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Conjugates of Heme-Thiolate Enzymes with Photoactive Metal-Diimine Wires

Contakes, Stephen M. and Nguyen, Yen Hoang Le and Gray, Harry B. and Glazer, Edith C. and Hays, Anna-Maria and Goodin, David B. (2006) Conjugates of Heme-Thiolate Enzymes with Photoactive Metal-Diimine Wires. In: Photofunctional Transition Metal Complexes. Structure and Bonding. No.123. Springer Berlin Heidelberg , Berlin, Heidelberg, pp. 177-203. ISBN 9783540368090.

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Heme-thiolate enzymes, notably cytochromes P450 and nitric oxide synthases, use dioxygen to oxygenatesubstrates. Photoactive metal-diimine molecular wires that are capable of effecting rapid redox state changesat buried active sites have been developed to generate intermediates in the catalytic cycles of these enzymes.Wires that feature a photoactive head group tethered to an active-site ligand bind P450CAM and induciblenitric oxide synthase (iNOS) primarily by hydrophobic interactions. The wire-binding specificity of eachenzyme is critically dependent on the structural flexibility of the protein. P450CAM:wire conjugates canadopt open or partially open conformations, thereby accommodating a wide range of wires, whereas onlylong wires with smaller [Re(CO)_3(bpy)Im]^+ head groupsare able to bind tightly in the rigid active-site channel of iNOS. Dansyl-terminated molecular wires functionas highly sensitive and isoform specific fluorescent sensors for P450CAM.

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Gray, Harry B.0000-0002-7937-7876
Additional Information:© Springer-Verlag Berlin Heidelberg 2006. Figure 11 was adopted from a version prepared by Alex Dunn. We thank him and others in the Caltech molecular wires group (Ivan Dmochowski, Jon Wilker, Corinna Hess, Wendy Belliston-Bittner, Nick Halpern-Manners) for contributions that are summarized in this chapter. Our work is supported by NIH, NSF, the Ellison Medical Foundation Senior Scholar Award in Aging (to HBG), and the Arnold and Mabel Beckman Foundation.
Funding AgencyGrant Number
Ellison Medical FoundationUNSPECIFIED
Arnold and Mabel Beckman FoundationUNSPECIFIED
Subject Keywords:Molecular Wires · Cytochromes P450 · Nitric Oxide Synthase · Photochemistry · Electron Transfer
Series Name:Structure and Bonding
Issue or Number:123
Record Number:CaltechAUTHORS:20190828-102318186
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:98304
Deposited By: George Porter
Deposited On:28 Aug 2019 17:33
Last Modified:16 Nov 2021 17:38

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