RESUMO
New screen-printed sensor with a boron-doped diamond working electrode (SP/BDDE) was fabricated using a large-area linear antenna microwave chemical deposition vapor system (LA-MWCVD) with a novel precursor composition. It combines the advantages of disposable printed sensors, such as tailored design, low cost, and easy mass production, with excellent electrochemical properties of BDDE, including a wide available potential window, low background currents, chemical resistance, and resistance to passivation. The newly prepared SP/BDDEs were characterized by scanning electron microscopy (SEM) and Raman spectroscopy. Their electrochemical properties were investigated by cyclic voltammetry and electrochemical impedance spectroscopy using inner sphere ([Fe(CN)6]4-/3-) and outer sphere ([Ru(NH3)6]2+/3+) redox probes. Moreover, the applicability of these new sensors was verified by analysis of the anti-inflammatory drug lornoxicam in model and pharmaceutical samples. Using optimized differential pulse voltammetry in Britton-Robinson buffer of pH 3, detection limits for lornoxicam were 9 × 10-8 mol L-1. The oxidation mechanism of lornoxicam was investigated using bulk electrolysis and online electrochemical cell with mass spectrometry; nine distinct reaction steps and corresponding products and intermediates were identified.
Assuntos
Boro , Eletrólise , Boro/química , Eletrodos , Oxirredução , Análise Espectral RamanRESUMO
Voltammetric behavior of muscle relaxant dantrolene sodium (DAN) was studied and the voltammetric methods for its determination using polished and mercury meniscus modified silver solid amalgam electrodes (p-AgSAE and m-AgSAE) as well as using bismuth film electrode (BiFE, ex situ plating on GCE) have been proposed. These working electrodes represent the most commonly used alternatives to mercury ones which come wrongfully into disfavor because of alleged toxicity of mercury. Within this work, the obtained results of DAN determination have been completed by corresponding statistical parameters and also some electrochemical characteristics of AgSAEs and BiFE were assessed, especially in comparison with the mercury electrodes.
RESUMO
Triacetone triperoxide (3,3,6,6,9,9-hexamethyl-1,2,4,5,7,8-hexoxonane, TATP) is nowadays one of the most commonly used improvised explosives. It is prepared by the action of hydrogen peroxide on acetone in an acidic environment. Easily available mineral acids - hydrochloric, sulfuric, nitric and perchloric - are the most often recommended on the extremist web pages dealing with improvised production of explosives. The various TATP producers' choice of acid mainly depends on the author's experiences and the local availability of the acid. A knowledge of the kind of acid used for TATP production can help in detecting the person who has made the TATP, or who has committed a criminal act using TATP. Therefore, a capillary isotachophoretic method was developed for determination of residual anions (originating from the acid used during TATP synthesis) in the resulting TATP crystals. This analytical method has proved to be reliable; the acid used for TATP synthesis was correctly identified in all samples analyzed.
RESUMO
Silver solid amalgam electrode (AgSAE) was used for differential pulse voltammetric (DPV) measurements of cysteine and cysteine-containing peptides, glutathione, gamma-Glu-Cys-Gly and phytochelatin (gamma-Glu-Cys)(3)-Gly (PC3), in the presence of Co(II) ions. It had been established earlier that cysteine-containing peptides and proteins catalyze hydrogen evolution at mercury electrodes in presence of cobalt salts; these processes are known as the Brdicka reaction. DPV signals measured with the AgSAE, the surfaces of which had been modified by mercury meniscus or mercury film, were qualitatively the same as those obtained with the hanging mercury drop electrode (HMDE). With these electrodes the number and the intensity of Brdicka signals of cysteine, glutathione and PC3 differed, making a distinction among them possible. On the other hand, with the polished silver solid amalgam electrode (the surface of which was completely free of liquid mercury) all three compounds produced only one but strikingly intense peak in the region of Brdicka reaction. Using this signal, cysteine, glutathione as well as PC3 could be determined at 10(-8)M level, representing sensitivity up to 2 orders of magnitude better than attained with the mercury-modified AgSAEs or HMDE.