蓝色荧光发色团激发态分子内质子转移的理论研究
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- 英文论文题名：Investigation on Excited-State Intramolecular Proton Transfer in a BFP Chromophore
- 论文作者：吴丹 ; 崔刚龙 ; 方维海
- 英文论文作者：Dan Wu ; Ganglong Cui ; Wei-Hai Fang ; Key Laboratory of Theoretical and Computational Photochemistry ; Ministry of Education ; College of Chemistry ; Beijing Normal University
- 年：2016
- 作者机构：北京师范大学化学学院教育部理论与计算光化学重点实验室;
- 论文关键词：蓝色荧光蛋白 ; 激发态质子转移 ; 光化学
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第十八分会：电子结构理论方法的发展与应用
- 语种：中文
- 分类号：O644.1
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第十八分会 ; 电子结构理论方法的发展与应用
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：165k
- 原文格式：D
- 会议级别：全国
摘要
与绿色荧光蛋白发色团相比,最近新合成的一种蓝色荧光蛋白发色团表现出一些奇特的光化学性质,比如双荧光发射,量子产率显著提高,激发态质子转移过程较慢等;但是它的光化学机理尚不清楚。~([1])在本工作中,我们采用CASSCF和CASPT2方法研究了这类合成的蓝色荧光生色团模型的光化学机理。~([2-3])计算发现该体系在激发态以S_1极小点为起点有两条相竞争的失活途径,一条是直接经过一个圆锥交叉区弛豫到S_0态。另一条是先经历分子内激发态质子转移(ESIPT)过程,然后经过另一个圆锥交叉结构失活回到基态。较大的ESIPT能垒与激发态失活能垒导致双荧光的发射和量子产率提高。
Compared with GFP(Green Fluorescence Protein) chromophores, the recently synthesized BFP(Blue Fluorescence Protein) chromophore presents intriguing photochemical properties, e.g.dual fluorescence emission, enhanced fluorescence quantum yield, and ultra-slow excited-state intramolecular proton transfer(ESIPT), however, its photochemical mechanism is still elusive.Herein we have employed CASSCF and CASPT2 methods to study the mechanism of a BFP chromophore variant.We have found the system has two competitive excited state relaxation pathways from the S1-MIN.One runs into a conical intersection region then hopes to the S_0, the other is the ESIPT path and then jumps to the S0 state through the other conical intersection.The considerable barrier in ESIPT process is similar to the deactivation barriers, resulting in the dual fluorescence emission and higher quantum yield.
Compared with GFP(Green Fluorescence Protein) chromophores, the recently synthesized BFP(Blue Fluorescence Protein) chromophore presents intriguing photochemical properties, e.g.dual fluorescence emission, enhanced fluorescence quantum yield, and ultra-slow excited-state intramolecular proton transfer(ESIPT), however, its photochemical mechanism is still elusive.Herein we have employed CASSCF and CASPT2 methods to study the mechanism of a BFP chromophore variant.We have found the system has two competitive excited state relaxation pathways from the S1-MIN.One runs into a conical intersection region then hopes to the S_0, the other is the ESIPT path and then jumps to the S0 state through the other conical intersection.The considerable barrier in ESIPT process is similar to the deactivation barriers, resulting in the dual fluorescence emission and higher quantum yield.
引文
[1]Fang,X.X.;Wang,Y.;Wang,D.;Zhao,G.Y.;Zhang,W.W.;Ren,A.M.;Wang,H.Y.;Xu,J.W.;Gao,B.R.;Yang,W.J.Phys.Chem.Lett.,2014,5:92.
[2]Cui,G.L.;Lan,Z.;Thiel,W.J.Am.Chem.Soc.2012,134:1662.
[3]Liu,X.-Y.;Chang,X.-P.;Xia,S.-H.;Cui,G.L.;Thiel,W.J.Chem.Theory Comput.,2016,16:753.
[2]Cui,G.L.;Lan,Z.;Thiel,W.J.Am.Chem.Soc.2012,134:1662.
[3]Liu,X.-Y.;Chang,X.-P.;Xia,S.-H.;Cui,G.L.;Thiel,W.J.Chem.Theory Comput.,2016,16:753.
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