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Effect of water microsolvation on the excited-state proton transfer of 3-hydroxyflavone enclosed in -cyclodextrin
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Document Title
Effect of water microsolvation on the excited-state proton transfer of 3-hydroxyflavone enclosed in -cyclodextrin
Author
Kerdpol K., Daengngern R., Sattayanon C., Namuangruk S., Rungrotmongkol T., Wolschann P., Kungwan N., Hannongbua S.
Name from Authors Collection
Affiliations
Center of Excellence in Computational Chemistry (CECC), Department of Chemistry, Faculty of Science, Chulalongkorn University, Bangkok, 10330, Thailand; Department of Chemistry, Faculty of Science, King Mongkut’s Institute of Technology Ladkrabang, Bangkok, 10520, Thailand; Integrated Applied Chemistry Research Unit, Faculty of Science, King Mongkut’s Institute of Technology Ladkrabang, Bangkok, 10520, Thailand; National Nanotechnology Center (NANOTEC), NSTDA, 111 Thailand Science Park, Pahonyothin Road, Klong Luang, 12120, Thailand; Structural and Computational Biology Research Unit, Department of Biochemistry, Faculty of Science, Chulalongkorn University, Bangkok, 10330, Thailand; Program in Bioinformatics and Computational Biology, Graduate School, Chulalongkorn University, Bangkok, 10330, Thailand; Molecular Sensory Science Center, Faculty of Science, Chulalongkorn University, Bangkok, 10330, Thailand; Department of Pharmaceutical Chemistry, University of Vienna, Vienna, 1090, Austria; Institute of Theoretical Chemistry, University of Vienna, Vienna, 1090, Austria; Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai, 50200, Thailand; Center of Excellence in Materials Science and Technology, Chiang Mai University, Chiang Mai, 50200, Thailand
Type
Article
Source Title
Molecules
ISSN
14203049
Year
2021
Volume
26
Issue
4
Open Access
Gold
Publisher
MDPI AG
DOI
10.3390/molecules26040843
Format
Abstract
The effect of microsolvation on excited-state proton transfer (ESPT) reaction of 3-hydroxyflavone (3HF) and its inclusion complex with -cyclodextrin (-CD) was studied using computational approaches. From molecular dynamics simulations, two possible inclusion complexes formed by the chromone ring (C-ring, Form I) and the phenyl ring (P-ring, Form II) of 3HF insertion to -CD were observed. Form II is likely more stable because of lower fluctuation of 3HF inside the hydrophobic cavity and lower water accessibility to the encapsulated 3HF. Next, the conformation analysis of these models in the ground (S0) and the first excited (S1) states was carried out by density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations, respectively, to reveal the photophysical properties of 3HF influenced by the -CD. The results show that the intermolecular hydrogen bonding (interHB) between 3HF and -CD, and intramolecular hydrogen bonding (intraHB) within 3HF are strengthened in the S1 state confirmed by the shorter interHB and intraHB distances and the red-shift of O-H vibrational modes involving in the ESPT process. The simulated absorption and emission spectra are in good agreement with the experimental data. Significantly, in the S1 state, the keto form of 3HF is stabilized by -CD, explaining the increased quantum yield of keto emission of 3HF when complexing with -CD in the experiment. In the other word, ESPT of 3HF is more favorable in the -CD hydrophobic cavity than in aqueous solution. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.
Funding Sponsor
Chulalongkorn University; Thailand Research Fund
License
CC BY
Rights
Author
Publication Source
Scopus
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Effect of Water Microsolvation on the Excited-State Proton Transfer of 3-Hydroxyflavone EnclosedDownload