Intramolecular Hydrogen Bonding Plays a Crucial Role in the Photophysics and Photochemistry of the GFP Chromophore | |
Cui, Ganglong1; Lan, Zhenggang2; Thiel, Walter1 | |
2012-01-25 | |
发表期刊 | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY |
卷号 | 134期号:3页码:1662-1672 |
摘要 | In commonly studied GFP chromophore analogues such as 4-(4-hydroxybenzylidene)-1,2-dimethyl-1H-imidazol-5(4H)-one (PHBDI), the dominant photoinduced processes are cis–trans isomerization and subsequent S1 → S0 decay via a conical intersection characterized by a highly twisted double bond. The recently synthesized 2-hydroxy-substituted isomer (OHBDI) shows an entirely different photochemical behavior experimentally, since it mainly undergoes ultrafast intramolecular excited-state proton transfer, followed by S1 → S0 decay and ground-state reverse hydrogen transfer. We have chosen 4-(2-hydroxybenzylidene)-1H-imidazol-5(4H)-one (OHBI) to model the gas-phase photodynamics of such 2-hydroxy-substituted chromophores. We first use various electronic structure methods (DFT, TDDFT, CC2, DFT/MRCI, OM2/MRCI) to explore the S0 and S1 potential energy surfaces of OHBI and to locate the relevant minima, transition state, and minimum-energy conical intersection. These static calculations suggest the following decay mechanism: upon photoexcitation to the S1 state, an ultrafast adiabatic charge-transfer induced excited-state intramolecular proton transfer (ESIPT) occurs that leads to the S1 minimum-energy structure. Nearby, there is a S1/S0 minimum-energy conical intersection that allows for an efficient nonadiabatic S1 → S0 internal conversion, which is followed by a fast ground-state reverse hydrogen transfer (GSHT). This mechanism is verified by semiempirical OM2/MRCI surface-hopping dynamics simulations, in which the successive ESIPT-GSTH processes are observed, but without cis–trans isomerization (which is a minor path experimentally with less than 5% yield). These gas-phase simulations of OHBI give an estimated first-order decay time of 476 fs for the S1 state, which is larger but of the same order as the experimental values measured for OHBDI in solution: 270 fs in CH3CN and 230 fs in CH2Cl2. The differences between the photoinduced processes of the 2- and 4-hydroxy-substituted chromophores are attributed to the presence or absence of intramolecular hydrogen bonding between the two rings. ; In commonly studied GFP chromophore analogues such as 4-(4-hydroxybenzylidene)-1,2-dimethyl-1H-imidazol-5(4H)-one (PHBDI), the dominant photoinduced processes are cis-trans isomerization and subsequent S-1 -> S-0 decay via a conical intersection characterized by a highly twisted double bond. The recently synthesized 2-hydroxy-substituted isomer (OHBDI) shows an entirely different photochemical behavior experimentally, since it mainly undergoes ultrafast intramolecular excited-state proton transfer, followed by S-1 -> S-0 decay and ground-state reverse hydrogen transfer. We have chosen 4-(2-hydroxybenzylidene)-1H-imidazol-5(4H)-one (OHBI) to model the gas-phase photodynamics of such 2-hydroxy-substituted chromophores. We first use various electronic structure methods (DFT, TDDFT, CC2, DFT/MRCI, OM2/MRCI) to explore the S-0 and S-1 potential energy surfaces of OHBI and to locate the relevant minima, transition state, and minimum-energy conical intersection. These static calculations suggest the following decay mechanism: upon photoexcitation to the S-1 state, an ultrafast adiabatic charge-transfer induced excited-state intramolecular proton transfer (ESIPT) occurs that leads to the S-1 minimum-energy structure. Nearby, there is a S-1/S-0 minimum-energy conical intersection that allows for an efficient nonadiabatic S-1 -> S-0 internal conversion, which is followed by a fast ground-state reverse hydrogen transfer (GSHT). This mechanism is verified by semiempirical OM2/MRCI surface-hopping dynamics simulations, in which the successive ESIPT-GSTH processes are observed, but without cis-trans isomerization (which is a minor path experimentally with less than 5% yield). These gas-phase simulations of OHM give an estimated first-order decay time of 476 Is for the S-1 state, which is larger but of the same order as the experimental values measured for OHBDI in solution: 270 Is in CH3CN and 230 fs in CH2Cl2. The differences between the photoinduced processes of the 2- and 4-hydroxy-substituted chromophores are attributed to the presence or absence of intramolecular hydrogen bonding between the two rings. |
文章类型 | Article |
学科领域 | 仿真与模拟 |
WOS标题词 | Science & Technology ; Physical Sciences |
DOI | 10.1021/ja208496s |
关键词[WOS] | GREEN FLUORESCENT PROTEIN ; EXCITED-STATE DYNAMICS ; CONICAL INTERSECTION DYNAMICS ; PROTON-TRANSFER PROCESSES ; GAUSSIAN-BASIS SETS ; ELECTRONIC EXCITATIONS ; MOLECULAR-DYNAMICS ; IDENTITY APPROXIMATION ; SEMIEMPIRICAL METHODS ; MODEL CC2 |
收录类别 | SCI |
语种 | 英语 |
WOS研究方向 | Chemistry |
WOS类目 | Chemistry, Multidisciplinary |
WOS记录号 | WOS:000301084400052 |
引用统计 | |
文献类型 | 期刊论文 |
条目标识符 | http://ir.qibebt.ac.cn/handle/337004/1320 |
专题 | 蛋白质设计研究组 |
作者单位 | 1.Max Planck Inst Kohlenforsch, D-45470 Mulheim, Germany 2.Chinese Acad Sci, Qingdao Inst Bioenergy & Bioproc Technol, Qingdao 266101, Peoples R China |
推荐引用方式 GB/T 7714 | Cui, Ganglong,Lan, Zhenggang,Thiel, Walter. Intramolecular Hydrogen Bonding Plays a Crucial Role in the Photophysics and Photochemistry of the GFP Chromophore[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2012,134(3):1662-1672. |
APA | Cui, Ganglong,Lan, Zhenggang,&Thiel, Walter.(2012).Intramolecular Hydrogen Bonding Plays a Crucial Role in the Photophysics and Photochemistry of the GFP Chromophore.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,134(3),1662-1672. |
MLA | Cui, Ganglong,et al."Intramolecular Hydrogen Bonding Plays a Crucial Role in the Photophysics and Photochemistry of the GFP Chromophore".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 134.3(2012):1662-1672. |
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