摘要
Any method that can enhance the fluorescence of fluorophores is highly desirable. Fluorescence enhancement accomplished by restricted Z/E photoisomerization through intramolecular steric hindrance or relatively high bond order of a C?C double bond in a S1 excited state has rarely been studied. In this article, we used green fluorescent protein (GFP) chromophore analogues as a model to get new physical insights into the restricted Z/E photoisomerization and E/Z thermoisomerization phenomena. We found that the S1 and S0 potential energy surfaces (PESs) of the GFP chromophore analogues experience two dramatically different types of restricted rotation, and 2b can be a representative example. In its S1 PES, it is not the intramolecular steric hindrance between the out-of-plane benzyl group and the in-plane m-pyridinium group but the relatively high bond order of the I-bond in the S1 excited state of 2b that makes it have a higher barrier for the Z/E photoisomerization, a smaller Z/E photoisomerization quantum yield, and a higher fluorescence quantum yield. In its S0 PES, it is not the reduced bond order of the I-bond in the S0 ground state of 2b but the intramolecular steric hindrance between the out-of-plane benzyl group and the in-plane m-pyridinium group that makes it have an extra higher barrier for E/Z thermoisomerization and a much smaller E/Z thermoisomerization rate constant.
| 原文 | English |
|---|---|
| 頁（從 - 到） | 4708-4716 |
| 頁數 | 9 |
| 期刊 | Journal of Physical Chemistry A |
| 卷 | 123 |
| 發行號 | 22 |
| DOIs | |
| 出版狀態 | Published - 2019 六月 6 |
指紋
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
引用此文
}
S1/S0 Potential Energy Surfaces Experience Different Types of Restricted Rotation : Restricted Z/ e Photoisomerization and E/ Z Thermoisomerization by an Out-of-Plane Benzyl Group or In-Plane m-Pyridinium Group? / Xu, Jun Jia; Sung, Robert; Sung, Kuang-Sen.
於: Journal of Physical Chemistry A, 卷 123, 編號 22, 06.06.2019, p. 4708-4716.研究成果: Article
TY - JOUR
T1 - S1/S0 Potential Energy Surfaces Experience Different Types of Restricted Rotation
T2 - Restricted Z/ e Photoisomerization and E/ Z Thermoisomerization by an Out-of-Plane Benzyl Group or In-Plane m-Pyridinium Group?
AU - Xu, Jun Jia
AU - Sung, Robert
AU - Sung, Kuang-Sen
PY - 2019/6/6
Y1 - 2019/6/6
N2 - Any method that can enhance the fluorescence of fluorophores is highly desirable. Fluorescence enhancement accomplished by restricted Z/E photoisomerization through intramolecular steric hindrance or relatively high bond order of a C?C double bond in a S1 excited state has rarely been studied. In this article, we used green fluorescent protein (GFP) chromophore analogues as a model to get new physical insights into the restricted Z/E photoisomerization and E/Z thermoisomerization phenomena. We found that the S1 and S0 potential energy surfaces (PESs) of the GFP chromophore analogues experience two dramatically different types of restricted rotation, and 2b can be a representative example. In its S1 PES, it is not the intramolecular steric hindrance between the out-of-plane benzyl group and the in-plane m-pyridinium group but the relatively high bond order of the I-bond in the S1 excited state of 2b that makes it have a higher barrier for the Z/E photoisomerization, a smaller Z/E photoisomerization quantum yield, and a higher fluorescence quantum yield. In its S0 PES, it is not the reduced bond order of the I-bond in the S0 ground state of 2b but the intramolecular steric hindrance between the out-of-plane benzyl group and the in-plane m-pyridinium group that makes it have an extra higher barrier for E/Z thermoisomerization and a much smaller E/Z thermoisomerization rate constant.
AB - Any method that can enhance the fluorescence of fluorophores is highly desirable. Fluorescence enhancement accomplished by restricted Z/E photoisomerization through intramolecular steric hindrance or relatively high bond order of a C?C double bond in a S1 excited state has rarely been studied. In this article, we used green fluorescent protein (GFP) chromophore analogues as a model to get new physical insights into the restricted Z/E photoisomerization and E/Z thermoisomerization phenomena. We found that the S1 and S0 potential energy surfaces (PESs) of the GFP chromophore analogues experience two dramatically different types of restricted rotation, and 2b can be a representative example. In its S1 PES, it is not the intramolecular steric hindrance between the out-of-plane benzyl group and the in-plane m-pyridinium group but the relatively high bond order of the I-bond in the S1 excited state of 2b that makes it have a higher barrier for the Z/E photoisomerization, a smaller Z/E photoisomerization quantum yield, and a higher fluorescence quantum yield. In its S0 PES, it is not the reduced bond order of the I-bond in the S0 ground state of 2b but the intramolecular steric hindrance between the out-of-plane benzyl group and the in-plane m-pyridinium group that makes it have an extra higher barrier for E/Z thermoisomerization and a much smaller E/Z thermoisomerization rate constant.
UR - http://www.scopus.com/inward/record.url?scp=85067003284&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85067003284&partnerID=8YFLogxK
U2 - 10.1021/acs.jpca.9b02924
DO - 10.1021/acs.jpca.9b02924
M3 - Article
C2 - 31084005
AN - SCOPUS:85067003284
VL - 123
SP - 4708
EP - 4716
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 22
ER -