Superexchange in the fast lane – intramolecular electron transfer in a molecular triad occurs by conformationally gated superexchange

2019 ◽  
Vol 55 (36) ◽  
pp. 5251-5254 ◽  
Author(s):  
Yusen Luo ◽  
Maria Wächtler ◽  
Kevin Barthelmes ◽  
Andreas Winter ◽  
Ulrich S. Schubert ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Temperature Dependence ◽  
Photoinduced Electron Transfer ◽  
Intramolecular Electron Transfer ◽  
Fast Lane

Photoinduced electron transfer via hopping is generally considered to have a stronger temperature dependence than electron transfer via superexchange.

scholarly journals Two-photon sensitive protecting groups operating via intramolecular electron transfer: uncaging of GABA and tryptophan

2015 ◽  
Vol 6 (4) ◽  
pp. 2419-2426 ◽  
Author(s):  
Karolina A. Korzycka ◽  
Philip M. Bennett ◽  
Eduardo Jose Cueto-Diaz ◽  
Geoffrey Wicks ◽  
Mikhail Drobizhev ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Photoinduced Electron Transfer ◽  
High Sensitivity ◽  
Protecting Groups ◽  
Intramolecular Electron Transfer ◽  
Modular Approach ◽  
Two Photon ◽  
Photon Excitation ◽  
Two Photon Excitation

We present a modular approach to photo-labile protecting groups based on photoinduced electron transfer, providing high sensitivity to two-photon excitation.

scholarly journals Photoactivation of Cryptochromes Invokes Competing Inter- and Intramolecular Electron Transfer

2020 ◽  
Author(s):  
Ruslan N. Tazhigulov ◽  
Justin Provazza ◽  
David Coker ◽  
Ksenia B. Bravaya
Keyword(s):  
Electron Transfer ◽  
Photoinduced Electron Transfer ◽  
Migratory Birds ◽  
Intramolecular Electron Transfer ◽  
Tryptophan Residues ◽  
Theoretical Evidence ◽  
Excited Charge Transfer State

<div>Growing experimental and theoretical evidence points to the key role of cryptochrome proteins in magnetoreception by migratory birds and insects. Cryptochrome photoactivation is achieved through a cascade of electron transfer events leading to formation of a long-lived spin-correlated radical pair. The electron transfer cascade is initiated by photoexcitation of the FAD cofactor and subsequent electron transfer through three conserved tryptophan residues, the so-called tryptophan triad. Presence of ATP was shown to increase the yield of the semireduced form of FAD. While electron transfer through the tryptophan triad is well characterized by both theoretical and experimental methods, the effects of ATP binding are still not well understood. The present work aims to unravel the mechanism of ultrafast photoinduced electron transfer in a cryptochrome protein with a focus on effects of ATP on the FAD photoreduction process. Photoinduced electron transfer is described by means of state-of-the-art theoretical methods: a hybrid quantum-classical polarizable embedding scheme is utilized to accurately parameterize a generalized local excited/charge transfer state system-bath model Hamiltonian and the photoinduced electron transfer process is described by a semiclassical path integral-based dynamics method. The results draw attention to the crucial role of the intramolecular electron transfer from adenine to the flavin moiety of the FAD cofactor for formation of the semireduced form of FAD, providing an explanation for the increased yield of the semireduced form in the presence of the cellular metabolites <i>in vitro</i> and <i>in vivo</i>.</div>

Morpholinyl dendrimer phthalocyanine: synthesis, photophysical properties and photoinduced intramolecular electron transfer

2018 ◽  
Vol 47 (37) ◽  
pp. 13164-13170 ◽  
Author(s):  
Qiumei Guo ◽  
Limin Chen ◽  
Sujuan Pan ◽  
Dongdong Ma ◽  
Xiwen Liu ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Photoinduced Electron Transfer ◽  
Photophysical Properties ◽  
Intramolecular Electron Transfer ◽  
Phthalocyanine Ring

The photophysical properties of a novel series of morpholinyl dendrimer phthalocyanines exhibited dependence on the number of morpholinyl groups and the central ion. The photoinduced electron transfer from the morpholinyl units to phthalocyanine ring was evidenced.

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