Cd2+ Sorption Alterations in Ultisol Soils Triggered by Different Engineered Nanoparticles and Incubation Times.

The progressive influx of engineered nanoparticles (ENPs) into the soil matrix catalyses a fundamental transformation in the equilibrium dynamics between the soil and the edaphic solution. This all-encompassing investigation is geared towards unravelling the implications of an array of ENP types, diverse dosages and varying incubation durations on the kinetics governing Cd2+ sorption within Ultisol soils. These soils have been subjected to detailed characterizations probing their textural and physicochemical attributes in conjunction with an exhaustive exploration of ENP composition, structure and morphology. To decipher the intricate nuances of kinetics, discrete segments of Ultisol soils were subjected to isolated systems involving ENP dosages of 20 and 500 mg ENPs·kg-1 (AgNPs, CuNPs and FeNPs) across intervals of 1, 3 and 6 months. The comprehensive kinetic parameters were unveiled by applying the pseudo-first-order and pseudo-second-order models. At the same time, the underlying sorption mechanisms were studied via the intra-particle diffusion model. This study underscores the substantial impact of this substrate on the kinetic behaviours of contaminants such as Cd, emphasizing the need for its consideration in soil-linked economic activities and regulatory frameworks to optimize resource management.

Evaluating the inhibitory activity of ferrocenyl Schiff bases derivatives on 5-lipoxygenase: Computational and biological studies.

In the search for new 5-LOX inhibitors, two ferrocenyl Schiff base complexes functionalized with catechol ((ƞ5-(E)-C5H4-NCH-3,4-benzodiol)Fe(ƞ5-C5H5) (3a)) and vanillin ((ƞ5-(E)-C5H4-NCH-3-methoxy-4-phenol)Fe(ƞ5-C5H5) (3b)) were obtained. Complexes 3a and 3b were biologically evaluated as 5-LOX inhibitors showed potent inhibition compared to their organic analogs (2a and 2b) and known commercial inhibitors, with IC50 = 0.17 ± 0.05 µM for (3a) and 0.73 ± 0.06 µM for (3b) demonstrated a highly inhibitory and potent effect against 5-LOX due to the incorporation of the ferrocenyl fragment. Molecular dynamic studies showed a preferential orientation of the ferrocenyl fragment toward the non-heme iron of 5-LOX, which, together with electrochemical and in-vitro studies, allowed us to propose a competitive redox deactivation mechanism mediated by water, where Fe(III)-enzyme can be reduced by the ferrocenyl fragment. An Epa/IC50 relationship was observed, and the stability of the Schiff bases was evaluated by SWV in the biological medium, observing that the hydrolysis does not affect the high potency of the complexes, making them interesting alternatives for pharmacological applications.

Enhanced removal of mercury and lead by a novel and efficient surface-functionalized imogolite with nanoscale zero-valent iron material.

A novel hybrid nanomaterial, nanoscale zero-valent iron (nZVI)-grafted imogolite nanotubes (Imo), was synthesized via a fast and straightforward chemical procedure. The as-obtained nanomaterial (Imo-nZVI) was characterized using transmission electron microscopy (TEM), electrophoretic mobility (EM), and vibrating sample magnetometry (VSM). The prepared Imo-nZVI was superparamagnetic at room temperature and could be easily separated by an external magnetic field. Sorption batch experiments were performed for single- and multicomponent systems and demonstrated that Hg2+ and Pb2+ could be quantitatively adsorbed at pH 3.0. For multicomponent systems, maximum adsorption capacities of 61.6 mg·g-1 and 76.9 mg·g-1 were obtained for Hg2+ and Pb2+ respectively. It was observed that the functional groups in Imo-nZVI interact preferentially with analytes according to the Misono softness parameter. The higher performance of Imo-nZVI compared with Imo and nZVI is related to the increased number of adsorption sites in the functionalized nanomaterial. The sorption equilibrium data obeyed the Langmuir model, while kinetic studies demonstrated that the sorption processes of Hg2+ and Pb2+ followed the pseudo-second-order model. This study suggests that the Imo-nZVI composite can be used as a promising sorbent to provide a simple and fast separation method to remove Hg and Pb ions from contaminated water.

Mechanistic insights into simultaneous removal of copper, cadmium and arsenic from water by iron oxide-functionalized magnetic imogolite nanocomposites.

