Inserting a Hydrogen-Bond Relay between Proton Exchanging Sites in Proton-Coupled Electron Transfers

2010 ◽  
Vol 122 (22) ◽  
pp. 3891-3894 ◽  
Author(s):  
Cyrille Costentin ◽  
Marc Robert ◽  
Jean-Michel Savéant ◽  
Cédric Tard
Keyword(s):  
Hydrogen Bond ◽  
Electron Transfers

Correction to Hydrogen-Bond Relays in Concerted Proton–Electron Transfers

2013 ◽  
Vol 46 (8) ◽  
pp. 1910-1910
Author(s):  
Julien Bonin ◽  
Cyrille Costentin ◽  
Marc Robert ◽  
Jean-Michel Savéant ◽  
Cédric Tard
Keyword(s):  
Hydrogen Bond ◽  
Electron Transfers

A molecular mediator for reductive concerted proton-electron transfers via electrocatalysis

Science ◽  
2020 ◽  
Vol 369 (6505) ◽  
pp. 850-854 ◽  
Author(s):  
Matthew J. Chalkley ◽  
Pablo Garrido-Barros ◽  
Jonas C. Peters
Keyword(s):  
Hydrogen Bond ◽  
Electron Transfer ◽  
Bond Strength ◽  
Hydrogen Evolution ◽  
Redox Mediator ◽  
Cathodic Reduction ◽  
Hydrogen Bond Strength ◽  
Brönsted Acid ◽  
Nitrogen Hydrogen Bond ◽  
Electron Transfers

Electrocatalytic approaches to the activation of unsaturated substrates via reductive concerted proton-electron transfer (CPET) must overcome competing, often kinetically dominant hydrogen evolution. We introduce the design of a molecular mediator for electrochemically triggered reductive CPET through the synthetic integration of a Brønsted acid and a redox mediator. Cathodic reduction at the cobaltocenium redox mediator substantially weakens the homolytic nitrogen-hydrogen bond strength of a Brønsted acidic anilinium tethered to one of the cyclopentadienyl rings. The electrochemically generated molecular mediator is demonstrated to transform a model substrate, acetophenone, to its corresponding neutral α-radical via a rate-determining CPET.

Hydrogen-Bond Relays in Concerted Proton–Electron Transfers

2011 ◽  
Vol 45 (3) ◽  
pp. 372-381 ◽  
Author(s):  
Julien Bonin ◽  
Cyrille Costentin ◽  
Marc Robert ◽  
Jean-Michel Savéant ◽  
Cédric Tard
Keyword(s):  
Hydrogen Bond ◽  
Electron Transfers

scholarly journals Inserting a Hydrogen-Bond Relay between Proton Exchanging Sites in Proton-Coupled Electron Transfers

2010 ◽  
Vol 49 (22) ◽  
pp. 3803-3806 ◽  
Author(s):  
Cyrille Costentin ◽  
Marc Robert ◽  
Jean-Michel Savéant ◽  
Cédric Tard
Keyword(s):  
Hydrogen Bond ◽  
Electron Transfers

A Hydrogen Bond Between Linear Tetrapyrrole and Conserved Aspartate Causes the Far-Red Shifted Absorption of Phytochrome Photoreceptors

2020 ◽  
Author(s):  
Egle Maximowitsch ◽  
Tatiana Domratcheva
Keyword(s):  
Hydrogen Bond ◽  
Light Adaptation ◽  
Positive Charge ◽  
Pyrrole Ring ◽  
Md Simulations ◽  
Spectral Shift ◽  
Specific Domain ◽  
Study Guides ◽  
Rational Engineering ◽  
Tuning Mechanism

Photoswitching of phytochrome photoreceptors between red-absorbing (Pr) and far-red absorbing (Pfr) states triggers light adaptation of plants, bacteria and other organisms. Using quantum chemistry, we elucidate the color-tuning mechanism of phytochromes and identify the origin of the Pfr-state red-shifted spectrum. Spectral variations are explained by resonance interactions of the protonated linear tetrapyrrole chromophore. In particular, hydrogen bonding of pyrrole ring D with the strictly conserved aspartate shifts the positive charge towards ring D thereby inducing the red spectral shift. Our MD simulations demonstrate that formation of the ring D–aspartate hydrogen bond depends on interactions between the chromophore binding domain (CBD) and phytochrome specific domain (PHY). Our study guides rational engineering of fluorescent phytochromes with a far-red shifted spectrum.

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