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The present study utilizes molecular dynamics simulations to examine how different anions compete for protein solvation in aqueous solutions of ionic liquids (ILs). Ubiquitin is used as model protein and studied in IL mixtures sharing the same cation, 1-ethyl-3-methylimidazolium (EMIM), and two different anions in the same solution, from combinations of dicyanamide (DCA), chloride (Cl), nitrate (NO3), and tetrafluoroborate (BF4). Our findings reveal that specific interactions between anions and the protein are paramount in IL solvation, but that combinations of anions are not additive. For example, DCA exhibits a remarkable ability to form hydrogen bonds with the protein, resulting in a significantly stronger preferential binding to the protein than other anions. However, the combination of DCA with NO3, which also forms hydrogen bonds with the protein, results in a smaller preferential solvation of the protein than the combination of DCA with chloride ions, which are weaker binders. Thus, combining anions with varying affinities for the protein surface modulates the overall ion accumulation through nonadditive mechanisms, highlighting the importance of the understanding of competition for specific interaction sites, cooperative binding, bulk-solution affinity, and overall charge compensations, on the overall solvation capacity of the solution. Such knowledge may allow for the design of novel IL-based processes in biotechnology and material science, where fine-tuning protein solvation is crucial for optimizing performance and functionality.

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Alzheimer's disease (AD) is a multifactorial and fatal neurodegenerative disorder. Acetylcholinesterase (AChE) plays a key role in the regulation of the cholinergic system and particularly in the formation of amyloid plaques; therefore, the inhibition of AChE has become one of the most promising strategies for the treatment of AD, particularly concerning AChE inhibitors that interact with the peripheral anionic site (PAS). Ceanothic acid isolated from the Chilean Rhamnaceae plants is an inhibitor of AChE through its interaction with PAS. In this study, six ceanothic acid derivatives were prepared, and all showed inhibitory activity against AChE. The structural modifications were performed starting from ceanothic acid by application of simple synthetic routes: esterification, reduction, and oxidation. AChE activity was determined by the Ellmann method for all compounds. Kinetic studies indicated that its inhibition was competitive and reversible. According to the molecular coupling and displacement studies of the propidium iodide test, the inhibitory effect of compounds would be produced by interaction with the PAS of AChE. In silico predictions of physicochemical properties, pharmacokinetics, drug-likeness, and medicinal chemistry friendliness of the ceanothane derivatives were performed using the Swiss ADME tool.

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The aim to access linked tetravanadate [V4O12]4- anion with mixed copper(II) complexes, using α-amino acids and phenanthroline-derived ligands, resulted in the formation of four copper(II) complexes [Cu(dmb)(Gly)(OH2)]2[Cu(dmb)(Gly)]2[V4O12]·9H2O (1) [Cu(dmb)(Lys)]2[V4O12]·8H2O (2), [Cu(dmp)2][V4O12]·C2H5OH·11H2O (3), and [Cu(dmp)(Gly)Cl]·2H2O (4), where dmb = 4,4'-dimethioxy-2,2'-bipyridine; Gly = glycine; Lys = lysine; and dmp = 2,9-dimethyl-1,10-phenanthroline. The [V4O12]4- anion is functionalized with mixed copper(II) units in 1 and 2; while in 3, it acts as a counterion of two [Cu(dmp)]2+ units. Compound 4 crystallized as a unit that did not incorporate the vanadium cluster. All compounds present magnetic couplings arising from Cu⋯O/Cu⋯Cu bridges. Stability studies of water-soluble 3 and 4 by UV-Vis spectroscopy in cell culture medium confirmed the robustness of 3, while 4 appears to undergo ligand scrambling over time, resulting partially in the stable species [Cu(dmp)2]+ that was also identified by electrospray ionization mass spectrometry at m/z = 479. The in vitro cytotoxicity activity of 3 and 4 was determined in six cancer cell lines; the healthy cell line COS-7 was also included for comparative purposes. MCF-7 cells were more sensitive to compound 3 with an IC50 value of 12 ± 1.2 nmol. The tested compounds did not show lipid peroxidation in the TBARS assay, ruling out a mechanism of action via reactive oxygen species formation. Both compounds inhibited cell migration at 5 µM in wound-healing assays using MCF-7, PC-3, and SKLU-1 cell lines, opening a new window to study the anti-metastatic effect of mixed vanadium-copper(II) systems.

