarkable electrocatalytic activity for the hydrogen evolution reaction (HER). The kinetic constants for HER were comparatively investigated at different layers Of SiW12/CoTMPyP multilayer film-modified electrodes by hydrogen evolution voltammetry. In addition, rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) voltammetric methods confirm that SiW12/CoTMPyP (CoTMPyP as the outermost layer) multilayer films catalyze almost a two-electron reduction of O-2 to H2O2 in pH 1-6 buffer solutions. Furthermore, P2W18/CoTMPyP films were also assembled, and their catalytic activity for HER is very different from that Of SiW12/CoTMPyP multilayer films.

Study of the ion channel behavior of didodecyldimethylammonium bromide formed bilayer lipid membrane stimulated by PF6-

Bilayer lipid membranes ( BLM) formed from didode-cyldimethylammonium bromide were made on the freshly exposed surface of a glassy carbon (GC) and were demonstrated by the ac impedance spectroscopy. The ion channels of membrane properties induced by PF6- were studied by the cyclic voltammetric methods. Experimental results indicated that the ion channel of BLM was open in the presence of the PF6- due to the interaction of PF6- with the BLM, while it was switched off in the absence of PF6-. Because the ion channel behavior was affected by the concentration of PF6-, a sensor for PF6- can be developed.

Electrochemical analysis of opiates—an overview

The analysis of opiates is of vital interest in drug abuse monitoring and research. This review presents a general overview of the electrochemical methods used for detection and quantification of opiates in a variety of matrices. Emphasis has been placed on the voltammetric methods used for study and determination of morphine, codeine, and heroin. Specific issues that need to be solved and better explained as well as future trends in the use of electrochemical methods in the examination of opiates are also discussed.

Deteção eletroquímica da norfloxacina e trimetoprim em amostras de urina utilizando polímero molecularmente impresso modificado e grafeno

A norfloxacina e o trimetoprim são dois antibióticos antibacterianos usados para o tratamento de infeções urinárias, intestinais e respiratórias. A maioria dos fármacos exige uma dosagem que garanta os níveis de segurança e eficácia de atuação. A necessidade de dosear os medicamentos e os seus metabolitos é assim um controlo imperioso e em muitos casos regular no tratamento de um paciente. Neste trabalho desenvolveram-se dois sensores eletroquímicos para a deteção da norfloxacina (NFX) e do trimetoprim (TMP), usando como superfície de suporte o carbono vítreo. A busca de novos materiais que conferiram maior seletividade e sensibilidade aos sistemas de deteção e por outro lado apresentem menores riscos para o paciente quando usados em dispositivos que permitam uma análise point-of-care, é especialmente importante e pode ser uma parte crucial do processo de decisão clínica. Assim, os polímeros molecularmente impresos enquadram-se nesse perfil e o seu uso tem vindo a ser cada vez mais avaliado. A impressão molecular é uma tecnologia capaz de produzir polímeros que incorporam as moléculas do analito e que após remoção por solventes específicos, permitem dotá-los de locais específicos de reconhecimento estereoquímico. A seleção do pirrol como polímero molecularmente impresso (MIP) permitiu construir com sucesso os sensores para doseamento dos antibióticos. A fim de aumentar a sensibilidade do método incorporou-se grafeno na superfície do elétrodo. Este material tem vindo a ser largamente utilizado devido às suas propriedades: estrutura molecular, condutividade elétrica e aumento da superfície são algumas das características que mais despertam o interesse para a sua aplicação neste projeto. Os sensores desenvolvidos foram incorporados em sistemas eletroquímicos. Os métodos voltamétricos aplicados foram a voltametria cíclica, a voltametria de onda quadrada e ainda a impedância. As condições de análise foram otimizadas no que respeita à polimerização do pirrol (concentração do polímero, número de ciclos de eletropolimerização e respetivos potenciais aplicados, tempo de incubação, solvente de remoção do analito), ao pH da solução do fármaco, à gama de concentrações dos antibióticos e aos parâmetros voltamétricos dos métodos de análise. Para cada um dos antibióticos um elétrodo não-impresso foi também preparado, usando o procedimento de polimerização mas sem a presença da molécula do analito, e foi usado como controlo. O sensor desenvolvido para o trimetoprim foi usado no doseamento do fármaco em amostras de urina. As amostras foram analisadas sem qualquer diluição, apenas foram centrifugadas para remoção de proteínas e algum interferente. Os sensores construídos apresentaram comportamento linear na gama de concentrações entre 102 e 107 mol/L. Os resultados mostram boa precisão (desvios padrão inferiores a 11%) e os limites de deteção foram de 8,317 e 1,307 mol/L para a norfloxacina e o trimetoprim, respetivamente. Para validação do método foram ainda efetuados ensaios de recuperação tendo obtido valores superiores a 94%.

