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ID 37980
file
creator
Morishima, Fumiya
NDC
Chemistry
abstract
The structures of estrogens (estrone, β-estradiol, estriol) and their 1:1 hydrogen-bonded (hydrated) clusters with water formed in supersonic jets have been investigated by various laser spectroscopic methods and quantum chemical calculations. In the S1-S0 electronic spectra, all the three species exhibit the band origin in the 35050-35200 cm-1 region. By applying ultraviolet-ultraviolet hole-burning (UV-UV HB) spectroscopy, two conformers, four conformers and eight conformers, arising from different orientation of OH group(s) in the A-ring and D-ring, were are identified for estrone, β-estradiol, and estriol, respectively. The Infrared-ultraviolet double resonance (IR-UV DR) spectra in the OH stretching vibration were observed to discriminate different conformers of the D-ring OH for β-estradiol and estriol, and it is suggested that in estriol only the intramolecular hydrogen bonded conformer exists in the jet. For the 1:1 hydrated cluster of estrogens, the S1-S0 electronic transition energy is quite different depending on whether the water molecule is bound to A-ring OH or D-ring OH. It is found that the water molecule prefers to form an H-bond to the A-ring OH for estrone and β-estradiol due to the higher acidity of phenolic OH than that of the alcoholic OH. On the other hand, in estriol the water molecule prefers to be bound to the D-ring OH due to the formation of a stable ring-structure H-bonding network with two OH groups. From these results, we conclude that estriol has a hydrogen bonding ability quite different from that of β-estradiol although their difference is just only one substituent.
description
This is a preprint of an article published by American Chemical Society in Journal of Physical Chemistry A, 2013, available online: http://pubs.acs.org/doi/abs/10.1021/jp407438j.
journal title
Journal of Physical Chemistry A
volume
Volume 117
issue
Issue 50
start page
13543
end page
13555
date of issued
2013-12-09
publisher
American Chemical Society
issn
1089-5639
publisher doi
pubmed id
language
eng
nii type
Journal Article
HU type
Journal Articles
DCMI type
text
format
application/pdf
text version
author
rights
Copyright (c) 2013 American Chemical Society
relation is version of URL
http://dx.doi.org/10.1021/jp407438j
department
Graduate School of Science



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