Electrochemical and quantum chemical approaches to the study of dopamine sensing using bentonite and l-cysteine modified carbon paste electrode.

This work presents a significant investigation involving both electrochemical experiment and quantum chemical simulation approaches. The objective was to characterize the electrochemical detection of dopamine (DA). The detection was carried out using a modified carbon paste electrode (CPE) incorporating bentonite (Bent) and l-cysteine (CySH) (named as CySH/Bent/CPE). To understand and explain the oxidation mechanism of DA on the CySH/Bent modified electrode surface, the coupling of the two approaches were exploited. The CySH/Bent/CPE showed excellent electroactivity toward DA such as good sensibility, selectivity, stability, and regenerative ability. The developed sensor shows a dynamic linear range from 0.8 to 80 µM with a limit of detection and quantification of 0.5 µM and 1.5 µM, respectively. During the quantitative analysis of DA in presence of ascorbic acid (AA) and uric acid (UA) the electrochemical oxidation signals of AA, DA, and UA distinctly appear as three separate peaks. The potential differences between the peaks are 190 mv, 150 mv, and 340 mV for the AA-DA, DA-UA, and AA-UA oxidation pairs, respectively. These observations stem from square wave voltammetry (SWV) studies, along with the corresponding redox peak potential separations. The developed sensor is simple and accurate to monitor DA in human serum samples. On the other hand, CySH acts as an electrocatalyst on the CySH/Bent/CPE surface by increasing its active electron transfer sites, as suggested by the quantum chemical modeling with analytical results of Fukui. Furthermore, the voltammetric results obtained agree well with the theoretical calculations.

Detection of paracetamol by a montmorillonite-modified carbon paste sensor: A study combining MC simulation, DFT computation and electrochemical investigations.

This study aims to develop a suitable electrochemical electrode through the incorporation of potassium montmorillonite (MMTK10)clay into the carbon matrix for the direct and sensitive determination of paracetamol (PAR) in pharmaceutical formulations. Electrochemical characterization of the electrodes involves the use of techniques such as cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and differential pulse voltammetry (DPV). The results reveal that the voltammetric response of PAR is linear over a wide concentration range (1.0-15 µM), with a low detection limit of 0.46 µM. Analytically, PAR recovery results were around 94%, indicating that the developed electrode is highly suitable for PAR detection in pharmaceutical formulation. Additionally, density functional theory (DFT) is employed to investigate the reactivity of PAR and explain the interaction process of PAR on the electrode surface at different pH values. A Monte Carlo simulations model is developed to provide a deeper understanding of the adsorption mechanism, particularly to comprehend molecular interactions and preferential orientations of PAR with MMT fractions at the electrode surface. Reduced Density Gradient is calculated and discussed using techniques such as Multiwfn and Visualization of Molecular Dynamics. The developed CPE-MMTK10 sensor provided a simple preparation method, rapid response, high sensitivity, reproducibility, strong selectivity, and extended stability. Moreover, there is a good correlation between most parameters calculated by DFT and experimental results, thereby reinforcing the validity of the theoretical approach in this study.

A Carbon Paste Electrode Modified by Bentonite and l-Cysteine for Simultaneous Determination of Ascorbic and Uric Acids: Application in Biological Fluids.

A novel modification of a paste carbon electrode by Bentonite (Bent) and l-Cysteine (l-Cyst) was carried out for uric acid (UA) and ascorbic acid (AA) detection and quantification. Morphological and compositional characterization of the electrode surface were carried out using electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopic analysis (EDS). Cyclic voltammetry (CV) and square wave voltammetry (SWV) techniques were used to analyze UA and AA. The obtained sensor shows a good stability, sensibility, selectivity, and regeneration ability. Accordingly, the limit of detection (LOD) is found to be 0.031 µm and 9.6 µm for UA and AA, respectively. A good linearity in the range of 0.1 to 100 µm for UA and 10 to 1000 µm for AA was obtained. The peak-to-peak separation of UA-AA (ΔEUA-AA ) was determined to be 330 mV. In addition, the sensor is applied successfully to monitor UA and AA in serum samples.

A novel l-leucine modified Sol-Gel-Carbon electrode for simultaneous electrochemical detection of homovanillic acid, dopamine and uric acid in neuroblastoma diagnosis.

Neuroblastoma is a pediatric neuroblastic tumor arising in the sympathetic nervous crest cells. A high grade of Neuroblastoma is characterized by a high urinary excretion of homovanillic acid and dopamine. In this work l-leucine modified Sol-Gel-Carbon electrode was used for a sensitive voltammetric determination of homovanillic acid and dopamine in urine. The electrochemical response characteristics were investigated by cyclic and differential pulse voltammetry; the modified electrode has shown an increase in the effective area of up to 40%, a well-separated oxidation peaks and an excellent electrocatalytic activity. High sensitivity and selectivity in the linear range of 0,4-100µML-1 of homovanillic acid and 10-120µML-1 of dopamine were also obtained. Moreover, a sub-micromolar limit of detection of 0.1µM for homovanillic acid and 1.0µM for the dopamine was achieved. Indeed, high reproducibility with simple preparation and regeneration of the electrode surface made this electrode very suitable for the determination of homovanillic acid and dopamine in pharmaceutical and clinical preparations. The mechanism of homovanillic acid and the electrochemical oxidation at l-leucine modified Sol-Gel-Carbon electrode is described out the B3P86/6-31+G(d,p) level of theory as implemented in Gaussian software.

beta-Sonogel-carbon electrodes: a new alternative for the electrochemical determination of catecholamines.

