Testing mixed metal bimetallic, and monometallic, cryptates for electrocatalytic hydrogen evolution.

Appropriately designed catalysts help to minimise the energy required to convert the energy-poor feedstock HO into energy-rich molecular H. Herein, two families of pyridazine-based cryptates, mononuclear [MLi](BF) and mixed metal dinuclear [MCuLi](BF) (M = Fe, Co, Cu or Zn; Li is the Schiff base cryptand made by 2 : 3 condensation of tris(2-aminoethyl)amine and 3,6-diformylpyridazine), are investigated as potential electrocatalysts for the hydrogen evolution reaction (HER) in MeCN with acetic acid as the proton source. The synthesis and structures of a new mixed metal cryptate, [ZnCuLi](BF), and the tetrafluoroborate analogue of the previously reported perchlorate salt of the mono-zinc cryptate, [ZnLi](BF)·0.

The Role of Torsion on the Force-Coupled Reactivity of a Fluorenyl Naphthopyran Mechanophore.

The unique reactivity of molecules under force commands an understanding of structure-mechanochemical activity relationships. While conceptual frameworks for understanding force transduction in many systems are established, systematic investigations into force-coupled molecular torsions are limited. Here, we describe a novel fluorenyl naphthopyran mechanophore for which mechanical force is uniquely coupled to the torsional motions associated with the overall chemical transformation as a result of the conformational rigidity imposed by the fluorene group.

Coherent Excitation of the CH Stretching Vibrations in CH : The Role of the Derivative Coupling Studied by the Quantum Ehrenfest Method.

We report nonadiabatic dynamics computations on CH initiated on a coherent superposition of the five lowest cationic states, employing the Quantum Ehrenfest method. In addition to the totally symmetric carbon-carbon double bond stretch and carbon-hydrogen stretches, we see that the three non-totally symmetric modes become stimulated; torsion and three different CH stretching patterns. Thus, a coherent superposition of states, of the type involved in an attochemistry experiment, leads to the stimulation of specific non-totally symmetric motions.

Single-cell analyses reveal that monocyte gene expression profiles influence HIV-1 reservoir size in acutely treated cohorts.

Elimination of latent HIV-1 is a major goal of AIDS research but the host factors determining the size of these reservoirs are poorly understood. Here, we investigated whether differences in host gene expression modulate the size of the HIV-1 reservoir during suppressive ART. Peripheral blood mononuclear cells (PBMC) from fourteen individuals initiating ART during acute infection who demonstrated effective viral suppression but varying magnitude of total HIV-1 DNA were characterized by single-cell RNA sequencing (scRNA-seq).

Real-Time CASSCF (Ehrenfest) Modeling of Electron Dynamics in Organic Semiconductors. Dynamics Reaction Paths Driven by Quantum Coherences. Application to a Radical Organic Semiconductor.

We present a strategy for the modeling of charge carrier dynamics in organic semiconductors using conventional quantum chemistry methods, including the analytic gradient for nuclear motion. The theoretical approach uses real-time CASSCF (Ehrenfest) all-electron dynamics coupled to classical nuclear dynamics for the special case of a small number (4-8) of molecular units. The objective is to obtain mechanistic/atomistic insight at the electronic structure level, relating to spin density dynamics, to the effect of crystal structure (e.