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Excitation wavelength dependent O2 release from copper(II)-superoxide compounds: laser flash-photolysis experiments and theoretical studies.

ABSTRACT: Irradiation of the copper(II)-superoxide synthetic complexes [(TMG3tren)Cu(II)(O2)](+) (1) and [(PV-TMPA)Cu(II)(O2)](+) (2) with visible light resulted in direct photogeneration of O2 gas at low temperature (from -40 °C to -70 °C for 1 and from -125 to -135 °C for 2) in 2-methyltetrahydrofuran (MeTHF) solvent. The yield of O2 release was wavelength dependent: ?exc = 436 nm, ? = 0.29 (for 1), ? = 0.11 (for 2), and ?exc = 683 nm, ? = 0.035 (for 1), ? = 0.078 (for 2), which was followed by fast O2-recombination with [(TMG3tren)Cu(I)](+) (3) and [(PV-TMPA)Cu(I)](+) (4). Enthalpic barriers for O2 rebinding to the copper(I) center (?10 kJ mol(-1)) and for O2 dissociation from the superoxide compound 1 (45 kJ mol(-1)) were determined. TD-DFT studies, carried out for 1, support the experimental results confirming the dissociative character of the excited states formed upon blue- or red-light laser excitation.

SUBMITTER: Saracini C

PROVIDER: S-EPMC3936478 | biostudies-literature | 2014 Jan

REPOSITORIES: biostudies-literature

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Excitation wavelength dependent O2 release from copper(II)-superoxide compounds: laser flash-photolysis experiments and theoretical studies.

Saracini Claudio C Liakos Dimitrios G DG Zapata Rivera Jhon E JE Neese Frank F Meyer Gerald J GJ Karlin Kenneth D KD

Journal of the American Chemical Society 20140115 4

Irradiation of the copper(II)-superoxide synthetic complexes [(TMG3tren)Cu(II)(O2)](+) (1) and [(PV-TMPA)Cu(II)(O2)](+) (2) with visible light resulted in direct photogeneration of O2 gas at low temperature (from -40 °C to -70 °C for 1 and from -125 to -135 °C for 2) in 2-methyltetrahydrofuran (MeTHF) solvent. The yield of O2 release was wavelength dependent: λexc = 436 nm, ϕ = 0.29 (for 1), ϕ = 0.11 (for 2), and λexc = 683 nm, ϕ = 0.035 (for 1), ϕ = 0.078 (for 2), which was followed by fast O2- ...[more]

PMID: 24428309

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Project description:p-Cresol methylhydroxylase, a heterodimer consisting of one flavoprotein subunit and one cytochrome c subunit, may be resolved into its subunits, and the holoenzyme may then be fully reconstituted from the pure subunits. In the present study we have characterized the reduction kinetics of the intact enzyme and its subunits, by using exogenous 5-deazariboflavin semiquinone radical generated in the presence of EDTA by the laser-flash-photolysis technique. Under anaerobic conditions the 5-deazariboflavin semiquinone radical reacts rapidly with the native enzyme with a rate constant approaching that of a diffusion-controlled reaction (k = 2.8 X 10(9) M-1 X s-1). Time-resolved difference spectra at pH 7.6 indicate that both flavin and haem are reduced initially by the deazariboflavin semiquinone radical, followed by an additional slower intramolecular electron transfer (k = 220 s-1) from the endogenous neutral flavin semiquinone radical to the oxidized haem moiety of the native enzyme. During the steady-state photochemical titration of the native enzyme at pH 7.6 with deazariboflavin semiquinone radical generated by light-irradiation the haem appeared to be reduced before the protein-bound flavin and was followed by the formation of the protein-bound anionic flavin radical. This result suggests that the redox potential of the haem is higher than that of the flavin, and that deprotonation of the flavin neutral radical occurred during the photochemical titration. Reduction kinetics of the flavoprotein and cytochrome subunits were also investigated by laser-flash photolysis. The protein-bound flavin of the isolated flavin subunit was reduced rapidly by the deazariboflavin semiquinone radical (k = 2.2 X 10(9) M-1 X s-1), as was the haem of the pure cytochrome c subunit (k = 3.7 X 10(9) M-1 X s-1). Flash-induced difference spectra obtained for the flavoprotein and cytochrome subunits at pH 7.6 were consistent with the formation of neutral flavin semiquinone radical and reduced haem, respectively. Investigation of the kinetic properties of the neutral flavin semiquinone radical of the flavoprotein subunit at pH 7.6 and at longer times (up to 5s) were consistent with a slow first-order deprotonation reaction (k = 1 s-1) of the neutral radical to its anionic form.

Dataset Information

Excitation wavelength dependent O2 release from copper(II)-superoxide compounds: laser flash-photolysis experiments and theoretical studies.

Publications

Excitation wavelength dependent O2 release from copper(II)-superoxide compounds: laser flash-photolysis experiments and theoretical studies.

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