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Research
Cytochrome c oxidase
Nitric
Oxide Reductase
Surface Modification
Metal–metal bonds
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Professor
Collman
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Department of Chemistry
Stanford University
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News and Views
- A Cytochrome c Oxidase Model
Catalyzes the Reduction of Oxygen to Water Under Rate-Limiting Electron
Flux
We studied the selectivity of a functional model of cytochrome
c oxidase's active site that mimics the coordination
environment and relative locations of Fea3, CuB, and Tyr244. To control
electron flux, we covalently attached this model and analogs lacking
copper and phenol onto self-assembled monolayer–coated gold
electrodes. When the electron transfer rate was made rate limiting, both
copper and phenol were required to enhance selective reduction of oxygen
to water. This finding supports the hypothesis that, during steady-state
turnover, the primary role of these redox
centers is to rapidly provide all the electrons needed to reduce oxygen
by four electrons, thus preventing the release of toxic partially
reduced oxygen species.: Science, 2007, 315, 5818,
1565-1568. DOI: 10.1126/science.1135844. Lead authors: Neal Devaraj, Richard Decreau.
- Syntheses
of Hemoprotein Models that can be Covalently Attached onto Electrode Surfaces by Click
Chemistry.
J.
Org. Chem., 2007, 72, 2794-2802. Lead Authors: Richard Decréau,
Ying Yang
Read Feature in Chemical
and Engineering News: An Electron Starved Enzyme Read Feature in Chemistry
World: Chemical Model Unlock’s Key
Enzyme’s Secrets
- Collmania 2006
Photos from the 2006 Collman Symposium are
available here.
- Selective
Functionalization of Independently Addressable
Microelectrode Arrays
By appropriately biasing adjacent electrodes, we have used copper(I)
catalyzed azide-alkyne cycloaddtions
(Sharpless “click” chemistry) to
selectively modified one of two chemically identical 10- m-wide
band electrodes separated by 10 m in an
interdigitated array (IDA) (shown above). The
ability to independently functionalize each electrode in an array will
allow electrically programmed functionality in sensor and actuator
arrays, as well as other multielectrode
devices.. Read about it in our recent article: J. Amer. Chem. Soc., 2006, 128(6), 1794-5. Read
feature in Science Magazine: Editor’s choice Lead Authors: Neal Devaraj / Peter Dinolfo.
- Synthesis of Nitric
Oxide Reductase Active Site Models Bearing Key
Components at Both Distal and Proximal Sites. Ligands for active-site models of bacterial
nitric oxide reductase (NOR) have been
synthesized. The compounds possess a distal trisimidazole
set, a distal carboxylic acid, and a proximal imidazole,
which constitute all the key features of the coordination environment of
the active site in Bacterial Nitric Oxide Reductase
(NOR) and make them the closest synthetic NOR model ligands
to date: Org.
Lett., 2007, 9 (15), 2855-2858. Lead authors:
Ying Yang, Richard Decréau
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