Direct Visualization of the Interfacial Degradation of Cathode Coatings in Solid State Batteries: A Combined Experimental and Computational Study

The interfacial instability between a thiophosphate solid electrolyte and oxide cathodes results in rapid capacity fade and has driven the need for cathode coatings. In this work, the stability, evolution, and performance of uncoated, Li₂ZrO₃‐coated, and Li₃B₁₁O₁₈‐coated LiNi_0.5Co_0.2Mn_0.3O₂ cathodes are compared using first‐principles computations and electron microscopy characterization. Li₃B₁₁O₁₈ is identified as a superior coating that exhibits excellent oxidation/chemical stability, leading to substantially improved performance over cells with Li₂ZrO₃‐coated or uncoated cathodes. The chemical and structural origin of the different performance is interpreted using different microscopy techniques which enable the direct observation of the phase decomposition of the Li₂ZrO₃ coating. It is observed that Li is already extracted from the Li₂ZrO₃ in the first charge, leading to the formation of ZrO₂ nanocrystallites with loss of protection of the cathode. After 50 cycles separated (Co, Ni)‐sulfides and Mn‐sulfides can be observed within the Li₂ZrO₃‐coated material. This work illustrates the severity of the interfacial reactions between a thiophosphate electrolyte and oxide cathode and shows the importance of using coating materials that are absolutely stable at high voltage.     

Ruthenium Triazine Composite: A Good Match for Increasing Hydrogen Evolution Activity through Contact Electrification

The development of Pt‐free catalysts for the alkaline hydrogen evolution reaction (HER), which is widely used in industrial scale water‐alkali electrolyzers, remains a contemporary and pressing challenge. Ruthenium (Ru) has excellent water‐dissociation abilities and could be an alternative water splitting catalyst. However, its large hydrogen binding energy limits HER activity. Here, a new approach is proposed to boost the HER activity of Ru through uniform loading of Ru nanoparticles on triazine‐ring (C₃N₃)‐doped carbon (triNC). The composite (Ru/triNC) exhibits outstanding HER activity with an ultralow overpotential of ≈2 mV at 10 mA cm^?2; thereby making it the best performing electrocatalyst hitherto reported for alkaline HER. The calculated metal mass activity of Ru/triNC is >10 and 15 times higher than that of Pt/C and Pt/triNC. Both theoretical and experimental studies reveal that the triazine‐ring is a good match for Ru to weaken the hydrogen binding on Ru through interfacial charge transfer via increased contact electrification. Therefore, Ru/triNC can provide the optimal hydrogen adsorption free energy (approaching zero), while maintaining the strong water‐dissociation activity. This study provides a new avenue for designing highly efficient and stable electrocatalysts for water splitting.     

Development and validation of an experimental and theoretical method for the chiral discrimination of dinotefuran

Dinotefuran is a low-cost agrochemical considered a highly toxic product. In this sense, there is a need for its constant environmental, biological, and food control, aiming to ensure its use to humans as well as to preserve biodiversity and ecosystems. In the present work, we developed an experimental and theoretical method for dinotefuran chiral discrimination. According to the main results, the dinotefuran enantioselective separation was efficiently optimized by high-performance liquid chromatography evaluating the influence of different percentage compositions in the mobile phase to improve the resolution of the peaks in the chromatogram. The novelty of this work was the proposition of a reduced molecular model for the chiral selector amylose-Tris-(3,5-dimethylphenylcarbamate) polysaccharide that was able to adequately describe at the molecular level its interaction with the dinotefuran enantiomers. Besides, the thermodynamic and structural parameters obtained via density functional theory calculations pointed out the chiral discrimination as well as the enantiomeric elution order of the analyte studied, confirming the experimental data, thus validating our proposed method. Finally, hydrogen bonds and repulsive interactions played a key role in the discrimination between the diastereomeric complexes, and consequently, for the dinotefuran enantioselective separation.     

Eremophilane Sesquiterpenes and Benzene Derivatives from the Endophyte Microdiplodia sp. WGHS5

Three new eremophilane sesquiterpenes phomadecalins G−I ( 1 – 3 ) and two new benzene derivatives microdiplzenes A and B ( 12 and 13 ), together with nine known eremophilane sesquiterpenes ( 4 – 11 and 14 ) were isolated from an endophytic fungus, Microdiplodia sp. WGHS5. Their structures were elucidated by the interpretation of HR-ESI-MS and NMR data; meanwhile, the absolute configurations of new compounds were determined on the base of ECD calculations. All compounds were evaluated for the antimicrobial activities and antiproliferative effect on human gastric cancer cell lines (BGC-823).     

Nicotinamide Adenine Dinucleotide a Unique Compound for Theoretical and Synthetic Model Studies: Chirality as Source for High Stereospecificity

Abstract

A dynamic model is given for the hydride transfer of the redox couple NAD⁺-NADH with model systems and quantum chemical calculations.     