In this work, a new alternative for the electrochemical determination of catecholamines based on beta-cyclodextrin-Sonogel-Carbon electrodes is reported. The incorporation of beta-CD and graphite in the preparation of the Sonogel-Carbon material leads to a modification of the electrode surface properties which causes a significant increase in the oxidation peak current of biomolecules such as dopamine, L-epinephrine, D,L-norepinephrine and catechol. This phenomenon might be attributed to the formation of an inclusion complex between beta-CD and the catecholamines. The amount of beta-CD necessary to form the Sonogel electrode was studied and optimization of electrochemical parameters, perm selectivity and mechanical stability of the sensor are discussed. Scanning electron microscopy and electrochemical impedance spectroscopy measurements were employed to characterize the electrical parameters and the structural properties of the new electrode surface, respectively. Cyclic voltammetry (CV) and Adsorptive differential pulse voltammetry (AdDPV) measurements were also used to explore the electrochemical behaviour of the electrode versus the quoted catecholamines. The beta-CD-Sonogel-Carbon electrode offers fast and linear responses towards dopamine, norepinephrine, epinephrine and catechol, with good and low detection limits: 0.164, 0.294, 0.699 and 0.059 micromol L(-1), respectively.

A novel electrochemical synthesis of poly-3-methylthiophene-gamma-cyclodextrin film Application for the analysis of chlorpromazine and some neurotransmitters.

Gamma-cyclodextrin is an eight glucose unit conical structure, which possesses a hydrophobic internal cavity exhibiting supramolecular complexing properties and a hydrophilic exterior due to the presence of hydroxyl groups. In this work, we have synthesized for the first time a functionalized stable film of poly-3-methylthiophene combined with gamma-cyclodextrin (P3MT/gamma-CD) in tetrabutylammonium hexafluorophosphate/acetonitrile solution. A potentiostatic mode was employed for the film growth. Cyclic voltammetry and electrochemical impedance spectroscopy were used for the characterization of the new film. The resulting conducting polymer sensor offers interesting analytical performances such as: (a) fast and linear responses towards the neurotransmitters dopamine and l-dopa towards the neuroleptic chlorpromazine with low detection limits of 2 x 10(-7), 10(-6), and 10(-7)M, respectively, and (b) simultaneous detection and well-resolved signals between the compounds of interest and ascorbic acid. To the best of our knowledge, these LOD are among the lowest found in the literature. Optimization of parameters such as interference effect, perm-selectivity, and mechanical stability of the sensor are discussed.

Electrosynthesis and analytical performances of functionalized poly (pyrrole/beta-cyclodextrin) films.

The supramolecular complexing properties of cyclodextrins (CDs) have been investigated inside a conducting polymer environment. In this work, we report the synthesis and characterization of a polypyrrole/beta-cyclodextrin (Ppy/beta-CD) film at a glassy carbon (GC) electrode surface. The polypyrrole/beta-cyclodextrin (Ppy/beta-CD) film was prepared by a simple electropolymerization of a 20:1 mixture of the CD and the pyrrole monomer LiClO(4) supporting electrolyte. The resulting functionalized polymer film features interesting electrochemical properties such as selective, simultaneous and quantitative detection of some organic compounds of interest such as polyhydroxyphenyls and neurotransmitters derived from pyrogallol and catechol. The fabricated electrochemical sensor exhibits a fast and reversible linear response toward catechol within the concentration range of 1.5x10(-7) to 8x10(-6)M and towards pyrogallol within the concentration range of 1x10(-6) to 1x10(-5)M. The detection limit was 4x10(-7) and 1.8x10(-6)M for catechol and pyrogallol, respectively. Studies of neurotransmitters such as epinephrine, metanephrine and l-dopa (l-3,4-dihydroxyphenylalanine), showed better response toward epinephrine and l-dopa than for metanephrine. Calibration curves for these two neurotransmitters were linear over the concentration range of 1x10(-6) to 1x10(-5)M. The detection limit was 4x10(-6) and 1x10(-6), respectively. The complexation capability of the Ppy/beta-CD system is addressed here in terms of structure-electrochemical activity relationship. The mechanical stability of the film is also discussed. Measurements were performed using cyclic voltammetry (CV), scanning electron microscopy (SEM) coupled to energy dispersive analysis of X-ray (EDAX) and electrochemical impedance spectroscopy (EIS).