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Isomerization mechanism of the HcRed fluorescent protein chromophore
Sun, Qiao1; Li, Zhen2; Lan, Zhenggang3,4; Pfisterer, Christoph5; Doerr, Markus3,6,7; Fischer, Stefan5; Smith, Sean C.1,8; Thiel, Walter3
2012
发表期刊PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷号14期号:32页码:11413-11424
摘要

To understand how the protein achieves fluorescence, the isomerization mechanism of the HcRed chromophore is studied both under vacuum and in the solvated red fluorescent protein. Quantum mechanical (QM) and quantum mechanical/molecular mechanical (QM/MM) methods are applied both for the ground and the first excited state. The photoinduced processes in the chromophore mainly involve torsions around the imidazolinone-bridge bond (τ) and the phenoxy-bridge bond (φ). Under vacuum, the isomerization of the cis-trans chromophore essentially proceeds by τ twisting, while the radiationless decay requires φ torsion. By contrast, the isomerization of the cis-trans chromophore in HcRed occurs via simultaneous τ and φ twisting. The protein environment significantly reduces the barrier of this hula twist motion compared with vacuum. The excited-state isomerization barrier via the φ rotation of the cis-coplanar conformer in HcRed is computed to be significantly higher than that of the trans-non-coplanar conformer. This is consistent with the experimental observation that the cis-coplanar-conformation of the chromophore is related to the fluorescent properties of HcRed, while the trans-non-planar conformation is weakly fluorescent or non-fluorescent. Our study shows how the protein modifies the isomerization mechanism, notably by interactions involving the nearby residue Ile197, which keeps the chromophore coplanar and blocks the twisting motion that leads to photoinduced radiationless decay.

 
; To understand how the protein achieves fluorescence, the isomerization mechanism of the HcRed chromophore is studied both under vacuum and in the solvated red fluorescent protein. Quantum mechanical (QM) and quantum mechanical/molecular mechanical (QM/MM) methods are applied both for the ground and the first excited state. The photoinduced processes in the chromophore mainly involve torsions around the imidazolinone-bridge bond (tau) and the phenoxy-bridge bond (phi). Under vacuum, the isomerization of the cis-trans chromophore essentially proceeds by tau twisting, while the radiationless decay requires phi torsion. By contrast, the isomerization of the cis-trans chromophore in HcRed occurs via simultaneous tau and phi twisting. The protein environment significantly reduces the barrier of this hula twist motion compared with vacuum. The excited-state isomerization barrier via the phi rotation of the cis-coplanar conformer in HcRed is computed to be significantly higher than that of the trans-non-coplanar conformer. This is consistent with the experimental observation that the cis-coplanar-conformation of the chromophore is related to the fluorescent properties of HcRed, while the trans-non-planar conformation is weakly fluorescent or non-fluorescent. Our study shows how the protein modifies the isomerization mechanism, notably by interactions involving the nearby residue Ile197, which keeps the chromophore coplanar and blocks the twisting motion that leads to photoinduced radiationless decay.
文章类型Article
学科领域仿真与模拟
WOS标题词Science & Technology ; Physical Sciences
DOI10.1039/c2cp41217a
关键词[WOS]PHOTOINDUCED NONADIABATIC DYNAMICS ; ELECTRONIC-STRUCTURE CALCULATIONS ; 2ND-ORDER PERTURBATION-THEORY ; PHOTOACTIVE YELLOW PROTEIN ; DENSITY-FUNCTIONAL THEORY ; SEMIEMPIRICAL METHODS ; MOLECULAR-DYNAMICS ; CRYSTAL-STRUCTURE ; PROTON-TRANSFER ; STRUCTURAL BASIS
收录类别SCI
语种英语
WOS研究方向Chemistry ; Physics
WOS类目Chemistry, Physical ; Physics, Atomic, Molecular & Chemical
WOS记录号WOS:000306708300020
引用统计
被引频次:21[WOS]   [WOS记录]     [WOS相关记录]
文献类型期刊论文
条目标识符http://ir.qibebt.ac.cn/handle/337004/1312
专题蛋白质设计研究组
作者单位1.Univ Queensland, Ctr Computat Mol Sci, Australian Inst Bioengn & Nanotechnol, Brisbane, Qld 4072, Australia
2.Univ Wollongong, ISEM, Wollongong, NSW 2500, Australia
3.Max Planck Inst Kohlenforsch, D-45470 Mulheim, Germany
4.Chinese Acad Sci, Qingdao Inst Bioenergy & Bioproc Technol, Qingdao 266101, Peoples R China
5.Univ Heidelberg, IWR, D-69120 Heidelberg, Germany
6.Univ Santo Tomas, Fac Quim Ambiental, Bucaramanga, Colombia
7.Univ Ind Santander, Escuela Quim, Grp Bioquim Teor, Bucaramanga, Colombia
8.Oak Ridge Natl Lab, Ctr Nanophase Mat Sci, Oak Ridge, TN 37831 USA
推荐引用方式
GB/T 7714
Sun, Qiao,Li, Zhen,Lan, Zhenggang,et al. Isomerization mechanism of the HcRed fluorescent protein chromophore[J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS,2012,14(32):11413-11424.
APA Sun, Qiao.,Li, Zhen.,Lan, Zhenggang.,Pfisterer, Christoph.,Doerr, Markus.,...&Thiel, Walter.(2012).Isomerization mechanism of the HcRed fluorescent protein chromophore.PHYSICAL CHEMISTRY CHEMICAL PHYSICS,14(32),11413-11424.
MLA Sun, Qiao,et al."Isomerization mechanism of the HcRed fluorescent protein chromophore".PHYSICAL CHEMISTRY CHEMICAL PHYSICS 14.32(2012):11413-11424.
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