Ring A rearranged limonoids from the fruits of Aphanamixis grandifolia and their cytotoxicity evaluation

Two new limonoids aphanamolides C (1) and D (2), together with two known limonoids aphanamolide A (3) and aphapolynin A (4), were isolated from the fruits of Aphanamixis grandifolia. Their structures were assigned on the basis of spectroscopic data, with the absolute configurations of 1 and 2 being established by electronic circular dichroism (ECD) spectroscopic analyses. Those limonoids varied in the ring A: aphanamolide C featured two oxygenated bridges, and aphanamolide D was the second example containing β-hydroxy-α,β:γ,δ-dienoate moiety. The cytotoxic activities were also evaluated in vitro against four human cancer cell lines (MCF-7, A549, SMMC-7721, and HL-60).     

Binding mechanism of spinosine and venenatine molecules with p300 HAT enzyme: Molecular screening,molecular dynamics and free-energy analysis

The chromatin modification is regulated by the histone acetyltransferase (HAT) and histone deacetyltransferase (HDAC) enzymes; abnormal function of these enzymes leads to several malignant diseases. The inhibition of these enzymes using natural ligand molecules is an emerging technique to cure these diseases. The in vitro analysis of natural molecules, venenatine, spinosine, palmatine and taxodione are giving the best inhibition rate against p300 HAT enzyme. However, the detailed understanding of binding and the stability of these molecules with p300 HAT is not yet known. The aim of the present study is focused to determine the binding strength of the molecules from molecular dynamics simulation analysis. The docking analysis confirms that, the venenatine (−6.97 kcal/mol - conformer 8), spinosine (−6.52 kcal/mol conformer −10), palmatine (−5.72 kcal/mol conformer-3) and taxodione (−4.99 kcal/mol conformer-4) molecules form strong hydrogen bonding interactions with the key amino acid residues (Arg1410, Thr1411 and Trp1466) present in the active site of p300. In the molecular dynamics (MD) simulation, the spinosine retain these key interactions with the active site amino acid residues (Arg1410, Thr1411, and Trp1466) than venenatine and are stable throughout the simulation. The RMSD value of spinosine (0.5 to 1.3 Å) and venenatine (0.3 to 1.3 Å) are almost equal during the MD simulation. However, during the MD simulation, the intermolecular interaction between venenatine and the active site amino acid residues (Arg1410, Thr1411, and Trp1466) decreased on comparing with the spinosine-p300 interaction. The binding free energy of the spinosine (−15.30 kcal/mol) is relatively higher than the venenatine (−11.8 kcal/mol); this increment is attributed to the strong hydrogen bonding interactions of spinosine molecule with the active site amino acid residues of p300.     

Protonation state of the selectivity filter of bacterial voltage-gated sodium channels is modulated by ions

The selectivity filter (SF) of bacterial voltage-gated sodium channels consists of four glutamate residues arranged in a C₄ symmetry. The protonation state population of this tetrad is unclear. To address this question, we simulate the pore domain of bacterial voltage-gated sodium channel of Magnetococcus sp. (Na_vMs) through constant pH methodology in explicit solvent and free energy perturbation calculations. We find that at physiological pH the fully deprotonated as well as singly and doubly protonated states of the SF appear feasible, and that the calculated pKa decreases with each additional bound ion, suggesting that a decrease in the number of ions in the pore can lead to protonation of the SF. Previous molecular dynamics simulations have suggested that protonation can lead to a decrease in the conductance, but no pKa calculations were performed. We confirm a decreased ionic population of the pore with protonation, and also observe structural symmetry breaking triggered by protonation; the SF of the deprotonated channel is closest to the C₄ symmetry observed in crystal structures of the open state, while the SF of protonated states display greater levels of asymmetry which could lead to transition to the inactivated state which possesses a C₂ symmetry in the crystal structure. We speculate that the decrease in the number of ions near the mouth of the channel, due to either random fluctuations or ion depletion due to conduction, could be a self-regulatory mechanism resulting in a nonconducting state that functionally resembles inactivated states.     

Role of tyrosine hot‐spot residues at the interface of colicin E9 and immunity protein 9: A comparative free energy simulation study

The endonuclease activity of the bacterial colicin 9 enzyme is controlled by the specific and high‐affinity binding of immunity protein 9 (Im9). Molecular dynamics simulation studies in explicit solvent were used to investigate the free energy change associated with the mutation of two hot‐spot interface residues [tyrosine (Tyr): Tyr54 and Tyr55] of Im9 to Ala. In addition, the effect of several other mutations (Leu33Ala, Leu52Ala, Val34Ala, Val37Ala, Ser48Ala, and Ile53Ala) with smaller influence on binding affinity was also studied. Good qualitative agreement of calculated free energy changes and experimental data on binding affinity of the mutations was observed. The simulation studies can help to elucidate the molecular details on how the mutations influence protein–protein binding affinity. The role of solvent and conformational flexibility of the partner proteins was studied by comparing the results in the presence or absence of solvent and with or without positional restraints. Restriction of the conformational mobility of protein partners resulted in significant changes of the calculated free energies but of similar magnitude for isolated Im9 and for the complex and therefore in only modest changes of binding free energy differences. Although the overall binding free energy change was similar for the two Tyr–Ala mutations, the physical origin appeared to be different with solvation changes contributing significantly to the Tyr55Ala mutation and to a loss of direct protein–protein interactions dominating the free energy change due to the Tyr54Ala mutation. Proteins 2013. © 2012 Wiley Periodicals, Inc.