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Sulfur-bridged chromophores for photofunctional materials: using sulfur oxidation state to tune electronic and structural properties.

ABSTRACT: The use of a heteroatom, such as sulfur, as a linker or bridge, in π-conjugated materials has advantages over purely carbon-based ones due to the accessibility of higher oxidation states as a result of hypervalence. Materials containing a sulfide bridge (S) can be systemically oxidized into sulfoxides (SO) and sulfones (SO₂), each of which can then influence how a material interacts with light, playing a large role in dictating the photophysical and sometimes photochemical properties. In this perspective, we summarize the progress that our group and others have made, showing how oxidation of a sulfur bridge in symmetric bichromophoric dimers and in diimine ligands can influence the excited state behavior in organic π-conjugated materials and metal complexes.

SUBMITTER: Yuan J

PROVIDER: S-EPMC9116371 | biostudies-literature | 2022 May

REPOSITORIES: biostudies-literature

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Sulfur-bridged chromophores for photofunctional materials: using sulfur oxidation state to tune electronic and structural properties.

Yuan Jennifer J Xu Zhen Z Wolf Michael O MO

Chemical science 20220428 19

The use of a heteroatom, such as sulfur, as a linker or bridge, in π-conjugated materials has advantages over purely carbon-based ones due to the accessibility of higher oxidation states as a result of hypervalence. Materials containing a sulfide bridge (S) can be systemically oxidized into sulfoxides (SO) and sulfones (SO<sub>2</sub>), each of which can then influence how a material interacts with light, playing a large role in dictating the photophysical and sometimes photochemical properties. ...[more]

PMID: 35694344

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Project description:Sequenced genomes of dissimilatory sulfur-oxidizing and sulfate-reducing bacteria containing genes coding for DsrAB, the enzyme dissimilatory sulfite reductase, inevitably also contain the gene coding for the 12-kDa DsrC protein. DsrC is thought to have a yet unidentified role associated with the activity of DsrAB. Here we report the solution structure of DsrC from the sulfur-oxidizing purple sulfur bacterium Allochromatium vinosum determined with NMR spectroscopy in reducing conditions, and we describe the redox behavior of two conserved cysteine residues upon transfer to an oxidizing environment. In reducing conditions, the DsrC structure is disordered in the highly conserved carboxy-terminus. We present multiple lines of evidence that, in oxidizing conditions, a strictly conserved cysteine (Cys111) at the penultimate position in the sequence forms an intramolecular disulfide bond with Cys100, which is conserved in DsrC in all organisms with DsrAB. While an intermolecular Cys111-Cys111 disulfide-bonded dimer is rapidly formed under oxidizing conditions, the intramolecularly disulfide-bonded species (Cys100-Cys111) is the thermodynamically stable form of the protein under these conditions. Treatment of the disulfidic forms with reducing agent regenerates the monomeric species that was structurally characterized. Using a band-shift technique under nondenaturing conditions, we obtained evidence for the interaction of DsrC with heterohexameric DsrEFH, a protein encoded in the same operon. Mutation of Cys100 to serine prevented formation of the DsrC species assigned as an intramolecular disulfide in oxidizing conditions, while still allowing formation of the intermolecular Cys111-Cys111 dimer. In the reduced form, this mutant protein still interacted with DsrEFH. This was not the case for the Cys111Ser and Cys100Ser/Cys111Ser mutants, both of which also did not form protein dimers. Our observations highlight the central importance of the carboxy-terminal DsrC cysteine residues and are consistent with a role as a sulfur-substrate binding/transferring protein, as well as with an electron-transfer function via thiol-disulfide interchanges.

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Sulfur-bridged chromophores for photofunctional materials: using sulfur oxidation state to tune electronic and structural properties.

Publications

Sulfur-bridged chromophores for photofunctional materials: using sulfur oxidation state to tune electronic and structural properties.

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