Dynamics of Bacteriorhodopsin in the Dark-Adapted State from Solution Nuclear Magnetic Resonance Spectroscopy

To achieve efficient proton pumping in the light-driven proton pump bacteriorhodopsin (bR), the protein must be tightly coupled to the retinal to rapidly convert retinal isomerization into protein structural rearrangements. Methyl group dynamics of bR embedded in lipid nanodiscs were determined in the dark-adapted state, and were found to be mostly well ordered at the cytosolic side. Methyl groups in the M145A mutant of bR, which displays only 10 % residual proton pumping activity, are less well ordered, suggesting a link between side-chain dynamics on the cytosolic side of the bR cavity and proton pumping activity. In addition, slow conformational exchange, attributed to low frequency motions of aromatic rings, was indirectly observed for residues on the extracellular side of the bR cavity. This may be related to reorganization of the water network. These observations provide a detailed picture of previously undescribed equilibrium dynamics on different time scales for ground-state bR.     

The coupled-cluster formalism – a mathematical perspective

ABSTRACT

The Coupled-Cluster (CC) theory is one of the most successful high precision methods used to solve the stationary Schrödinger equation. In this article, we address the mathematical foundation of this theory with focus on the advances made in the past decade. Rather than solely relying on spectral gap assumptions (non-degeneracy of the ground state), we highlight the importance of coercivity assumptions – Gårding type inequalities – for the local uniqueness of the CC solution. Based on local strong monotonicity, different sufficient conditions for a local unique solution are suggested. One of the criteria assumes the relative smallness of the total cluster amplitudes (after possibly removing the single amplitudes) compared to the Gårding constants. In the extended CC theory the Lagrange multipliers are wave function parameters and, by means of the bivariational principle, we here derive a connection between the exact cluster amplitudes and the Lagrange multipliers. This relation might prove useful when determining the quality of a CC solution. Furthermore, the use of an Aubin–Nitsche duality type method in different CC approaches is discussed and contrasted with the bivariational principle.     

Formation of Finely Dispersed Structures in Alloys of Aluminum with Cobalt and Zirconium

Russian Journal of Physical Chemistry A - Rapidly quenched alloys of aluminum with cobalt and zirconium are investigated using a combination of means of physicochemical analysis to study the...     

Single-emissive-layer all-perovskite white light-emitting diodes employing segregated mixed halide perovskite crystals

Metal halide perovskites have demonstrated impressive properties for achieving efficient monochromatic light-emitting diodes. However, the development of white perovskite light-emitting diodes (PeLEDs) remains a big challenge. Here, we demonstrate a single-emissive-layer all-perovskite white PeLED using a mixed halide perovskite film as the emissive layer. The perovskite film consists of separated mixed halide perovskite phases with blue and red emissions, which are beneficial for suppressing halide anion exchange and preventing charge transfer. As a result, the white PeLED shows balanced white light emission with Commission Internationale de L''Eclairage coordinates of (0.33, 0.33). In addition, we find that the achievement of white light emission from mixed halide perovskites strongly depends on effective modulation of the halide salt precursors, especially lead bromide and benzamidine hydrochloride in our case. Our work provides very useful guidelines for realizing single-emissive-layer all-perovskite white PeLEDs based on mixed halide perovskites, which will spur the development of high-performance white PeLEDs.

We demonstrated a single-emissive-layer all-perovskite white light-emitting diode based on a mixed halide perovskite film.     

Organocatalytic asymmetric chlorinative dearomatization of naphthols

An organocatalytic asymmetric chlorinative dearomatization of naphthols was realized for the first time, providing chiral naphthalenones with a Cl-containing all-substituted stereocenter in excellent yields and enantioselectivity (up to 97% yield and 96% ee). The reaction features mild reaction conditions, good tolerance of diverse functional groups and simple reaction operation.