The Mechanism of Biochemical NO-Sensing: Insights from Computational Chemistry

The binding of small gas molecules such as NO and CO plays a major role in the signaling routes of the human body. The sole NO-receptor in humans is soluble guanylyl cyclase (sGC) – a histidine-ligated heme protein, which, upon NO binding, activates a downstream signaling cascade. Impairment of NO-signaling is linked, among others, to cardiovascular and inflammatory diseases. In the present work, we use a combination of theoretical tools such as MD simulations, high-level quantum chemical calculations and hybrid QM/MM methods to address various aspects of NO binding and to elucidate the most likely reaction paths and the potential intermediates of the reaction. As a model system, the H-NOX protein from Shewanella oneidensis (So H-NOX) homologous to the NO-binding domain of sGC is used. The signaling route is predicted to involve NO binding to form a six-coordinate intermediate heme-NO complex, followed by relatively facile His decoordination yielding a five-coordinate adduct with NO on the distal side with possible isomerization to the proximal side through binding of a second NO and release of the first one. MD simulations show that the His sidechain can quite easily rotate outward into solvent, with this motion being accompanied in our simulations by shifts in helix positions that are consistent with this decoordination leading to significant conformational change in the protein.     

An improvement on geometrical parameterizations by transfinite maps

We present a method to generate a non-affine transfinite map from a given reference domain to a family of deformed domains. The map is a generalization of the Gordon–Hall transfinite interpolation approach. It is defined globally over the reference domain. Once we have computed some functions over the reference domain, the map can be generated by knowing the parametric expressions of the boundaries of the deformed domain. Being able to define a suitable map from a reference domain to a desired deformation is useful for the management of parameterized geometries.     

Size‐Mediated Recurring Spinel Sub‐nanodomains in Li‐ and Mn‐Rich Layered Cathode Materials

Li‐ and Mn‐rich layered oxides are among the most promising cathode materials for Li‐ion batteries with high theoretical energy density. Its practical application is, however, hampered by the capacity and voltage fade after long cycling. Herein, a finite difference method for near‐edge structure (FDMNES) code was combined with in situ X‐ray absorption spectroscopy (XAS) and transmission electron microscopy/electron energy loss spectroscopy (TEM/EELS) to investigate the evolution of transition metals (TMs) in fresh and heavily cycled electrodes. Theoretical modeling reveals a recurring partially reversible LiMn₂O₄‐like sub‐nanodomain formation/dissolution process during each charge/discharge, which accumulates gradually and accounts for the Mn phase transition. From the modeling of spectra and maps of the valence state over large regions of the cathodes, it was found that the phase change is size‐dependent. After prolonged cycling, the TMs displayed different levels of inactivity.     

Ternary Sn-Ti-O Electrocatalyst Boosts the Stability and Energy Efficiency of CO2 Reduction

Simultaneously improving energy efficiency (EE) and material stability in electrochemical CO₂ conversion remains an unsolved challenge. Among a series of ternary Sn-Ti-O electrocatalysts, 3D ordered mesoporous (3DOM) Sn_0.3Ti_0.7O₂ achieves a trade-off between active-site exposure and structural stability, demonstrating up to 71.5 % half-cell EE over 200 hours, and a 94.5 % Faradaic efficiency for CO at an overpotential as low as 430 mV. DFT and X-ray absorption fine structure analyses reveal an electron density reconfiguration in the Sn-Ti-O system. A downshift of the orbital band center of Sn and a charge depletion of Ti collectively facilitate the dissociative adsorption of the desired intermediate COOH* for CO formation. It is also beneficial in maintaining a local alkaline environment to suppress H₂ and formate formation, and in stabilizing oxygen atoms to prolong durability. These findings provide a new strategy in materials design for efficient CO₂ conversion and beyond.     

Fluorescence Enhancement of Aflatoxins Using Native and Substituted Cyclodextrins

Cyclodextrins have been used as fluorescence enhancers in HPLC to improve thedetection limits of aflatoxins, cancerogens which can be found in severalfoodstuffs. In this work, a screening of several cyclodextrins has been performedin order to find the factors affecting the fluorescence enhancement. Evidence for formationof a 1 : 1 AF-CD inclusion complex has been achieved by titration and competitiveexperiments with adamantanecarboxylic acid and by fluorescence quenching by KI.Stability constants of the AF-CD complexes were evaluated.     

The first total synthesis of (R)-convolutamydine A

The first total synthesis of (R)-convolutamydine A has been achieved by the organocatalytic addition of acetone to 4,6-dibromoisatin. The absolute configuration was determined by single crystal X-ray diffraction. DFT studies were used to model the transition states for the aldol reaction and equilibrium geometries of the post-aldol reaction intermediates. The DFT study revealed that the aldol bond forming reaction was considerably endothermic.