Polymer Connectivity Governs Electrophotocatalytic Activity in the Solid State.

The reductive functionalization of inert substrates like chloroarenes is a critical yet challenging transformation relevant to both environmental remediation and organic synthesis. Combining electricity and light is an emerging approach to access the deeply reducing potentials required for single electron transfer to chloroarenes, yet this approach is held back by the poor stability and mechanistic ambiguity of current homogeneous systems. Incorporating redox-active moieties into insoluble organic materials represents a promising strategy to unlock new heterogeneous catalytic activity while improving catalyst stability.

Solvent-tunable exciton-charge transfer mixed state enhances emission of functionalized benzo[]pentaphene through symmetry breaking.

A benzo[]pentaphene (BPP) substituted by two bis(methoxyphenyl)amino (MeOPA) groups (BPP-MeOPA) was synthesized and clearly characterized by NMR and single-crystal X-ray analysis. Detailed investigations of its photophysical properties, including transient absorption spectroscopy analyses, revealed that the introduction of the MeOPA groups breaks the symmetry of the BPP core, improving its absorption and emission from an S state with both excitonic and charge-transfer character.

Complexation of Astatine(III) with Ketones: Roles of NO Counterion and Exploration of Possible Binding Modes.

Ketones have been proven effective in extracting astatine(III) from aqueous solvents. Previous theoretical studies suggested a mechanism where the "sp" lone pair on the carbonyl oxygen donates electron density into the π system of the AtO molecular cation to form a dative-type bond. In this study, co-extraction of NO as AtO(NO)·(O═CRR) species into the organic phase appears to be a key factor.

Investigation of the pH-dependence of the oxidation of FAD in VcCRY-1, a member of the cryptochrome-DASH family.

Vibrio cholerae cryptochrome-1 (VcCRY-1) is a member of the cryptochrome DASH family. The flavoprotein appears to use blue light both for repair of cyclobutane pyrimidine dimers (CPDs) on DNA and signal transduction. Earlier, we found that it was almost impossible to oxidize the FADH· state upon binding to a CPD, and, in the absence of substrate, the rate of FADH· oxidation was much larger at high pH (Gindt et al.