Imogolite and magnetic imogolite-Fe oxide nanocomposites (Imo-Fe50 and Imo-Fe25, at 50 and 25 % Fe loading (w/w), respectively) were synthesized and tested for the removal of aqueous copper (Cu), cadmium (Cd), and arsenic (As) pollutants. The materials were characterized by transmission electron microscopy, and specific surface area and isoelectric point measurements. The Fe-containing samples were additionally characterized by Mössbauer spectroscopy and vibrating-sample magnetometry. Significant differences were found in the morphological, electrophoretic, and magnetic characteristics between imogolite and the nanocomposites. The in-situ Fe-oxide precipitation process modified the active surface sites of the imogolite. The Fe-oxide, mainly magnetite, favored the contaminants' adsorption over the pristine imogolite. The adsorption kinetics of these pollutants were adequately described by the pseudo-second order and intraparticle diffusion models. The kinetic models showed that surface adsorption was more important than intraparticle diffusion in the removal of the pollutants by all the adsorbents. The Langmuir-Freundlich model described the experimental adsorption data, and both nanocomposites showed greater adsorption capacity than the imogolite. The adsorption of Cu and Cd was sensitive to cationic competition, showing a decrease of the adsorption capacity when the two cations coexisted, while their adsorption increased in the presence of arsenate.

Excited States versus Reaction Intermediates as Active Species in Photoinduced Redox Reactions of Cyrhetrenyl and Ferrocenyl Chalcones: A 351 nm Flash Photolysis Study.

The photoinduced redox reactions of two organometallic chalcones: trans, E, (η5-C5H4C(O)CH═CH-4-benzo-15-crown-5)Re(CO)3, 1, and trans, E, (η5-C5H4C(O)CH═CH-4-benzo-15-crown-5)Fe(η5-C5H4C(O)CH═CH-4-benzo-15-crown-5), 2, were investigated in fluid solution using the flash photolysis technique. For a better understanding of the photoinduced redox processes of these organometallic chalcones, an electron donor, triethylamine (TEA), and an electron acceptor, methylviologen dichloride (MVCl2), were chosen. Two parallel reaction paths for the decay of the intermediate 1-I, that is, the anion radical of 1, were observed in the presence of TEA. One generates a radical anion, while the other reaction path produces the Z isomer. Instead, the photoinduced reaction of 2 with TEA in MeOH generates an intense absorption band at λmax = 660 nm, which is attributed to a 2-I·MeOH adduct. The oxidative process between 1-I and MV2+ in CH3CN generates transient spectra consistent with the formation of the radical cation MV•+. In contrast, the photoinduced reaction between 2 and MV2+ showed that the generation of MV•+ occurs through a complex mechanism. MV•+ is formed in two steps where the first one is the formation of an adduct between the long-lived metal-to-ligand charge transfer (MLCT)Fe→Chalcone excited state and MV2+. These results have shown that intermediates 1-I and 2-I can function as photo-oxidants and photoreductants better than the chalcone short-lived excited states.

Organometallic Chalcones Functioning as Radical Traps: Observations on the Solvated Electron Reduction and the C·H2OH and C·H2Cl Addition Processes. A Time-Resolved, Mechanistic Study.

The pulse radiolysis method was used to investigate reactions between organometallic chalcones derived from ferrocene, cyrhetrene, and cymantrene substituted with a phenyl (R1) or a 4'-benzo-15-crown-5 (B1) moiety and the solvated electron e-sol and two radicals. The principal spectroscopic transformations resolved with the e-sol reactions reveal that the chalcone compounds react under a diffusion controlled condition. The chromophore in the reaction product is the radical anion chalcone, -C(═O)CH═CH-. The kinetics of the redox processes are consistent with the formation of the radical anion in a first step, followed by an E/Z isomerization reaction in the second step. The rate of the E/Z isomerization reaction is dependent on the chalcone substituent. Reactions with C·H2OH and C·H2Cl radicals are strongly affected by the nature of the organometallic fragment. The transient spectra for the reactions between C·H2OH and C·H2Cl radicals with the phenyl-substituted chalcone show weak, broad absorption bands at λob < 400 nm. Only the ferrocenyl derivatives showed an intense absorption band with λmax = 350 nm. The C-centered radicals react with organometallic chalcones with lifetimes less than or equal to a few microseconds, and the products are assigned as adducts of the C-centered radicals to the chalcone.