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The photodetachment and stability of R-Mandelate, the deprotonated form of the R-Mandelic acid, was investigated by observing the neutral species issued from either simple photodetachment or dissociative photodetachment in a cold anions set-up. R-Mandalate has the possibility to form an intramolecular ionic hydrogen-bond between adjacent hydroxyl and carboxylate groups. The potential energy surface along the proton transfer (PT) coordinate between both groups (O- …H+ …- OCO) features a single local minima, with the proton localized on the O- group (OH…- OCO). However, the structure with the proton localized on the - OCO group (O- …HOCO) is also observed because it falls within the extremity of the vibrational wavefunction of the OH…- OCO isomer along the PT coordinate. The stability of the corresponding radicals, produced upon photodetachment, is strongly dependent on the position of the proton in the anion: the radicals produced from the OH…- OCO isomer decarboxylate without barrier, while the radicals produced from the O- …HOCO isomer are stable.

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Shrimp is one of the most traded fishery products in the world. The shrimp-farming water ionic composition is fundamental to the growth and survival of these specimens. Therefore, this study is aimed to develop a method for the simultaneous separation of Cl-, SO42-, NO3-, NO2-, and HCO3- in this sample by capillary zone electrophoresis with UV indirect detection, without any prior sample treatment, besides dilution. The background electrolyte (BGE) was composed of CrO42- (60 mmol L-1), cetyltrimethylammonium bromide (CTAB, 2.5 mmol L-1), acetonitrile (0.875% (v/v)), and methanol (2.625% (v/v)). The mixture design optimized the BGE composition. Acetonitrile and methanol changed the degree of solvation of the anions, which decreased the radius, a phenomenon proven by calculating the radius of anions in all the conditions of the mixture design. The optimized and validated method allowed the simultaneous determination of the five above-mentioned anions in 10 min.

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The objective of this study was to identify the effect of pre and postpartum DCAD on serum levels of calcium, phosphorus, and magnesium in peripartum Holstein cows. Blood samples were collected from 56 cows (18 primiparous and 38 multiparous) on days -7, +7, +14 and +28 relative to parturition, to determine serum levels of total and ionized calcium, phosphorus, magnesium, and albumin; diet samples for determination of calcium, phosphorus, magnesium and DCAD were collected at the same moments and urine samples were collected at day -7 for measurement of urinary pH. Prepartum DCAD was positively correlated with total calcium (p = 0.02) and with corrected total calcium (p = 0.01) at day -7. There was a negative correlation between prepartum DCAD and magnesium levels at day -7 (p = 0.02). No influence of prepartum DCAD on phosphataemia was observed. Postpartum DCAD did not correlate with serum mineral levels at any time point. Our results demonstrate that prepartum DCAD can influence calcium and magnesium homeostasis, but not phosphorus. In addition, parity and time period should be considered when evaluating serum levels of these minerals in Holstein cows during transition period.

Objetivou-se identificar o efeito da DCAD pré e pós-parto nos níveis séricos de cálcio, fósforo e magnésio, em vacas Holandesas em periparto. Foram coletadas amostras de sangue de 56 vacas (18 primiparas e 38 multiparas) nos dias -7, +7, +14 e +28 em relação ao parto, para determinação dos níveis séricos de cálcio total e ionizado, fósforo, magnésio e albumina; amostras de alimento foram coletadas nos mesmos momentos para determinação dos níveis cálcio, fósforo, magnésio e DCAD dietético; e amostras de urina foram coletadas no dia -7, para mensuração do pH urinário. A DCAD pré-parto foi positivamente correlacionada com cálcio total (P = 0,02) e com cálcio total corrigido (P = 0,01) no dia -7. Houve correlação negativa entre a DCAD pré-parto e os níveis de magnésio no momento -7 (P = 0,02). Não houve influência da DCAD pré-parto na fosfatemia. A DCAD pós-parto não se correlacionou com os níveis séricos de minerais em nenhum momento. Os resultados demonstram que a DCAD pré-parto pode influenciar na homeostase do cálcio e do magnésio, mas não do fósforo. Além disso, as variáveis paridade e tempo devem ser consideradas ao se avaliarem os níveis séricos desses minerais em bovinos leiteiros da raça Holandesa em transição.

