Study of Sorption Kinetics and Sorption-Desorption Models to Assess the Transport Mechanisms of 2,4-Dichlorophenoxyacetic Acid on Volcanic Soils.

The sorption behavior of 2,4-dichlorophenoxyacetic acid (2,4-D) in the abundant agricultural volcanic ash-derived soils (VADS) is not well understood despite being widely used throughout the world, causing effects to the environment and human health. The environmental behavior and risk assessment of groundwater pollution by pesticides can be evaluated through kinetic models. This study evaluated the sorption kinetics and 2,4-D sorption-desorption in ten VADS through batch sorption experiments. Differences in the sorption extent for the fast and slow phases was observed through the IPD model where 2,4-D sorption kinetics was controlled by external mass transfer and intra organic matter diffusion in Andisols (C1 ≠ 0). We confirmed from the spectroscopic analysis that the carboxylate group directly drives the interaction of 2,4-D on Andisol soil. The MLR model showed that IEP, FeDCB, and pH×Silt are important soil descriptors in the 2,4-D sorption in VADS. The Freundlich model accurately represented sorption equilibrium data in all cases (Kf values between 1.1 and 24.1 µg1-1/n mL1/ng-1) with comparatively higher sorption capacity on Andisols, where the highest hysteresis was observed in soils that presented the highest and lowest OC content (H close to 0).

Nicosulfuron sorption kinetics and sorption/desorption on volcanic ash-derived soils: Proposal of sorption and transport mechanisms.

Nicosulfuron sorption/desorption kinetics were studied through batch sorption studies in ten volcanic ash-derived Andisol and Ultisol soils with acidic pH and variable surface charge. Two different kinetic models were used to fit the experimental data: i) Models to establish kinetic parameters (Pseudo-First and Pseudo-Second-Order), and ii) Models to describe solute transport mechanisms of organic compounds on sorbents (Intraparticle Diffusion, Dimensionless Intraparticle, Boyd, and Two-Site Nonequilibrium). Sorption kinetic data best fit the pseudo-second-order model. Application of these models to describe solute transport suggests that underlying mechanisms are complex in all soils due to: i) surface sorption, with mass transfers controlling sorption kinetics across the boundary layer; and ii) pore diffusion (i.e. intraparticle diffusion into macropores and micropores). The Freundlich model explained equilibrium sorption data in all cases (R2 > 0.9979) with Kf values higher than those reported for different class of soils (6.85-16.08 µg1-1/n mL1/n  g-1). The hysteresis was significant in all studied soils. The lower sorption rate on Ultisols must be considered in regards to Nicosulfuron leaching potential.

Electrochemical method to study the environmental behavior of Glyphosate on volcanic soils: Proposal of adsorption-desorption and transport mechanisms.

Glyphosate is used extensively worldwide, but current evidence suggests detrimental effects on the environment, pollinators, and human health. Glyphosate adsorption kinetics and adsorption/desorption were studied through batch sorption experiments in ten typical volcanic ash-derived soils from Andisol and Ultisol orders. Two kinetic models were used to fit the experimental data: i. Models that allowed establishment of principally kinetic parameters and modeling of the adsorption process, and ii. Models described solute transport mechanisms commonly used for remediation purposes. Adsorption kinetic data were best fitted by the pseudo-second-order kinetic model and Two-Site Nonequilibrium model. These models suggest that mechanisms are complex due to rapid surface adsorption in ultisols with mass transfer controlling adsorption kinetics across the boundary layer, as indicated by the highhand lowt1/2values. High intraparticle diffusion into macropores and micropores was observed for Andisols. The Freundlich model accurately represented adsorption equilibrium data in all cases (R2 > 0.9580) with comparatively higher adsorption capacity on Andisols. Kf values (2.50-52.28 µg1-1/n mL1/n g-1) and hysteresis were significant in all studied soils. Taken together, these data suggest that Glyphosate may be adsorbed more on Andisol soils in comparison to Ultisols.

