Theoretical Study of the ESIPT Process for a New Natural Product Quercetin.
Theoretical Study of the ESIPT Process for a New Natural Product Quercetin.
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新天然产物槲皮素ESIPT工艺的理论研究
DOI：
10.1038/srep32152
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发表时间：
2016-08-30
影响因子：
4.6
通讯作者：
Li Y
中科院分区：
文献类型：
--
作者：
Yang Y;Zhao J;Li Y
用密度泛函理论(DFT)和含时密度泛函理论(TDDFT)方法研究了天然产物槲皮素在二氯甲烷(DCM)溶剂中的激发态分子内质子转移(ESIPT)。为了区分不同类型的分子内相互作用，还使用了约化密度梯度(RDG)函数。在本研究中，我们阐明了ESIPT过程中产生的两种互变异构体(K1，K2)存在于第一电子激发态(S1)的观点。通过比较基态和第一激发态氢键基团的红外振动光谱和键参数的变化，证实了氢键相互作用增强的现象。前线分子轨道(MOS)提供了直观的电子密度重分布，进一步验证了氢键强化机理。值得注意的是，通过观察势能分布，K2型比K1型更容易发生ESIPT过程。此外，RDG等值面还表明，K2晶型的氢键作用比K1晶型强，这也是K2晶型更容易发生ESIPT过程的原因。
The investigation of excited-state intramolecular proton transfer (ESIPT) has been carried out via the density functional theory (DFT) and the time-dependent density functional theory (TDDFT) method for natural product quercetin in dichloromethane (DCM) solvent. For distinguishing different types of intramolecular interaction, the reduced density gradient (RDG) function also has been used. In this study, we have clearly clarified the viewpoint that two kinds of tautomeric forms (K1, K2)originated from ESIPT processconsist inthe first electronic excited state (S1). The phenomenon of hydrogen bonding interaction strengtheninghas been proved by comparing the changes of infrared (IR) vibrational spectra and bond parameters of the hydrogen bonding groups in the ground state with that in the first excited state. The frontier molecular orbitals (MOs)provided visual electron density redistribution have further verified the hydrogen bond strengthening mechanism. It should be noted that the ESIPT process of the K2form is easier to occur than that of the K1form via observing the potential energy profiles. Furthermore, the RDG isosurfaces has indicated that hydrogen bonding interaction of the K2form is stronger than that of the K1formin the S1state, which is also the reason why the ESIPT process of the K2form is easier to occur.
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影响因子：
4.6
作者：
Hämäläinen M;Nieminen R;Vuorela P;Heinonen M;Moilanen E
通讯作者：
Moilanen E
DOI：
10.1039/p29930000799
发表时间：
1993-05-01
期刊：
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2
影响因子：
--
作者：
KLAMT, A;SCHUURMANN, G
通讯作者：
SCHUURMANN, G
影响因子：
2.4
作者：
Graf, BA;Milbury, PE;Blumberg, JB
通讯作者：
Blumberg, JB
基于激发态分子内质子转移的水性氟化物化学传感器 BTPPB 传感机制的 DFT/TDDFT 研究
影响因子：
3.9
作者：
Chen, Jun-Sheng;Zhou, Pan-Wang;Chu, Tian-Shu
通讯作者：
Chu, Tian-Shu
影响因子：
3.5
作者：
CHOU, PT;MARTINEZ, ML;CHANG, CP
通讯作者：
CHANG, CP