Nonadiabatic Dynamics of Photoinduced Proton-Coupled Electron Transfer in Solvated Molecules and Photoreceptor Proteins
Abstract
Photoreceptor proteins enable the use of light to control biological processes with high spatial and temporal resolution. These photoreceptor proteins play an essential role in the field of optogenetics, where light is used to manipulate and monitor cells in living tissue, typically individual neurons. Such tools are of interest to the Air Force because they may be designed to influence human performance. Often photoreceptor proteins require the coupled movement of electrons and protons following photoexcitation upon the application of light. These types of photoinduced proton-coupled electron transfer (PCET) reactions also play an essential role in many devices developed for the conversion of solar energy to chemical fuel and electrical power.The objective of this proposal is to elucidate the fundamental physical principles underlying photoinduced PCET processes to guide the design of more effective photoreceptor proteins for optogenetics and molecular catalysts for energy production and storage. Theoretical and computational methods for the simulation of photoinduced PCET processes will be developed and applied to experimentally studied systems. In particular, photoinduced PCET will be simulated using nonadiabatic molecular dynamics methods that include the explicit solvent and protein environment, as well as the electronic and key nuclear quantum mechanical effects. The simulations will provide insights into the roles of nonequilibrium dynamics of the environment, vibrational relaxation, and electron-proton coupling for both molecular systems and photoreceptor proteins. They will also predict the impact of modifying the substituents and solvent for molecular systems and the amino acids and chromophore for photoreceptor proteins. In addition, the photoreceptor protein studies will elucidate the relationship between the PCET mechanisms and the protein conformations and identify conformational differences between the resting and signaling states.
Document Details
- Document Type
- DoD Grant Award
- Publication Date
- Apr 09, 2018
- Source ID
- FA95501810134
Entities
People
- Sharon Hammes-Schiffer
Organizations
- Air Force Office of Scientific Research
- United States Air Force
- Yale University