Light-activated protein inhibition through photoinduced electron transfer of a ruthenium(II)–cobalt(III) bimetallic complex

Holbrook, Robert J.; Weinberg, David J.; Peterson, Mark D.; Weiss, Emily A.; Meade, Thomas J.

doi:10.1021/jacs.5b00342

Title: Light-activated protein inhibition through photoinduced electron transfer of a ruthenium(II)–cobalt(III) bimetallic complex

Journal Article · Wed Feb 11 04:00:00 UTC 2015 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.5b00342 · OSTI ID:1345974

Holbrook, Robert J. ^[1]; Weinberg, David J. ^[2]; Peterson, Mark D. ^[2]; Weiss, Emily A. ^[2]; Meade, Thomas J. ^[2]

Northwestern Univ., Evanston, IL (United States); Office of Scientific and Technical Information (OSTI)
Northwestern Univ., Evanston, IL (United States)

In this paper, we describe a mechanism of light activation that initiates protein inhibitory action of a biologically inert Co(III) Schiff base (Co(III)-sb) complex. Photoinduced electron transfer (PET) occurs from a Ru(II) bipyridal complex to a covalently attached Co(III) complex and is gated by conformational changes that occur in tens of nanoseconds. Reduction of the Co(III)-sb by PET initiates displacement of the inert axial imidazole ligands, promoting coordination to active site histidines of α-thrombin. Upon exposure to 455 nm light, the rate of ligand exchange with 4-methylimidazole, a histidine mimic, increases by approximately 5-fold, as observed by NMR spectroscopy. Similarly, the rate of α-thrombin inhibition increases over 5-fold upon irradiation. Finally, these results convey a strategy for light activation of inorganic therapeutic agents through PET utilizing redox-active metal centers.

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Research Organization:: Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC05-06OR23100

OSTI ID:: 1345974

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 9 Vol. 137; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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