Electron transfer and spin dynamics of the radical-pair in the cryptochrome from Chlamydomonas reinhardtii by computational analysis
Abstract
In an effort to elucidate the origin of avian magnetoreception, it was postulated that a radical-pair formed in a cryptochrome upon light activation provided the basis for the mechanism that enables an inclination compass sensitive to the geomagnetic field. Photoreduction in this case involves formation of a flavin adenine dinucleotide (FAD)-tryptophan (TRP) radical-pair, following electron transfer within a conserved TRP triad in the cryptochrome. Recently, an animal-like cryptochrome from Chlamydomonas reinhardtii (CraCRY) was analyzed, demonstrating the role of a fourth aromatic residue, which serves as a terminal electron donor in the photoreduction pathway, resulting in the creation of a more distal radical-pair and exhibiting fast electron transfer. In this work, we investigated the electron transfer in CraCRY with a combination of free energy molecular dynamics (MD) simulations, frozen density functional theory, and QM/MM MD simulations, supporting the suggestion of a proton coupled electron transfer mechanism. Spin dynamics simulations discerned details on the dependence of the singlet yield on the direction of the external magnetic field for the [FAD•− TYRH•+] and [FAD•− TYR•] radical-pairs in CraCRY, in comparison with the previously modeled [FAD•− TRPH•+] radical-pair.
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- Feb 10, 2020
- Source ID
- 10.1063/1.5133019
Entities
People
- Gongyi Hong
- Lars-Oliver Essen
- Ruth Pachter
- Thorsten Ritz
Organizations
- Air Force Office of Scientific Research
- Air Force Research Laboratory
- University of Marburg