Solvent effects on the vibrational activity and photodynamics of the green fluorescent protein chromophore: A quantum-chemical study

被引:141
作者
Altoe, P
Bernardi, F
Garavelli, M
Orlandi, G
Negri, F
机构
[1] Univ Bologna, Dipartimento Chim G Ciamician, I-40126 Bologna, Italy
[2] UdR, INSTM, Bologna, Italy
关键词
D O I
10.1021/ja0451517
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Vibrational activities in the Raman and resonance Raman spectra of the cationic, neutral, and anionic forms of 4'-hydroxybenzylidene-2,3-dimethyl-imidazolinone, a model compound for the green fluorescent protein chromophore, have been obtained from quantum-chemical calculations in vacuo and with the inclusion of solvent effects through the polarizable continuum model. It is found that inclusion of solvent effects improves slightly the agreement with experimental data for the cationic and neutral forms, whose spectra are qualitatively well-described already by calculations in vacuo. In contrast, inclusion of solvent effects is crucial to reproduce correctly the activities of the anionic form. The structural effects of solvation are remarkable both in the ground and in the lowest excited state of the anionic chromophore and influence not only the vibrational activity but also the photodynamics of the lowest excited state. CASPT2//CASSCF photoreaction paths, computed by including solvent effects at the CASSCF level, indicate a facile torsional deformation around both exocyclic CC bonds. Rotation around the exocyclic CC double bond is shown to lead to a favored radiationless decay channel, more efficient than that in gas phase, and which explains the ultrafast fluorescence decay and ground-state recovery observed in solution. Conversely, rotation around the exocyclic CC single bond accounts for the bottleneck observed in the ground-state recovery cycle. It is also speculated that the ultrafast radiationless decay channel would be hampered in protein for unfavorable electrostatic interactions and steric reasons.
引用
收藏
页码:3952 / 3963
页数:12
相关论文
共 35 条
[1]   A distinctive example of the cooperative interplay of structure and environment in tuning of intramolecular charge transfer in second-order nonlinear optical chromophores [J].
Abbotto, A ;
Beverina, L ;
Bradamante, S ;
Facchetti, A ;
Klein, C ;
Pagani, GA ;
Redi-Abshiro, M ;
Wortmann, R .
CHEMISTRY-A EUROPEAN JOURNAL, 2003, 9 (09) :1991-2007
[2]  
ANDERSSON K, 1999, MOLCAS 5 0
[3]   Probing the ground state structure of the green fluorescent protein chromophore using Raman spectroscopy [J].
Bell, AF ;
He, X ;
Wachter, RM ;
Tonge, PJ .
BIOCHEMISTRY, 2000, 39 (15) :4423-4431
[4]   Light-driven decarboxylation of wild-type green fluorescent protein [J].
Bell, AF ;
Stoner-Ma, D ;
Wachter, RM ;
Tonge, PJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (23) :6919-6926
[5]   Structural basis for dual excitation and photoisomerization of the Aequorea victoria green fluorescent protein [J].
Brejc, K ;
Sixma, TK ;
Kitts, PA ;
Kain, SR ;
Tsien, RY ;
Ormo, M ;
Remington, SJ .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 1997, 94 (06) :2306-2311
[6]   Electronic structure of the chromophore in green fluorescent protein (GFP) [J].
Bublitz, G ;
King, BA ;
Boxer, SG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (36) :9370-9371
[7]   Ultra-fast excited state dynamics in green fluorescent protein: Multiple states and proton transfer [J].
Chattoraj, M ;
King, BA ;
Bublitz, GU ;
Boxer, SG .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 1996, 93 (16) :8362-8367
[8]   Coherent dynamics of photoexcited green fluorescent proteins [J].
Cinelli, RAG ;
Tozzini, V ;
Pellegrini, V ;
Beltram, F ;
Cerullo, G ;
Zavelani-Rossi, M ;
De Silvestri, S ;
Tyagi, M ;
Giacca, M .
PHYSICAL REVIEW LETTERS, 2001, 86 (15) :3439-3442
[9]   Ab initio study of solvated molecules: A new implementation of the polarizable continuum model [J].
Cossi, M ;
Barone, V ;
Cammi, R ;
Tomasi, J .
CHEMICAL PHYSICS LETTERS, 1996, 255 (4-6) :327-335
[10]   Vibrational spectroscopy and mode assignments for an analog of the green fluorescent protein chromophore [J].
Esposito, AP ;
Schellenberg, P ;
Parson, WW ;
Reid, PJ .
JOURNAL OF MOLECULAR STRUCTURE, 2001, 569 (1-3) :25-41