Quenching of giant hysteresis effects in La(1-z)Y(z)Hx switchable mirrors

Hydrogen atoms adsorbed on TiO2(110)-(1x1) surfaces have been characterized by scanning tunneling microscopy (STM) combined with electron stimulated desorption (ESD) technique. Certain amounts of H atoms are unexpectedly found on the TiO2 surfaces annealed at 900 K. Two forms of adsorption were discriminated in STM images from the different sensitivity to ESD and tentatively assigned to hydroxyl-type (O-H) and hydride-type (Ti-H) species.     

Modeling magnetic field effects in multispin systems

A model is proposed for calculating magnetic field effects formed in a radical triad composed of a biradical and a paramagnetic particle. To describe the influence of the “third” spin on the spin evolution in a biradical, the electron spin exchange interaction of the added spin with one of the paramagnetic centers of the biradical has been considered. Calculating the field dependence of the recombination probability of the biradical-oxygen complex revealed both an increase in recombination probability earlier attributed to spin catalysis and the influence of the values and signs of the exchange interaction in the complex on the shape of the magnetic-field effect dependence. Calculation results are in agreement with the experimental data on the photolysis of 7,7’-dimethyl-silanorbornadiene in aerated and deaerated solution.     

NADH model systems functionalized with Zn(II)-cyclen as flavin binding site-structure dependence of the redox reaction within reversible aggregates

The relative positions and conformations of the prosthetic group FAD and the cofactor NADH have been remarkably conserved within the structurally diverse group of flavin enzymes. To provide a chemical rational for such an obviously optimal relative disposition of the redox partners for efficient reaction we have synthesized NADH models with Zn(II)-cyclen substituents for reversible flavin binding in water. Altogether, four of these model systems with systematically varying spacer length between the recognition site and the redox active dihydronicotinamide were prepared. The binding of these model systems to riboflavin tetraacetate was confirmed by potentiometric pH titration in water and their reaction with flavin was followed by UV-vis spectroscopy in aqueous media under physiological conditions. The measurements reveal a significant rate enhancement of up to 175 times that of an intermolecular reaction. Moreover, a strong dependence of the reaction rate on the spacer length was observed, which clearly shows that within the dynamic reversible assembly only the optimal relative disposition of the redox partners ensures an efficient redox reaction.     

NMR and photo-CIDNP investigations of the glycyrrhizinic acid micelles influence on solubilized molecules

It was found that photolysis of N-acyl anthranilic acid methyl ester is very sensitive to solvent nature. This sensitivity was connected with the equilibrium between intramolecular and intermolecular hydrogen bonding. Also it has been established the glycyrrhizinic acid micelle formation in water-methanol mixture with CMC about 0.5–1 mM. Solubilization of N-acyl anthranilic acid methyl ester in glycyrrhizinic acid micelles decreases photoreaction efficiency comparing with the homogeneous solvent.     

Zum Forschen nach China

Michael Kruppa und Stefan Ritter haben während ihrer Doktorarbeit zwei Monate am Shanghai Institut of Organic Chemistry in China gearbeitet.     

Discrimination of Methionine Sulfoxide and Sulfone by Human Neutrophil Elastase

Human neutrophil elastase (HNE) is a uniquely destructive serine protease with the ability to unleash a wave of proteolytic activity by destroying the inhibitors of other proteases. Although this phenomenon forms an important part of the innate immune response to invading pathogens, it is responsible for the collateral host tissue damage observed in chronic conditions such as chronic obstructive pulmonary disease (COPD), and in more acute disorders such as the lung injuries associated with COVID-19 infection. Previously, a combinatorially selected activity-based probe revealed an unexpected substrate preference for oxidised methionine, which suggests a link to oxidative pathogen clearance by neutrophils. Here we use oxidised model substrates and inhibitors to confirm this observation and to show that neutrophil elastase is specifically selective for the di-oxygenated methionine sulfone rather than the mono-oxygenated methionine sulfoxide. We also posit a critical role for ordered solvent in the mechanism of HNE discrimination between the two oxidised forms methionine residue. Preference for the sulfone form of oxidised methionine is especially significant. While both host and pathogens have the ability to reduce methionine sulfoxide back to methionine, a biological pathway to reduce methionine sulfone is not known. Taken together, these data suggest that the oxidative activity of neutrophils may create rapidly cleaved elastase “super substrates” that directly damage tissue, while initiating a cycle of neutrophil oxidation that increases elastase tissue damage and further neutrophil recruitment.     

Photoinitiated Charge Transfer in a Triangular Silver(I) Hydride Complex and Its Oxophilicity

The photoexcitation of a triangular silver(I) hydride complex, [Ag₃(μ₃-H)(μ₂-dcpm)₃](PF₆)₂ ([ P ](PF₆)₂, dcpm=bis(dicyclohexylphosphino)methane), designed with “UV-silent” bis-phosphine ligands, provokes hydride-to-Ag₃ single and double electron transfer. The nature of the electronic transitions has been authenticated by absorption and photodissociation spectroscopy in parallel with high-level quantum-chemical computations utilizing the GW method and Bethe–Salpeter equation (GW-BSE). Specific photofragments of mass-selected [ P ]²⁺ ions testify to charge transfer and competing pathways resulting from the unique [Ag₃(μ₃-H)]²⁺ scaffold. This structural motif of [ P ](PF₆)₂ has been unequivocally verified by ¹H NMR spectroscopy in concert with DFT and X-ray diffraction structural analysis, which revealed short equilateral Ag–Ag distances (d_AgAg=3.08 Å) within the range of argentophilic interactions. The reduced radical cation [ P ] ^{. +} exhibits strong oxophilicity, forming [ P +O₂] ^.+ ,which is a model intermediate for silver oxidation catalysis.