Identification of potential trypanothione reductase inhibitors among commercially available ß-carboline derivatives using chemical space, lead-like and drug-like filters, pharmacophore models and molecular docking.

American trypanosomiasis or Chagas disease caused by the protozoan Trypanosoma cruzi (T. cruzi) is an important endemic trypanosomiasis in Central and South America. This disease was considered to be a priority in the global plan to combat neglected tropical diseases, 2008-2015, which indicates that there is an urgent need to develop more effective drugs. The development of new chemotherapeutic agents against Chagas disease can be related to an important biochemical feature of T. cruzi: its redox defense system. This system is based on trypanothione ([Formula: see text],[Formula: see text]-bis(glutathyonil)spermidine) and trypanothione reductase (TR), which are rather unique to trypanosomes and completely absent in mammalian cells. In this regard, tricyclic compounds have been studied extensively due to their ability to inhibit the T. cruzi TR. However, synthetic derivatives of natural products, such as [Formula: see text]-carboline derivatives ([Formula: see text]-CDs), as potential TR inhibitors, has received little attention. This study presents an analysis of the structural and physicochemical properties of commercially available [Formula: see text]-CDs in relation to compounds tested against T. cruzi in previously reported enzymatic assays and shows that [Formula: see text]-CDs cover chemical space that has not been considered for the design of TR inhibitors. Moreover, this study presents a ligand-based approach to discover potential TR inhibitors among commercially available [Formula: see text]-CDs, which could lead to the generation of promising [Formula: see text]-CD candidates.

Sorption kinetics of diuron on volcanic ash derived soils.

Diuron sorption kinetic was studied in Andisols, Inceptisol and Ultisols soils in view of their distinctive physical and chemical properties: acidic pH and variable surface charge. Two types of kinetic models were used to fit the experimental dates: those that allow to establish principal kinetic parameters and modeling of sorption process (pseudo-first-order, pseudo-second-order), and some ones frequently used to describe solute transport mechanisms of organic compounds on different sorbents intended for remediation purposes (Elovich equation, intraparticle diffusion, Boyd, and two-site nonequilibrium models). The best fit was obtained with the pseudo-second-order model. The rate constant and the initial rate constant values obtained through this model demonstrated the behavior of Diuron in each soil, in Andisols were observed the highest values for both parameters. The application of the models to describe solute transport mechanisms allowed establishing that in all soils the mass transfer controls the sorption kinetic across the boundary layer and intraparticle diffusion into macropores and micropores. The slowest sorption rate was observed on Ultisols, behavior which must be taken into account when the leaching potential of Diuron is considered.

Potent 5-nitrofuran derivatives inhibitors of Trypanosoma cruzi growth: electrochemical, spectroscopic and biological studies.

Cyclic voltammetry and electron spin resonance techniques were used in the investigation of several potential antiprotozoal containing thiosemicarbazone and carbamate nitrofurans. In the electrochemical behaviour, a self-protonation process involving the nitro group was observed. The reactivity of the nitro anion radical for these derivatives with glutathione, a biological relevant thiol, was also studied in means of cyclic voltammetry. These studies demonstrated that glutathione could react with radical species from 5-nitrofuryl system. Furthermore, from the voltammetric results, some parameters of biological significance as E(7)(1) (indicative of the biological nitro anion radical formation), and [Formula: see text] (thermodynamic indicator the of oxygen redox cycling) have been calculated. We also evaluated the stability of the nitro anion radical in terms of the dimerization constant (k(d)). The nitrofuran-free radicals from cyclic voltammetry were characterized by electron spin resonance. A clear dependence between both the thiosemicarbazone or carbamate substructure and the length of the linker, furyl- or furylpropenyl-spacer, and the delocalization of the unpaired electron was observed. Through of biological assays we obtained important parameters that account for the selective anti-trypanosomal activity of these derivatives. The trypomastigote viability study showed that all derivatives are as active as in the epimastigote form of the parasite in a doses dependent manner.