RESUMO
New voltammetric and flow amperometric methods for the determination of guaifenesin (GFE) using a perspective screen-printed sensor (SPE) with boron-doped diamond electrode (BDDE) were developed. The electrochemical oxidation of GFE was studied on the surface of the oxygen-terminated BDDE of the sensor. The GFE provided two irreversible anodic signals at a potential of 1.0 and 1.1 V (vs. Ag|AgCl|KCl sat.) in Britton-Robinson buffer (pH 2), which was chosen as the supporting electrolyte for all measurements. First, a voltammetric method based on differential pulse voltammetry was developed and a low detection limit (LOD = 41 nmol L-1), a wide linear dynamic range (LDR = 0.1-155 µmol L-1), and a good recovery in the analysis of model and pharmaceutical samples (RSD <3.0 %) were obtained. In addition, this sensor demonstrated excellent sensitivity and reproducibility in the analysis of biological samples (RSD <3.2 %), where the analysis took place in a drop of serum (50 µL) without pretreatment and additional electrolyte. Subsequently, SP/BDDE was incorporated into a flow-through 3D printed electrochemical cell and a flow injection analysis method with electrochemical detection (FIA-ED) was developed, resulting in excellent analytical parameters (LOD = 86 nmol L-1, LDR = 0.1-50 µmol L-1). Moreover, the mechanism of electrochemical oxidation of GFE was proposed based on calculations of HOMO spatial distribution and spectroelectrochemical measurements focused on IR identification of intermediates and products.
RESUMO
Screen-printed sensors with chemically deposited boron-doped diamond electrodes (BDDE) were modified with different types of gold nanoparticles (AuNPs) according to a new original procedure. Physically and electrochemically deposited AuNPs had various sizes and also nanoporous character. They also differ in shape and density of surface coverage. The developed sensors were characterized using scanning electron microscopy and Raman spectroscopy. Their electrochemical properties were studied using cyclic voltammetry and electrochemical impedance spectrometry of selected outer sphere ([Ru(NH3)6]Cl3) and inner sphere (K3[Fe(CN)6], dopamine) redox markers. The application possibilities of such novel screen-printed sensors with BDDE modified by AuNPs were verified in the analysis of the neurotransmitter dopamine. The best analytical performance was achieved using printed sensors modified with the smallest AuNPs. The achieved limit of detection values in nanomolar concentrations (2.5 nmol L-1) are much lower than those of unmodified electrodes, which confirms the significant catalytic effects of gold nanoparticles on the surface of the working electrode. Sensors with the best electrochemical properties were successfully applied in the analysis of a model solution and spiked urine samples.
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
The electrochemical behavior of folic acid (FA) on a polished silver solid amalgam electrode (p-AgSAE), as a liquid mercury free electrode, has been studied in this paper. Differential pulse voltammetry (DPV) was found as a suitable method for voltammetric determination of folic acid. A limit of detection as 5.88 × 10-10 M (after 60 s of accumulation) was calculated for FA determination in an acetate buffer (pH 5). P-AgSAE in connection with DPV with optimized parameters was successfully applied for the determined folic acid compound in two types of vitamin preparations and two kinds of fruit juices. It was found that p-AgSAE is an appropriate tool for voltammetric determination of this vitamin in these real samples and it can replace mercury electrodes in voltammetric analysis of folic acid.