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Sensing Mechanism for Biothiols Chemosensor DCO: Roles of Excited-State Hydrogen-Bonding and Intramolecular Charge Transfer

Chen, Junsheng LU ; Yuan, Ming-Hu; Wang, Jia-Pei; Yang, Yang and Chu, Tian-Shu (2014) In The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 118(39). p.8986-8995
Abstract
The biothiols sensing mechanism of (E)-7-(diethylamino)-3-(2-nitrovinyl)-2H-chromen-2-one (DCO) has been investigated using the density functional theory (DFT) and time-dependent DFT methods. The theoretical results indicate that the excited-state intermolecular hydrogen bonding (H-B) plays an important role for the biothiols sensing mechanism of the fluorescence sensor DCO. Multiple H-B interaction sites exist in DCO and in its Michael addition product DCOT, which then induce the formation of the H-B complexes with water molecules, DCOH2 and DCOTH4. In the first excited state, the intermolecular H-Bs between water molecule and DCO in DCOH2 are cooperatively and generally strengthened and thus induced the weak fluorescence emission of DCO,... (More)
The biothiols sensing mechanism of (E)-7-(diethylamino)-3-(2-nitrovinyl)-2H-chromen-2-one (DCO) has been investigated using the density functional theory (DFT) and time-dependent DFT methods. The theoretical results indicate that the excited-state intermolecular hydrogen bonding (H-B) plays an important role for the biothiols sensing mechanism of the fluorescence sensor DCO. Multiple H-B interaction sites exist in DCO and in its Michael addition product DCOT, which then induce the formation of the H-B complexes with water molecules, DCOH2 and DCOTH4. In the first excited state, the intermolecular H-Bs between water molecule and DCO in DCOH2 are cooperatively and generally strengthened and thus induced the weak fluorescence emission of DCO, while the cooperative H-Bs between water molecule and DCOT in DCOTH4 are overall weakened and thus responsible for the enhanced fluorescence emission of DCOT. Moreover, the theoretical results suggest that the blue shift of the UV-Vis absorption spectrum of DCOT can be attributed to the relatively weak excited-state intramolecular charge transfer in DCOT compared to DCO. (Less)
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organization
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Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
volume
118
issue
39
pages
8986 - 8995
publisher
The American Chemical Society
external identifiers
  • wos:000342651200013
  • scopus:84907800536
ISSN
1520-5215
DOI
10.1021/jp501946n
language
English
LU publication?
yes
id
e3fa88d0-44f0-4f27-ac5c-77f2e09a79fb (old id 4796307)
date added to LUP
2014-11-24 16:34:39
date last changed
2017-10-22 04:23:35
@article{e3fa88d0-44f0-4f27-ac5c-77f2e09a79fb,
  abstract     = {The biothiols sensing mechanism of (E)-7-(diethylamino)-3-(2-nitrovinyl)-2H-chromen-2-one (DCO) has been investigated using the density functional theory (DFT) and time-dependent DFT methods. The theoretical results indicate that the excited-state intermolecular hydrogen bonding (H-B) plays an important role for the biothiols sensing mechanism of the fluorescence sensor DCO. Multiple H-B interaction sites exist in DCO and in its Michael addition product DCOT, which then induce the formation of the H-B complexes with water molecules, DCOH2 and DCOTH4. In the first excited state, the intermolecular H-Bs between water molecule and DCO in DCOH2 are cooperatively and generally strengthened and thus induced the weak fluorescence emission of DCO, while the cooperative H-Bs between water molecule and DCOT in DCOTH4 are overall weakened and thus responsible for the enhanced fluorescence emission of DCOT. Moreover, the theoretical results suggest that the blue shift of the UV-Vis absorption spectrum of DCOT can be attributed to the relatively weak excited-state intramolecular charge transfer in DCOT compared to DCO.},
  author       = {Chen, Junsheng and Yuan, Ming-Hu and Wang, Jia-Pei and Yang, Yang and Chu, Tian-Shu},
  issn         = {1520-5215},
  language     = {eng},
  number       = {39},
  pages        = {8986--8995},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory},
  title        = {Sensing Mechanism for Biothiols Chemosensor DCO: Roles of Excited-State Hydrogen-Bonding and Intramolecular Charge Transfer},
  url          = {http://dx.doi.org/10.1021/jp501946n},
  volume       = {118},
  year         = {2014},
}