title: Dynamics on the electronically excited state surface of the bioluminescent firefly luciferase-oxyluciferin system.
abstract: Dynamics of the firefly luciferase-oxyluciferin complex in its electronic ground and excited states are studied using various theoretical approaches. By mimicking the physiological conditions with realistic models of the chromophore oxyluciferin, the enzyme luciferase, and solvating water molecules and by performing real time simulations with a molecular dynamics technique on the model surfaces, we reveal that the local chromophore-surrounding interaction patterns differ rather severely in the two states. Because of the presence of protein, the solvation dynamics of water around the chromophore is also peculiar and shows widely different time scales on the two terminal oxygen atoms. In addition, simulations of the emission with the quantum-mechanics/molecular-mechanics approach show a close relationship between the emission color variation and the environmental dynamics, mostly through electrostatic effects from the chromophore-surrounding interaction. We also discuss the importance of considering the time scales of the luminescence and the dynamics of the interaction.
authors: Institute of Theoretical and Computational Chemistry, Pohang University of Science and Technology (POSTECH), Pohang, 790-784 Korea.
authors: Chang-ik
authors: CI
authors: Song
authors: Young Min
authors: YM
authors: Rhee
mesh_terms: D004583:Electrons; D007211:Indoles / Q000737:chemistry*; D049409:Luciferases, Firefly / Q000737:chemistry* / Q000378:metabolism; D008163:Luminescent Measurements; D008958:Models, Molecular; D056004:Molecular Dynamics Simulation; D015394:Molecular Structure; D011719:Pyrazines / Q000737:chemistry*; D011789:Quantum Theory; D013237:Stereoisomerism; D013499:Surface Properties
chemical_list: D007211:Indoles; D011719:Pyrazines; C014730:oxyluciferin; D049409:Luciferases, Firefly