A diabatic three-state representation of photoisomerization in the green fluorescent protein chromophore

被引:53
|
作者
Olsen, Seth [1 ]
McKenzie, Ross H.
机构
[1] Univ Queensland, Ctr Organ Photon & Elect, Brisbane, Qld 4072, Australia
来源
JOURNAL OF CHEMICAL PHYSICS | 2009年 / 130卷 / 18期
基金
澳大利亚研究理事会;
关键词
biochemistry; fluorescence; isomerisation; molecular configurations; molecular electronic states; molecule-photon collisions; nonradiative transitions; perturbation theory; photochemistry; proteins; EXCITED-STATE DYNAMICS; AB-INITIO; CONICAL INTERSECTIONS; ELECTRONIC EXCITATIONS; BLOCK DIAGONALIZATION; CRYSTAL-STRUCTURE; SINGLE MOLECULES; STRUCTURAL BASIS; CHARGE-TRANSFER; CYANINE DYES;
D O I
10.1063/1.3121324
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We give a quantum chemical description of the photoisomerization reaction of green fluorescent protein (GFP) chromophores using a representation over three diabatic states. Photoisomerization leads to nonradiative decay, and competes with fluorescence in these systems. In the protein, this pathway is suppressed, leading to fluorescence. Understanding the electronic states relevant to photoisomerization is a prerequisite to understanding how the protein suppresses it, and preserves the emitting state of the chromophore. We present a solution to the state-averaged complete active space problem, which is spanned at convergence by three fragment-localized orbitals. We generate the diabatic-state representation by block diagonalization transformation of the Hamiltonian calculated for the anionic chromophore model HBDI with multireference, multistate perturbation theory. The diabatic states are charge localized and admit a natural valence-bond interpretation. At planar geometries, the diabatic picture of the optical excitation reduces to the canonical two-state charge-transfer resonance of the anion. Extension to a three-state model is necessary to describe decay via two possible pathways associated with photoisomerization of the (methine) bridge. Parametric Hamiltonians based on the three-state ansatz can be fit directly to data generated using the underlying active space. We provide an illustrative example of such a parametric Hamiltonian.
引用
收藏
页数:13
相关论文
共 50 条
  • [1] Reversible Photoisomerization of the Isolated Green Fluorescent Protein Chromophore
    Carrascosa, Eduardo
    Bull, James N.
    Scholz, Michael S.
    Coughlan, Neville J. A.
    Olsen, Seth
    Wille, Uta
    Bieske, Evan J.
    JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 2018, 9 (10): : 2647 - 2651
  • [2] Photoisomerization of green fluorescent protein and the dimensions of the chromophore cavity
    Chen, MC
    Lambert, CR
    Urgitis, JD
    Zimmer, M
    CHEMICAL PHYSICS, 2001, 270 (01) : 157 - 164
  • [3] Bond selection in the photoisomerization reaction of anionic green fluorescent protein and kindling fluorescent protein chromophore models
    Olsen, Seth
    Smith, Sean C.
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (27) : 8677 - 8689
  • [4] Detailed Photoisomerization Dynamics of a Green Fluorescent Protein Chromophore Based Molecular Switch
    Jiang, Chen-Wei
    Fang, Ai-Ping
    Zhao, Di
    Li, Hong-Rong
    Xie, Rui-Hua
    Li, Fu-Li
    INTERNATIONAL JOURNAL OF PHOTOENERGY, 2014, 2014
  • [5] Ultrafast excited state dynamics in the green fluorescent protein chromophore
    Toniolo, A
    Olsen, S
    Manohar, L
    Martínez, TJ
    FEMTOCHEMISTRY AND FEMTOBIOLOGY: ULTRAFAST EVENTS IN MOLECULAR SCIENCE, 2004, : 425 - 432
  • [6] Ground state isomerization of a model green fluorescent protein chromophore
    He, X
    Bell, AF
    Tonge, PJ
    FEBS LETTERS, 2003, 549 (1-3) : 35 - 38
  • [7] Ultrafast excited state relaxation of the chromophore of the green fluorescent protein
    Litvinenko, KL
    Webber, NM
    Meech, SR
    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 2002, 75 (05) : 1065 - 1070
  • [8] Ultrafast excited state relaxation of the chromophore of the green fluorescent protein
    Litvinenko, Konstantin Leonid
    Webber, Naomi Marica
    Meech, Stephen Roy
    Bulletin of the Chemical Society of Japan, 2002, 75 (05): : 1065 - 1070
  • [9] Excited-state dynamics in the green fluorescent protein chromophore
    Mandal, D
    Tahara, T
    Meech, SR
    JOURNAL OF PHYSICAL CHEMISTRY B, 2004, 108 (03): : 1102 - 1108
  • [10] Chromophore formation in green fluorescent protein
    Reid, BG
    Flynn, GC
    BIOCHEMISTRY, 1997, 36 (22) : 6786 - 6791