RESUMO
In this work, the electrochemical behavior of the glycosylated flavonoid kaempferitrin was studied, and an electroanalytical methodology was developed for its determination in infusions of Bauhinia forficata using a boron-doped diamond electrode (BDD). The electrochemical behavior of the flavonoid was studied by cyclic voltammetry, and two irreversible oxidation peaks at 0.80 and 1.0 V vs Ag/AgCl were observed. The influence of the pH on the voltammograms was examined, and higher sensitivity was found at pH 7.0. The electrochemical process corresponding to peak 1 at 0.80 V is predominantly diffusion-controlled, as the study shows at varying scan rates. An analytical plot was obtained by square wave voltammetry at optimized experimental conditions (frequency = 100 s-1, amplitude = 90 mV, and step potential = 8 mV) in the concentration range from 3.4 µmol L-1 to 58 µmol L-1, with a linearity of 0.99. The limit of detection and limit of quantification values were 1.0 µmol L-1 and 3.4 µmol L-1, respectively. Three samples of Bauhinia forficata infusions (2 g of sample in 100 mL of water) were analyzed, and the KF values found were 5.0 × 10-4 mol L-1, 3.0 × 10-4 mol L-1, and 7.0 × 10-4 mol L-1, with recovery percentages of 98 %, 106 % and 94 %, respectively. Finally, experiments were performed with two other flavonoids (chrysin and apeginin) to compare and propose an electrochemical oxidation mechanism for kaempferitrin, which was supported by quantum chemical calculations.
Assuntos
Técnicas Eletroquímicas , Quempferóis , Oxirredução , Quempferóis/química , Quempferóis/análise , Técnicas Eletroquímicas/métodos , Glicosilação , Eletrodos , Bauhinia/química , Teoria Quântica , Flavonoides/química , Flavonoides/análise , Limite de Detecção , Diamante/químicaRESUMO
In order to obtain higher agricultural yields, the use of chemical substances has been increased to prevent the proliferation of pests, as well as ensuring durability in the storage of the food produced. Such substances are known as pesticides that may well present risks to human health and the environment. In the presence of metal ions, these substances can interact forming new species with different characteristics. Carbendazim (MBC) is an example of a harmful pesticide, which has atoms of nitrogen and oxygen in its structure that can form complexes with metal ions. Thus, in this work has studied the interaction between the copper (II) metal ion and carbendazim and its formation in natural water. The Cu-MBC complex showed a reduction peak of 0.007 V and an oxidation peak of 0.500 V, with characteristics of a quasi-reversible process under a glassy carbon electrode. By anodic stripping voltammetry, a different behavior was observed in the interaction of copper and carbendazim in ultrapure water and Billings dam water; however, it was possible to observe the complex in both samples. Carbendazim in the presence of the metal shows lower oxidation potential value, indicating the influence of the metal on the electrochemical response of the pesticide.
Assuntos
Benzimidazóis/química , Carbamatos/química , Cobre/química , Poluentes Químicos da Água/química , Carbono/química , Técnicas Eletroquímicas/métodos , Eletrodos , OxirreduçãoRESUMO
A simple, rapid and effective analytical method based on fluorescence spectroscopy for the determination of coumarin in pharmaceutical formulations without pre-treatment or pre-concentration step was development. Coumarin had maximum excitation and emission at 310 nm and 390 nm, respectively. Optimum conditions for the detection of coumarin were investigated. Under optimized conditions, we observed a linear behavior for the sign of coumarin in the concentration range of 2.5 × 10(-6) to 1.0 × 10(-4) mol L(-1), with linearity of 0.998 and sensitivity of 2.9 × 10(10) u.a/mol L(-1). The proposed method was validated in terms of accuracy, precision and specificity of coumarin using the standard addition and external calibration. It was noted that the results support (P<0.05), indicating that the matrices were not an interference in the determination of coumarin by fluorescence spectroscopy. The results were favorable compared with those obtained by reference chromatographic methods.
Assuntos
Cumarínicos/análise , Espectrometria de Fluorescência/métodos , Comprimidos/química , Cumarínicos/química , Concentração de Íons de Hidrogênio , Limite de Detecção , Solventes/químicaRESUMO
Potentially useful stead-state fluorimetric technique was used to determine the critical micellar concentrations (CMC(1) and CMC(2)) for two micellar media, one formed by SDS and the other by SDS/Brij 30. A comparative study based on conductimetric and surfacial tension measurements suggests that the CMC(1) estimated by the fluorimetric method is lower than the value estimated by these other techniques. Equivalent values were observed for SDS micelles without Brij 30 neutral co-surfactant. The use of acridine orange as fluorescent probe permitted to determine both CMC(1) and CMC(2). Based on it an explanation on aspects of micelle formation mechanism is presented, particularly based on a spherical and a rod like structures.
Assuntos
Fluorometria/métodos , Micelas , Polietilenoglicóis/química , Dodecilsulfato de Sódio/química , Laranja de Acridina , Polidocanol , Tensoativos/químicaRESUMO
The microenvironment formed by lauroyl and stearoyl derivatives of chitosan in solution has been studied using two fluorescent probes, pyrene and nabumetone. Existence or not of microdomains formed by polymolecular associations, the inherent hydrophobicity of them in aqueous solution, and the influence of degree of substitution (DS) of derivatives were investigated by emission properties of pyrene and strengthened by the photophysical behavior of nabumetone. Additionally, the ratio between the fluorescence intensities of first (approximately 372 nm) to the third (approximately 384 nm) bands of the emission spectrum of pyrene was used to determine the critical aggregation concentration (CAC). In a previous work, it was already reported the characterization of chitosan derivatives by three spectroscopic techniques ((13)C-NMR, (1)H-NMR and infrared), as well as data on the solubility and swelling-index of them. In addition of that, the new results show that the investigated lauroyl and stearoyl derivatives of chitosan are expected to be potential models for applications in the medical field.
Assuntos
Anti-Inflamatórios não Esteroides/química , Butanonas/química , Quitosana/química , Corantes Fluorescentes/química , Pirenos/química , Interações Hidrofóbicas e Hidrofílicas , Nabumetona , Espectrometria de FluorescênciaRESUMO
Monolayers of 3,3'-dithiodipropionic acid (DTDPA) were prepared on a polycrystalline gold electrode through a self-assembly procedure to produce a gold 3,3'-dithiodipropionic acid self-assembled monolayer (AuDTDPA) modified electrode. The characterization of the AuDTDPA electrode was investigated by cyclic voltammetry and ac impedance using the [Fe(CN)(6)](3-/4-) redox couple. The electrochemical behavior of DA on the modified electrode AuDTDPA was studied by cyclic and square-wave voltammetries, using phosphate buffer as supporting electrolyte. The oxidation peak current for DA increases linearly with concentration in the range of 0.35x10(-5) to 3.4x10(-5)molL(-1). The performance of the AuDTDPA modified electrode was evaluated for the electroanalytical determination of dopamine (DA) in a pharmaceutical formulation. The AuDTDPA modified electrode showed a stable behavior and the presence of surface-COOH groups avoided the passivation of the electrode surface during the dopamine oxidation.