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Zeitschrift für Physikalische Chemie

International journal of research in physical chemistry and chemical physics

Editor-in-Chief: Rademann, Klaus

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Volume 229, Issue 10-12


Excited State Dynamics of Selected All-trans C40 Xanthophyll Carotenoids

Florian Ehlers
  • Georg-August-Universität Göttingen, Institut für Physikalische Chemie, Tammannstr. 6, 37077 Göttingen, Germany
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/ Mirko Scholz / Thomas Lenzer / Kawon Oum
Published Online: 2015-07-24 | DOI: https://doi.org/10.1515/zpch-2015-0605


We investigated the excited state dynamics of selected all-trans C40 xanthophyll carotenoids by ultrafast pump-supercontinuum probe (PSCP) spectroscopy in the spectral range 350–770 nm upon photoexcitation by a femtosecond laser (ca. 80 fs pulse length) near 500 nm in acetone. The following carotenoids were selected considering a systematic variation of the number and position of carbonyl (CO) and hydroxyl (OH) functional groups on the β-ionone rings and the change of the effective conjugation length of the polyene system: β-cryptoxanthin (1), echinenone (2), 3-hydroxyechinenone (3), 3′-hydroxyechinenone (4), canthaxanthin (5), adonirubin (6) and astaxanthin (7). The carotenoids featuring an increasing conjugation length, for example, (1), (3) and (6), showed a systematically shorter S1 lifetime of 8.7, 6.2 and 4.7 ps, respectively. Carotenoids with OH groups adjacent to a CO group showed slightly broader steady-state and transient absorption bands, but the influence on the S1 lifetime was minor compared to the case of CO substitution. Moreover, in all cases we observed clearly visible “S* signals”, namely a longer-lived characteristic S0 → S2 red-edge absorption and a negative signal in the S0 → S2 bleach region. This spectral signature is assigned to highly vibrationally excited molecules in the ground electronic state S0* which are generated by internal conversion from S1. The S0* species cool with a time constant of 9.2–9.6 ps in the case of the keto-substituted carotenoids (2)–(7), whereas we obtain a larger value of 13.2 ps for (1) which does not have a keto group. Our findings are supported by results from a global kinetic analysis procedure.

Keywords: Kinetics; Xanthophyll Carotenoids; Ultrafast Dynamics; Collisional Energy Transfer

About the article

Accepted: 2015-06-18

Received: 2015-03-29

Published Online: 2015-07-24

Published in Print: 2015-10-28

Citation Information: Zeitschrift für Physikalische Chemie, Volume 229, Issue 10-12, Pages 1815–1830, ISSN (Online) 2196-7156, ISSN (Print) 0942-9352, DOI: https://doi.org/10.1515/zpch-2015-0605.

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Archives of Biochemistry and Biophysics, 2018
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The Journal of Physical Chemistry A, 2017

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