Quantitative prediction of excited-state decay rates for radical anion photocatalysts.

We present a computational approach for predicting key properties of organic radical anions, including excited-state lifetimes and redox potentials. The approach shows good agreement with experimental data and has potential for in silico screening to facilitate the rational design of photocatalysts.

Unravelling the Effect of Water Addition in Consecutive Photocatalysis with Naphthalene Diimide.

We describe the effect of water addition in the catalyst performance for a C-H functionalization of benzene. Improved yields and selectivity were achieved in a consecutive photoredox catalysis in contrast to the reaction without water. Mechanistic analysis demonstrated this is due to a better catalyst stability and faster kinetic rather than a change in the different steps of the mechanism. The addition of water constitutes a convenient approach to improve catalyst performance, and it was also observed with other catalysts.

Psychosine remodels model lipid membranes at neutral pH.

ß-Galactosylsphingosine or psychosine (PSY) is a single chain sphingolipid with a cationic group, which is degraded in the lysosome lumen by ß-galactosylceramidase during sphingolipid biosynthesis. A deficiency of this enzyme activity results in Krabbe's disease and PSY accumulation. This favors its escape to extralysosomal spaces, with its pH changing from acidic to neutral. We studied the interaction of PSY with model lipid membranes in neutral conditions, using phospholipid vesicles and monolayers as classical model systems, as well as a complex lipid mixture that mimics the lipid composition of myelin. At pH 7.4, when PSY is mainly neutral, it showed high surface activity, self-organizing into large structures, probably lamellar in nature, with a CMC of 38 ±â€¯3 µM. When integrated into phospholipid membranes, PSY showed preferential partition into disordered phases, shifting phase equilibrium. The presence of PSY reduces the compactness of the membrane, making it more easily compressible. It also induces lipid domain disruption in vesicles composed of the main myelin lipids. The surface electrostatics of lipid membranes was altered by PSY in a complex manner. A shift to positive zeta potential values evidenced its presence in the vesicles. Furthermore, the increase of surface potential and surface water structuring observed may be a consequence of its location at the interface of the positively charged layer. As Krabbe's disease is a demyelinating process, PSY alteration of the membrane phase state, lateral lipid distribution and surface electrostatics appears important to the understanding of myelin destabilization at the supramolecular level.