Chemically Modified Glassy Carbon Electrode as Sensors for Various Pharmaceuticals

Voltammetric methods are applicable for the determination of a wide variety of both organic and inorganic species. Its features are compact equipment, simple sample preparation, short analysis time, high accuracy and sensitivity. Voltammetry is especially suitable for laboratories in which only a few parameters have to be monitored with a moderate sample throughput. Of various electrode materials, glassy carbon electrode is particularly useful because of its high electrical conductivity, impermeability to gases, high chemical resistance, reasonable mechanical and dimensional stability and widest potential range of all carbonaceous electrodes. Electrode modification is a vigorous research area by which the electrochemical determination of various analyte species is facilitated. The scope of pharmaceutical analysis includes the analytical investigation of pure drug, drug formulations, impurities and degradation products of drugs, biological samples containing the drugs and their metabolites with the aim of obtaining data that can contribute to the maximal efficacy and maximal safety of drug therapy. This thesis presents the modification of glassy carbon electrode using metalloporphyrin and dyes and subsequently using these modified electrodes for the determination of various pharmaceuticals. The thesis consists of 9 chapters.

Electrochemical studies of copper, copper-aluminium and copper-aluminium-silver alloys: Impedance results in 0.5M NaCl

The electrochemical behaviour of Cu, Cu-Al and Cu-Al-Ag alloys in aqueous solutions of NaCl (0.5 M, pH = 3.00) was studied by means of voltammetric methods and electrochemical impedance spectroscopy. The surfaces were examined by SEM and EDX analysis. Cu-Al-Ag alloy shows a potentiodynamic behaviour similar to that of the pure copper electrode while the Cu-Al alloy presents some minor differences. In the active dissolution region the electrodes suffer pitting corrosion and in the other potential regions there are the formation of a passivant film with composition depending on the potential. The impedance responses of the electrodes are discussed. An electrodissolution mechanism is proposed and the effect of the alloying elements upon the impedance response and polarisation curves is explained. The main effects are due to the production of copper and silver chlorides and aluminium oxides/ hydroxides at the corroding interface. The addition of Al or (Al + Ag) increases the corrosion resistance of pure copper. © 1995.

Determinação voltamétrica de zinco empregando eletrodos quimicamente modificados com bismuto

This dissertation presents the development of voltammetric methods to zinc determination in multivitamin commercial samples, talc, and art materials for painting (soft pastel) combining an alkaline extraction with 1.0 mol L-1 NaOH aqueous solution and bismuth modified electrodes. Two electrodes were used to zinc quantification in the samples, bismuth film electrode (BiFE) plated in situ onto glassy carbon and carbon paste electrode chemically modified with strongly acidic ion exchange resin Amberlite® IR 120 and bismuth nanostructures (EPCAmbBi). It was verified that the best concentration of Bi3+ for Bi film deposition onto glassy carbon was 4.0 μmol L-1 using an 0.1 mol L-1 acetate buffer aqueous solution (pH = 4.5) as supporting electrolyte. The best condition to formation of Bi nanostructures in the EPC modified with 10 % Amberlite® IR 120 was the use of 30 s to pre-concentration (open circuit) in 0.5 mmol L-1 Bi3+ aqueous solution (pH 5.5) prepared with supporting electrolyte solution. The obtained analytical curve for Zn2+ using BiFE presented linear range from 0.5 to 5.0 μmol L-1, the limit of detection (LD) was 41 nmol L-1. For EPCAmbBi only one linear range was observed for the analytical curve varying the Zn2+ concentration from 0.05 to 8.2 μmol L-1, LD obtained in this curve it was equal to 10 nmol L-1. The EPCAmbBi presented the most intense and sharp anodic stripping peaks for Zn2+ presenting, therefore, a better voltammetric profile, with sensitivity higher than obtained with the BiFE. Moreover, the EPCAmbBi presented a LD lower than that obtained with the BiFE. Alkaline extraction was an efficient sample pretreatment to extract Zn2+ from solid samples, besides that, this procedure was less susceptible to interferences from Cu2+, since it remains at extracting vessel as insoluble Cu(OH)2. The combination of alkaline extraction with the EPCAmbBi is a simple, fast, efficient and low cost for the zinc determination in pharmaceutical formulations and art materials for painting (soft pastel) samples, which can be employed as a low-cost alternative method to the atomic absorption spectroscopy.

