A theoretical assignment on excited-state intramolecular proton transfer mechanism for quercetin

	A theoretical assignment on excited-state intramolecular proton transfer mechanism for quercetin
	Yang, Guang 2; Zhao, Jinfeng 3; Zheng, Rui 1; Wang, Yusheng 1; Yang, Dapeng 1,3; Lv, Jian 1
刊名	JOURNAL OF PHYSICAL ORGANIC CHEMISTRY
	2017-11-01
卷号	30 期号:11
关键词	AIM ESIPT IR vibrational spectra MOs potential energy curves
英文摘要	In the present work, we investigate a new chromophore (ie, quercetin) (Simkovitch et al J Phys Chem B 119 [2015] 10244) about its complex excited-state intramolecular proton transfer (ESIPT) process based on density functional theory and time-dependent density functional theory methods. On the basis of the calculation of electron density rho(r) and Laplacian del(2)rho(r) at the bond critical point using atoms-in-molecule theory, the intramolecular hydrogen bonds (O-1-H2 center dot center dot center dot O5 and O-3-H4 center dot center dot center dot O5) have been supported to be formed in the S-0 state. Comparing the prime structural variations of quercetin involved in its 2 intramolecular hydrogen bonds, we find that these 2 hydrogen bonds should be strengthened in the S-1 state, which is a fundamental precondition for facilitating the ESIPT process. Concomitantly, infrared vibrational spectra analysis further verifies this viewpoint. In good agreement with previous experimental spectra results, we find that quercetin reveals 2 kinds of excited-state structures (quercetin* and quercetin-PT1*) in the S-1 state. Frontier molecular orbitals depict the nature of electronically excited state and support the ESIPT reaction. Our scanned potential energy curves according to variational O-1-H-2 and O-3-H-4 coordinates demonstrate that the proton transfer process should be more likely to occur in the S-1 state via hydrogen bond wire O-1-H2 center dot center dot center dot O5 rather than O-3-H4 center dot center dot center dot O5 because of the lower potential energy barrier 2.3kcal/mol. Our present work explains previous experimental result and makes up the deficiency of mechanism in previous experiment. In the end, we make a reasonable assignment for ESIPT process of quercetin.
WOS标题词	Science & Technology ; Physical Sciences
类目[WOS]	Chemistry, Organic ; Chemistry, Physical
研究领域[WOS]	Chemistry
关键词[WOS]	DENSITY-FUNCTIONAL THEORY ; HYDROGEN-BONDING DYNAMICS ; PIGMENT YELLOW 101 ; ANISOTROPIC DIELECTRICS ; FLUORESCENCE PROBE ; SENSING MECHANISM ; ELECTRON-DENSITY ; CHARGE-TRANSFER ; ACID SYSTEM ; TD-DFT
收录类别	SCI
语种	英语
WOS记录号	WOS:000412844400004
内容类型	期刊论文
源URL	[http://cas-ir.dicp.ac.cn/handle/321008/150229]
专题	大连化学物理研究所_中国科学院大连化学物理研究所
作者单位	1.North China Univ Water Resources & Elect Power, Coll Math & Informat Sci, Zhengzhou 450045, Henan, Peoples R China 2.Jiaozuo Univ, Dept Basic Sci, Jiaozuo 454000, Peoples R China 3.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam Theoret & Computat, Dalian 116023, Peoples R China
推荐引用方式 GB/T 7714	Yang, Guang,Zhao, Jinfeng,Zheng, Rui,et al. A theoretical assignment on excited-state intramolecular proton transfer mechanism for quercetin[J]. JOURNAL OF PHYSICAL ORGANIC CHEMISTRY,2017,30(11).
APA	Yang, Guang,Zhao, Jinfeng,Zheng, Rui,Wang, Yusheng,Yang, Dapeng,&Lv, Jian.(2017).A theoretical assignment on excited-state intramolecular proton transfer mechanism for quercetin.JOURNAL OF PHYSICAL ORGANIC CHEMISTRY,30(11).
MLA	Yang, Guang,et al."A theoretical assignment on excited-state intramolecular proton transfer mechanism for quercetin".JOURNAL OF PHYSICAL ORGANIC CHEMISTRY 30.11(2017).