Dataset Information

Photocatalytic oxidation of benzene to phenol using dioxygen as an oxygen source and water as an electron source in the presence of a cobalt catalyst.

ABSTRACT: Photocatalytic hydroxylation of benzene to phenol by dioxygen (O₂) occurs under visible light irradiation of an O₂-saturated acetonitrile solution containing [Ru^II(Me₂phen)₃]²⁺ as a photocatalyst, [Co^III(Cp*)(bpy)(H₂O)]²⁺ as an efficient catalyst for both the water oxidation and benzene hydroxylation reactions, and water as an electron source in the presence of Sc(NO₃)₃. The present study reports the first example of photocatalytic hydroxylation of benzene with O₂ and H₂O, both of which are the most green reagents, under visible light irradiation to afford a high turnover number (e.g., >500). Mechanistic studies revealed that the photocatalytic reduction of O₂ to H₂O₂ is the rate-determining step, followed by efficient catalytic hydroxylation of benzene to phenol with H₂O₂, paving a new way for the photocatalytic oxygenation of substrates by O₂ and water.

SUBMITTER: Han JW

PROVIDER: S-EPMC5637359 | biostudies-literature | 2017 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Photocatalytic oxidation of benzene to phenol using dioxygen as an oxygen source and water as an electron source in the presence of a cobalt catalyst.

Han Ji Won JW Jung Jieun J Lee Yong-Min YM Nam Wonwoo W Fukuzumi Shunichi S

Chemical science 20170821 10

Photocatalytic hydroxylation of benzene to phenol by dioxygen (O2) occurs under visible light irradiation of an O2-saturated acetonitrile solution containing [RuII(Me2phen)3]2+ as a photocatalyst, [CoIII(Cp*)(bpy)(H2O)]2+ as an efficient catalyst for both the water oxidation and benzene hydroxylation reactions, and water as an electron source in the presence of Sc(NO3)3. The p ...[more]

PMID: 29147542

Similar Datasets

Project description:Anaerobic benzene oxidation coupled to the reduction of Fe(III) was studied in Ferroglobus placidus in order to learn more about how such a stable molecule could be metabolized under strict anaerobic conditions. F. placidus conserved energy to support growth at 85°C in a medium with benzene provided as the sole electron donor and Fe(III) as the sole electron acceptor. The stoichiometry of benzene loss and Fe(III) reduction, as well as the conversion of [14C]-benzene to [14C]-carbon dioxide, was consistent with complete oxidation of benzene to carbon dioxide with electron transfer to Fe(III). Benzoate, but not phenol or toluene, accumulated at low levels during benzene metabolism and [14C]-benzoate was produced from [14C]-benzene. Analysis of gene transcript levels revealed increased expression of genes encoding enzymes for anaerobic benzoate degradation during growth on benzene versus growth on acetate, but genes involved in phenol degradation were not up-regulated during growth on benzene. A gene for a putative carboxylase that was more highly expressed in benzene- versus benzoate-grown cells was identified. These results suggest that benzene is carboxylated to benzoate and that phenol is not an important intermediate in the benzene metabolism of F. placidus. This is the first demonstration of a microorganism in pure culture that can grow on benzene under strict anaerobic conditions and for which there is strong evidence for degradation of benzene via clearly defined anaerobic metabolic pathways. Thus, F. placidus provides a much needed pure culture model for further studies on the anaerobic activation of benzene in microorganisms. A six-chip study using total RNA recovered from three separate cultures of Ferroglobus placidus DSM 10642 grown with 1 mM benzene (experimental condition) and three separate cultures of Ferroglobus placidus DSM 10642 grown on 0.5 mM phenol (control condition). Each chip measures the expression level of 2,613 genes from Ferroglobus placidus DSM 10642 with nine 45-60-mer probe pairs (PM/MM) per gene, with three-fold technical redundancy.

Project description:Anaerobic benzene oxidation coupled to the reduction of Fe(III) was studied in Ferroglobus placidus in order to learn more about how such a stable molecule could be metabolized under strict anaerobic conditions. F. placidus conserved energy to support growth at 85°C in a medium with benzene provided as the sole electron donor and Fe(III) as the sole electron acceptor. The stoichiometry of benzene loss and Fe(III) reduction, as well as the conversion of [14C]-benzene to [14C]-carbon dioxide, was consistent with complete oxidation of benzene to carbon dioxide with electron transfer to Fe(III). Benzoate, but not phenol or toluene, accumulated at low levels during benzene metabolism and [14C]-benzoate was produced from [14C]-benzene. Analysis of gene transcript levels revealed increased expression of genes encoding enzymes for anaerobic benzoate degradation during growth on benzene versus growth on acetate, but genes involved in phenol degradation were not up-regulated during growth on benzene. A gene for a putative carboxylase that was more highly expressed in benzene- versus benzoate-grown cells was identified. These results suggest that benzene is carboxylated to benzoate and that phenol is not an important intermediate in the benzene metabolism of F. placidus. This is the first demonstration of a microorganism in pure culture that can grow on benzene under strict anaerobic conditions and for which there is strong evidence for degradation of benzene via clearly defined anaerobic metabolic pathways. Thus, F. placidus provides a much needed pure culture model for further studies on the anaerobic activation of benzene in microorganisms. A five-chip study using total RNA recovered from three separate cultures of Ferroglobus placidus DSM 10642 grown with 0.5 mM phenol (experimental condition) and two separate cultures of Ferroglobus placidus DSM 10642 grown on 1 mM benzoate (control condition). Each chip measures the expression level of 2,613 genes from Ferroglobus placidus DSM 10642 with nine 45-60-mer probe pairs (PM/MM) per gene, with three-fold technical redundancy.

Dataset Information

Photocatalytic oxidation of benzene to phenol using dioxygen as an oxygen source and water as an electron source in the presence of a cobalt catalyst.

Publications

Photocatalytic oxidation of benzene to phenol using dioxygen as an oxygen source and water as an electron source in the presence of a cobalt catalyst.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure