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Effect of Isomerization on Excited-State Dynamics of Carotenoid Fucoxanthin

Kuznetsova, Valentyna; Chábera, Pavel LU ; Litvín, Radek; Polívka, Tomáš and Fuciman, Marcel (2017) In Journal of Physical Chemistry B 121(17). p.4438-4447
Abstract

Ultrafast transient absorption spectroscopy and single-wavelength anisotropy measurements were used to study the effect of isomerization on the excited-state properties of fucoxanthin in polar and nonpolar solvents. The excitation wavelengths were 477 nm for all-trans-fucoxanthin, and 333 and 477 nm for cis-fucoxanthin. All transient absorption spectra of the fucoxanthin isomers in polar solvents show intramolecular charge transfer (ICT) state features, typical for carbonyl carotenoids. Global analysis of the data requires an additional fitting component, originated from the presence of blue and red forms of fucoxanthin in a polar protic solvent. Here we demonstrate that the ICT state decays faster than the S1 state, due to... (More)

Ultrafast transient absorption spectroscopy and single-wavelength anisotropy measurements were used to study the effect of isomerization on the excited-state properties of fucoxanthin in polar and nonpolar solvents. The excitation wavelengths were 477 nm for all-trans-fucoxanthin, and 333 and 477 nm for cis-fucoxanthin. All transient absorption spectra of the fucoxanthin isomers in polar solvents show intramolecular charge transfer (ICT) state features, typical for carbonyl carotenoids. Global analysis of the data requires an additional fitting component, originated from the presence of blue and red forms of fucoxanthin in a polar protic solvent. Here we demonstrate that the ICT state decays faster than the S1 state, due to the significant contribution of the red form to the ICT state dynamics. The isomerization does not affect the S1 lifetime, but induces a larger difference between the S1- and ICT-state lifetimes in cis-fucoxanthin, which is likely caused by alterations of ICT coupling to either the S1 or S0 states; the S∗-state signal is more pronounced for cis-isomers in a nonpolar solvent.

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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Physical Chemistry B
volume
121
issue
17
pages
10 pages
publisher
The American Chemical Society
external identifiers
  • scopus:85020228024
  • wos:000400881300012
ISSN
1520-6106
DOI
10.1021/acs.jpcb.7b02526
language
English
LU publication?
yes
id
bf0fcf87-7d26-434f-a6b4-3a608fcc33bf
date added to LUP
2017-06-28 10:42:37
date last changed
2017-09-18 11:43:26
@article{bf0fcf87-7d26-434f-a6b4-3a608fcc33bf,
  abstract     = {<p>Ultrafast transient absorption spectroscopy and single-wavelength anisotropy measurements were used to study the effect of isomerization on the excited-state properties of fucoxanthin in polar and nonpolar solvents. The excitation wavelengths were 477 nm for all-trans-fucoxanthin, and 333 and 477 nm for cis-fucoxanthin. All transient absorption spectra of the fucoxanthin isomers in polar solvents show intramolecular charge transfer (ICT) state features, typical for carbonyl carotenoids. Global analysis of the data requires an additional fitting component, originated from the presence of blue and red forms of fucoxanthin in a polar protic solvent. Here we demonstrate that the ICT state decays faster than the S<sub>1</sub> state, due to the significant contribution of the red form to the ICT state dynamics. The isomerization does not affect the S<sub>1</sub> lifetime, but induces a larger difference between the S<sub>1</sub>- and ICT-state lifetimes in cis-fucoxanthin, which is likely caused by alterations of ICT coupling to either the S<sub>1</sub> or S<sub>0</sub> states; the S∗-state signal is more pronounced for cis-isomers in a nonpolar solvent.</p>},
  author       = {Kuznetsova, Valentyna and Chábera, Pavel and Litvín, Radek and Polívka, Tomáš and Fuciman, Marcel},
  issn         = {1520-6106},
  language     = {eng},
  month        = {05},
  number       = {17},
  pages        = {4438--4447},
  publisher    = {The American Chemical Society},
  series       = {Journal of Physical Chemistry B},
  title        = {Effect of Isomerization on Excited-State Dynamics of Carotenoid Fucoxanthin},
  url          = {http://dx.doi.org/10.1021/acs.jpcb.7b02526},
  volume       = {121},
  year         = {2017},
}