Desenvolvimento de métodos electroquímicos de quantificação de fármacos em amostras de água contaminadas

Este trabalho teve como objectivo, o desenvolvimento de um método electroquímico, para quantificação do fármaco carbamazepina (CBZ) em águas contaminadas. Neste trabalho foram utilizados quatro métodos voltamétricos: a voltametria cíclica, a voltametria de varrimento linear, a voltametria de onda quadrada e a voltametria de impulso diferencial. Os eléctrodos de trabalho utilizados foram, o eléctrodo de mercúrio de gota suspensa, o eléctrodo de carbono vítreo clássico e um eléctrodo de carbono vítreo modificado com um filme de nanotubos de carbono de paredes múltiplas (MWCNTs). O eléctrodo de mercúrio de gota suspensa permitiu o estudo da redução da CBZ numa região de potencial mais catódico, e os eléctrodos de carbono vítreo, com e sem modificação, permitiram o estudo da oxidação da CBZ numa região de potencial mais anódico. Nas condições experimentais estudadas, o eléctrodo de mercúrio de gota suspensa revelou ser um sensor voltamétrico pouco eficaz na determinação quantitativa da carbamazepina, em amostras com uma matriz complexa. Entre os eléctrodos de carbono vítreo, o eléctrodo de carbono vítreo modificado com os MWCNTs revelou ser o sensor voltamétrico mais eficaz e sensível, na detecção e determinação da carbamazepina. Modificado com um filme de nanotubos de carbono de paredes múltiplas, que previamente foram dispersos em dihexadecilhidrogenofosfato (DHP) e água, este novo eléctrodo permitiu obter uma resposta electroquímica da CBZ, consideravelmente superior ao eléctrodo não modificado. Utilizando a voltametria de varrimento linear e as condições experimentais consideradas óptimas, o eléctrodo nanoestruturado permitiu obter uma relação linear entre o sinal medido e a concentração da CBZ no intervalo 0.13- 1.60 M (30.7- 378 g -1), com os limites de detecção e quantificação mais baixos, até à data reportados com métodos electroquímicos (0.04 e 0.14M, respectivamente). O eléctrodo modificado foi aplicado na quantificação da CBZ, em formulações farmacêuticas, em águas naturais tratadas e em amostras de águas residuais, ambas dopadas, obtendo-se taxas de recuperação consideravelmente elevadas (100.6%, 98.0%,95.8%, respectivamente). Os resultados obtidos, na análise da CBZ em amostras ambientais, com o eléctrodo modificado, foram comparados com resultados obtidos por HPLC-UV e LC­ ESI-MS/MS, validando o método electroquímico desenvolvido neste trabalho. ABSTRACT: The aim of this work was to develop a new electrochemical method for the quantification of carbamazepine (CBZ) in contaminated waters. ln this study, four voltammetric methods were used: cyclic voltammetry, linear sweep voltammetry, square wave voltammetry and differential pulse voltammetry. the working electrodes used were the hanging mercury drop electrode (HMDE), the classical glassy carbon electrode (GCE), and a glassy carbon electrode modified with a film of multi-walled carbon nanotubes (MWCNls). Using HMDE, the reduction of CBZ was studied in the cathodic potential region. the CGE sensors, with or without modification, allowed the study of CBZ oxidation in the anodic potential region. ln the tested conditions, the results obtained for the quantification of CBZ using the HMDE sensor were not very satisfactory, especially when more complex samples were analysed. When the MWCNls-dihexadecyl hydrogen phosphate (DHP) film­ coated GCE was used for the voltammetric determination of CBZ, the results obtained showed that this modified electrode exhibits excellent enhancement effects on the electrochemical oxidation of CBZ. the oxidation peak current of CBZ at this film­ modified electrode increased significantly, when compared with that at a bare glassy carbon electrode. The enhanced electrooxidation and voltammetry of CBZ at the surface of MWCNTs-DHP film coated GCE in phosphate buffer solution (pH 6.71) was attributed to the unique properties of MWCNTs such as large specific surface area and strong adsorptive properties providing more reaction sites. The proposed method was applied to the quantification of CBZ in pharmaceutical formulations, drinking water and wastewater samples with good recoveries and low limits of detection and quantification (0.04 and 0.14 M, respectively), and was positively compared with chromatographic techniques usually used in the quantification of pharmaceutical compounds in environmental samples. HPLC-UV and LC-ESI-MS/MS were also used in the quantification of CBZ in pharmaceutical formulations and wastewater samples to prove the importance and accuracy of his voltammetric method.