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Article

Regulatory Impact of the C-Terminal Tail on Charge Transfer Pathways in Drosophila Cryptochrome

Max-Born-Institut für Nichtlineare Optik und Kurzzeitspektroskopie, D-12489 Berlin, Germany
*
Author to whom correspondence should be addressed.
Current address: Institut für Physikalische Chemie, Friedrich-Schiller-Universität Jena, D-07743 Jena, Germany.
Academic Editor: Martin Brehm
Molecules 2020, 25(20), 4810; https://doi.org/10.3390/molecules25204810
Received: 30 September 2020 / Revised: 14 October 2020 / Accepted: 14 October 2020 / Published: 19 October 2020
(This article belongs to the Special Issue Describing Bulk Phase Effects with Ab Initio Methods)
Interconnected transcriptional and translational feedback loops are at the core of the molecular mechanism of the circadian clock. Such feedback loops are synchronized to external light entrainment by the blue light photoreceptor cryptochrome (CRY) that undergoes conformational changes upon light absorption by an unknown photoexcitation mechanism. Light-induced charge transfer (CT) reactions in Drosophila CRY (dCRY) are investigated by state-of-the-art simulations that reveal a complex, multi-redox site nature of CT dynamics on the microscopic level. The simulations consider redox-active chromophores of the tryptophan triad (Trp triad) and further account for pathways mediated by W314 and W422 residues proximate to the C-terminal tail (CTT), thus avoiding a pre-bias to specific W-mediated CT pathways. The conducted dissipative quantum dynamics simulations employ microscopically derived model Hamiltonians and display complex and ultrafast CT dynamics on the picosecond timescale, subtly balanced by the electrostatic environment of dCRY. In silicio point mutations provide a microscopic basis for rationalizing particular CT directionality and demonstrate the degree of electrostatic control realized by a discrete set of charged amino acid residues. The predicted participation of CT states in proximity to the CTT relates the directionality of CT reactions to the spatial vicinity of a linear interaction motif. The results stress the importance of CTT directional charge transfer in addition to charge transfer via the Trp triad and call for the use of full-length CRY models including the interactions of photolyase homology region (PHR) and CTT domains. View Full-Text
Keywords: electron transfer; circadian clock; cryptochrome; tryptophan electron transfer; circadian clock; cryptochrome; tryptophan
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MDPI and ACS Style

Richter, M.; Fingerhut, B.P. Regulatory Impact of the C-Terminal Tail on Charge Transfer Pathways in Drosophila Cryptochrome. Molecules 2020, 25, 4810. https://doi.org/10.3390/molecules25204810

AMA Style

Richter M, Fingerhut BP. Regulatory Impact of the C-Terminal Tail on Charge Transfer Pathways in Drosophila Cryptochrome. Molecules. 2020; 25(20):4810. https://doi.org/10.3390/molecules25204810

Chicago/Turabian Style

Richter, Martin, and Benjamin P. Fingerhut 2020. "Regulatory Impact of the C-Terminal Tail on Charge Transfer Pathways in Drosophila Cryptochrome" Molecules 25, no. 20: 4810. https://doi.org/10.3390/molecules25204810

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