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The study of new materials for radiation dosimetry is important to improve the present state of the art and to help in cases of accidents for retrospective dosimetry. Sulfites are compounds that contain a sulfur ion, widely used in the food industry. Due to the significant application of these compounds, sulfites are interesting candidates for accidental dosimetry, as fortuitous radiation detectors. The presence of the SO3- anion enables its detection by electron spin resonance (ESR) spectroscopy. The Dose-Response behavior, signal stability and other spectral features were investigated for sodium sulfite, sodium bisulfite, sodium metabisulfite and potassium metabisulfite, all in crystalline forms. The ESR spectrum of salts presented stability and proportional response with dose, presenting potential for dosimetry applications.

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We report a computational study of the anion states of the resveratrol (RV) and resorcinol (RS) molecules, also investigating dissociative electron attachment (DEA) pathways. RV has well-known beneficial effects in human health, and its antioxidant activity was previously associated with DEA reactions producing H2. Our calculations indicate a valence bound state (π1*) and four resonances (π2* to π5*) for that system. While the computed thermodynamic thresholds are compatible with DEA reactions producing H2 at 0 eV, the well-known mechanism involving vibrational Feshbach resonances built on a dipole bound state should not be present in RV. Our results suggest that the shallow π1* valence bound state is expected to account for H2 elimination, probably involving π1*/σOH* couplings along the vibration dynamics. The RS molecule is also an oxidant and a subunit of RV. Because two close-lying hydroxyl groups are found in the RS moiety, the H2-elimination reaction in RV should take place at the RS site. Our calculations point out a correspondence between the anion states of RV and RS and even between the thresholds. Nevertheless, the absence of bound anion states in RS, indicated by our calculations, is expected to suppress the H2-formation channel at 0 eV. One is led to conclude that the ethene and phenol subunits in RV stabilize the π1* state, thus switching on the DEA mechanism producing H2.

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The discharge of large amounts of effluents contaminated with gentian violet (GV) and phenol red (PR) threatens aquatic flora and fauna as well as human health, which is why these effluents must be treated before being discarded. This study seeks the removal of dyes, using water lily (Eichhornia crassipes) as an adsorbent with different pretreatments. PR and GV were analyzed by a UV-visible spectrophotometer. Equilibrium experimental data showed that Freundlich is the best model to fit PR and SIPS for GV, showing that the adsorption process for both dyes was heterogeneous, favorable, chemical (for GV), and physical (for PR). The thermodynamic analysis for the adsorption process of both dyes depends directly on the increase in temperature and is carried out spontaneously. The Pseudo first Order (PFO) kinetic model for GV and PR is the best fit for the dyes having an adsorption capacity of 91 and 198 mg/g, respectively. The characterization of the materials demonstrated significant changes in the bands of lignin, cellulose, and hemicellulose, which indicates that the functional groups could participate in the capture of the dyes together with the electrostatic forces of the medium, from which it be concluded that the adsorption process is carried out by several mechanisms.

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The interaction between polyamines and phosphate species is found in a wide range of biological and abiotic systems, yielding crucial consequences that range from the formation of supramolecular colloids to structure determination. In this work, the occurrence of phosphate-amino interactions is evidenced from changes in the electronic response of graphene field effect transistors (gFETs). First, the surface of the transistors is modified with poly(allylamine), and the effect of phosphate binding on the transfer characteristics is interpreted in terms of its impact on the surface charge density. The electronic response of the polyamine-functionalized gFETs is shown to be sensitive to the presence of different phosphate anions, such as orthophosphate, adenosine triphosphate, and tripolyphosphate, and a simple binding model is developed to explain the dependence of the shift of the Dirac point potential on the phosphate species concentration. Afterward, the impact of phosphate-amino interactions on the immobilization of enzymes to polyamine-modified graphene surfaces is investigated, and a decrease in the amount of anchored enzyme as the phosphate concentration increases is found. Finally, multilayer polyamine-urease biosensors are fabricated while increasing the phosphate concentration in the enzyme solution, and the sensing properties of the gFETs toward urea are evaluated. It is found that the presence of simple phosphate anions alters the nanoarchitecture of the polyelectrolyte-urease assemblies, with direct implications on urea sensing.

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