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.

Adsorption of Methylene Blue Dye and Analysis of Two Clays: A Study of Kinetics, Thermodynamics, and Modeling with DFT, MD, and MC Simulations.

The purpose of this research was to learn more about the primary and secondary properties of Moroccan natural clay in an effort to better investigate innovative adsorbents and gain access to an ideal adsorption system. Scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy analysis (SEM-EDX) and X-ray fluorescence were employed for identification. SEM revealed clay grains, including tiny particles and unevenly shaped sticks. First- and second-order rate laws, representing two distinct kinetic models, were applied in the kinetic approach. Adsorption of dye MB onto natural clay was studied, and the results agreed with the 2 s order model. The significant correlation coefficients support the inference that the adsorption process was governed by the Langmuir model. Subsequent DFT analyses demonstrated that the methylene blue dye's HOMO and LUMO surfaces are dispersed across most of the dye's components, pointing to a strong interaction with the clay. To determine how the dye might be adsorbed onto the clay, we employed quantum descriptors to locate its most nucleophilic and electrophilic centers. Endothermic reactions are evident during the MB adsorption process on clay, as indicated by the positive values of ΔH0 and ΔS0 (70.49 kJ mol-1of RC and 84.19 kJ mol-1 of OC and 10.45 J mol-1 K-1 of RC and 12.68 mol-1 K-1 of OC, respectively). Additionally dye molecules on the adsorbent exhibit a higher order of distribution than in the solution, indicating that the adsorption process is spontaneous.

Hybrid carbonaceous adsorbents based on clay and cellulose for cadmium recovery from aqueous solution.

The current work describes the synthesis of carbonaceous composites via pyrolysis, based on CMF, extracted from Alfa fibers, and Moroccan clay ghassoul (Gh), for potential use in heavy metal removal from wastewater. Following synthesis, the carbonaceous ghassoul (ca-Gh) material was characterized using X-ray fluorescence (XRF), Scanning Electron Microscopy coupled with Energy Dispersive X-ray (SEM-EDX), zeta-potential and Brunauer-Emmett-Teller (BET). The material was then used as an adsorbent for the removal of cadmium (Cd2+) from aqueous solutions. Studies were conducted into the effect of adsorbent dosage, kinetic time, initial concentration of Cd2+, temperature and also pH effect. Thermodynamic and kinetic tests demonstrated that the adsorption equilibrium was attained within 60 min allowing the determination of the adsorption capacity of the studied materials. The investigation of the adsorption kinetics also reveals that all the data could be fit by the pseudo-second-order model. The Langmuir isotherm model might fully describe the adsorption isotherms. The experimental maximum adsorption capacity was found to be 20.6 mg g-1 and 261.9 mg g-1 for Gh and ca-Gh, respectively. The thermodynamic parameters show that the adsorption of Cd2+ onto the investigated material is spontaneous and endothermic.

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.

Chitosan-Functionalized Graphene Nanocomposite Films: Interfacial Interplay and Biological Activity.

Graphene oxide (GO) has recently captured tremendous attention, but only few functionalized graphene derivatives were used as fillers, and insightful studies dealing with the thermal, mechanical, and biological effects of graphene surface functionalization are currently missing in the literature. Herein, reduced graphene oxide (rGO), phosphorylated graphene oxide (PGO), and trimethylsilylated graphene oxide (SiMe3GO) were prepared by the post-modification of GO. The electrostatic interactions of these fillers with chitosan afforded colloidal solutions that provide, after water evaporation, transparent and flexible chitosan-modified graphene films. All reinforced chitosan-graphene films displayed improved mechanical, thermal, and antibacterial (S. aureus, E. coli) properties compared to native chitosan films. Hemolysis, intracellular catalase activity, and hemoglobin oxidation were also observed for these materials. This study shows that graphene functionalization provides a handle for tuning the properties of graphene-reinforced nanocomposite films and customizing their functionalities.

Lead removal from aqueous solution by means of integral natural clays honeycomb monoliths.

Different natural Moroccan clays were used as adsorbents for the removal of lead from aqueous solution. The study was performed not only employing the starting clays in the form of powder but also after their extrusion as honeycomb monoliths, this representing the major novelty of this work respect to the current state-of-art. The experiments were done in batch conditions with continuous stirring and using a recirculated flow, respectively. In addition to an exhaustive characterization of the clays by means of X-ray fluorescence, X-ray diffraction, thermogravimetric analysis, laser granulometry, N2 physisorption, infrared spectroscopy, SEM-EDS and evaluation of the cation exchange capacity, special attention was paid to the influence on the lead adsorption of variables such as adsorbent dosage, pH, contact time with the adsorbate and initial concentration of lead. Considering the cheap and abundant character of the raw materials, their easy processing (no additives were required for their extrusion) and the time and energy save due to no need for further modification through chemical/thermal activation, the obtained results (with retention over 90% for 30 ppm of lead) demonstrated the potential of the proposed design as low cost solution that may be competitive versus other technologies for water depollution, especially in developing regions.

Changes in the persistence of two phenylurea herbicides in two Mediterranean soils under irrigation with low- and high-quality water: A laboratory approach.

The disappearance of two phenylurea herbicides, chlorotoluron (CHL) and isoproturon (IPU), in two Mediterranean soils, an agricultural calcareous soil (S5) and an organic forest soil (S2), was assessed under irrigation with high- and low-quality water. Irrigation with wastewater, as opposed to irrigation with high-quality water, increased the degradation rate of both herbicides in both soils. For each soil, the decay rate of IPU was always higher than that of CHL, and both pesticides disappeared more rapidly from S5 with lower clay and organic carbon content than from S2. The degradation rate was inversely related with pesticide sorption on soil, because increased sorption would reduce pesticide bioavailability for decomposition. In most cases the residual concentration in soil of both phenylurea herbicides was better fitted to a bi-exponential decay model than to first-order or first-order with plateau models. Dehydrogenase activity, used as an indication of microbial activity, was very high in S2 in comparison with S5, but was not related to pesticide disappearance.