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A "waiting" carbon nitride radical anion: a charge storage material and key intermediate in direct C-H thiolation of methylarenes using elemental sulfur as the "S"-source.

ABSTRACT: Potassium poly(heptazine imide), a carbon nitride based semiconductor with high structural order and a valence band potential of +2.2 V vs. NHE, in the presence of hole scavengers and under visible light irradiation gives the corresponding polymeric radical anion, in which the specific density of unpaired electrons reaches 112 ?mol g^-1. The obtained polymeric radical anion is stable under anaerobic conditions for several hours. It was characterized using UV-vis absorption, time resolved and steady state photoluminescence spectra. The electronic structure of the polymeric radical anion was confirmed by DFT cluster modelling. The unique properties of potassium poly(heptazine imide) for storing charges were employed in visible light photocatalysis. A series of substituted dibenzyldisulfanes was synthesized in 41-67% yield from the corresponding methylarenes via cleavage of the methyl C-H bond under visible light irradiation and metal-free conditions.

SUBMITTER: Savateev A

PROVIDER: S-EPMC5935028 | biostudies-literature | 2018 Apr

REPOSITORIES: biostudies-literature

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A "waiting" carbon nitride radical anion: a charge storage material and key intermediate in direct C-H thiolation of methylarenes using elemental sulfur as the "S"-source.

Savateev Aleksandr A Kurpil Bogdan B Mishchenko Artem A Zhang Guigang G Antonietti Markus M

Chemical science 20180314 14

Potassium poly(heptazine imide), a carbon nitride based semiconductor with high structural order and a valence band potential of +2.2 V <i>vs.</i> NHE, in the presence of hole scavengers and under visible light irradiation gives the corresponding polymeric radical anion, in which the specific density of unpaired electrons reaches 112 μmol g<sup>-1</sup>. The obtained polymeric radical anion is stable under anaerobic conditions for several hours. It was characterized using UV-vis absorption, time ...[more]

PMID: 29780491

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Project description:Insights into the Metabolism of Elemental Sulfur by the Hyperthermophilic Archaeon Pyrococcus furiosus: Characterization of a Coenzyme A-Dependent NAD(P)H Sulfur Oxidoreductase The hyperthermophilic archaeon Pyrococcus furiosus, uses carbohydrates as a carbon source and produces acetate, CO2 and H2 as end products. When S° is added to a growing culture, within 10 min the rate of H2 production rapidly decreases and H2S is detected. After one hour cells contain high NADPH- and coenzyme A-dependent S° reduction activity (0.7 units/mg, 85°C) located in the cytoplasm. The enzyme responsible for this activity was purified to electrophoretic homogeneity (specific activity, 100 units/mg) and is termed NAD(P)H elemental sulfur oxidoreductase (NSR). NSR is a homodimeric flavoprotein (Mr 100 kDa) and is encoded by PF1186. This was previously assigned to an enzyme that reduces coenzyme A disulfide, which is a side-reaction of NSR. Whole genome DNA microarray and quantitative PCR analyses showed that the expression of NSR is up-regulated up to 7-fold within 10 min of S° addition. This primary response to S° also involves the up-regulation (> 16-fold) of a 13 gene cluster encoding a membrane-bound oxidoreductase (MBX). MBX is proposed replace the homologous 14 gene cluster that encodes the ferredoxin-oxidizing, H2-evolving membrane-bound hydrogenase (MBH), which is down-regulated >12-fold within 10 min of S° addition. Although an activity for MBX could not be demonstrated, it is proposed to conserve energy by oxidizing ferredoxin and reducing NADP, which is used by NSR to reduce S°. A secondary response to S° is observed 30 min after S° addition and includes the up-regulation of genes encoding proteins involved in amino acid biosynthesis and iron metabolism, as well as two so-called sulfur-induced proteins, termed SipA and SipB. This novel S°-reducing system involving NSR and MBX is so far unique to the heterotrophic Thermococcales, and is in contrast to the cytochrome- and quinone-based S°-reducing system in autotrophic archaea and bacteria. Keywords: time course, kinetic, sulfur metabolism, archaea, Pyrococcus furiosus, hyperthermophile

Dataset Information

A "waiting" carbon nitride radical anion: a charge storage material and key intermediate in direct C-H thiolation of methylarenes using elemental sulfur as the "S"-source.

Publications

A "waiting" carbon nitride radical anion: a charge storage material and key intermediate in direct C-H thiolation of methylarenes using elemental sulfur as the "S"-source.

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