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Title: Spectroscopic and photochemical properties of open-chain carotenoids.

Abstract

The spectroscopic properties of open-chain, all-trans-C{sub 30} carotenoids having seven, eight and nine {pi}-electron conjugated carbon-carbon double bonds were studied using steady-state absorption, fluorescence, fluorescence excitation and time-resolved absorption spectroscopy. These diapocarotenes were purified by high performance liquid chromatography (HPLC) prior to the spectroscopic experiments. The fluorescence data show a systematic crossover from dominant S{sub 1} {yields} S{sub 0} (2{sup 1}Ag{yields} 1{sup 1}Ag) emission to dominant S{sub 2} {yields} S{sub 0} (1{sup 1}Bu {yields} 1{sup 1}Ag) with increasing extent of conjugation. The low temperatures facilitated the determination of the spectral origins of the S{sub 1} {yields} S{sub 0} (2{sup 1}Ag {yields} 1{sup 1}Ag) emissions, which were assigned by Gaussian deconvolution of the experimental line shapes. The lifetimes of the S{sub 1} states of the molecules were measured by transient absorption spectroscopy and were found to decrease as the conjugated chain length increases. The energy gap law for radiationless transitions is used to correlate the S{sub 1} energies with the dynamics. These molecules provide a systematic series for understanding the structural features that control the photochemical properties of open-chain, diapocarotenoids. The implications of these results on the roles of carotenoids in photosynthetic organisms are discussed.

Authors:
; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Institutes of Health (NIH); National Science Foundation (NSF); FOR
OSTI Identifier:
949639
Report Number(s):
ANL/CHM/JA-42767
Journal ID: ISSN 1089-5647; JPCBFK; TRN: US201012%%422
DOE Contract Number:  
DE-AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
J. Phys. Chem. B
Additional Journal Information:
Journal Volume: 106; Journal Issue: 8 ; Feb. 28, 2002; Journal ID: ISSN 1089-5647
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION; ABSORPTION SPECTROSCOPY; CAROTENOIDS; CHAINS; DOUBLE BONDS; ENERGY GAP; EXCITATION; FLUORESCENCE; HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY; RADIATIONLESS DECAY; TRANSIENTS

Citation Formats

Frank, H A, Josue, J S, Bautista, J A, van der Hoef, I, Jansen, F J, Lugtenburg, J, Wiederrecht, G, Christensen, R L, Chemistry, Univ. of Connecticut, Leiden Univ., and Bowdoin College. Spectroscopic and photochemical properties of open-chain carotenoids.. United States: N. p., 2002. Web. doi:10.1021/jp013321l.
Frank, H A, Josue, J S, Bautista, J A, van der Hoef, I, Jansen, F J, Lugtenburg, J, Wiederrecht, G, Christensen, R L, Chemistry, Univ. of Connecticut, Leiden Univ., & Bowdoin College. Spectroscopic and photochemical properties of open-chain carotenoids.. United States. https://doi.org/10.1021/jp013321l
Frank, H A, Josue, J S, Bautista, J A, van der Hoef, I, Jansen, F J, Lugtenburg, J, Wiederrecht, G, Christensen, R L, Chemistry, Univ. of Connecticut, Leiden Univ., and Bowdoin College. 2002. "Spectroscopic and photochemical properties of open-chain carotenoids.". United States. https://doi.org/10.1021/jp013321l.
@article{osti_949639,
title = {Spectroscopic and photochemical properties of open-chain carotenoids.},
author = {Frank, H A and Josue, J S and Bautista, J A and van der Hoef, I and Jansen, F J and Lugtenburg, J and Wiederrecht, G and Christensen, R L and Chemistry and Univ. of Connecticut and Leiden Univ. and Bowdoin College},
abstractNote = {The spectroscopic properties of open-chain, all-trans-C{sub 30} carotenoids having seven, eight and nine {pi}-electron conjugated carbon-carbon double bonds were studied using steady-state absorption, fluorescence, fluorescence excitation and time-resolved absorption spectroscopy. These diapocarotenes were purified by high performance liquid chromatography (HPLC) prior to the spectroscopic experiments. The fluorescence data show a systematic crossover from dominant S{sub 1} {yields} S{sub 0} (2{sup 1}Ag{yields} 1{sup 1}Ag) emission to dominant S{sub 2} {yields} S{sub 0} (1{sup 1}Bu {yields} 1{sup 1}Ag) with increasing extent of conjugation. The low temperatures facilitated the determination of the spectral origins of the S{sub 1} {yields} S{sub 0} (2{sup 1}Ag {yields} 1{sup 1}Ag) emissions, which were assigned by Gaussian deconvolution of the experimental line shapes. The lifetimes of the S{sub 1} states of the molecules were measured by transient absorption spectroscopy and were found to decrease as the conjugated chain length increases. The energy gap law for radiationless transitions is used to correlate the S{sub 1} energies with the dynamics. These molecules provide a systematic series for understanding the structural features that control the photochemical properties of open-chain, diapocarotenoids. The implications of these results on the roles of carotenoids in photosynthetic organisms are discussed.},
doi = {10.1021/jp013321l},
url = {https://www.osti.gov/biblio/949639}, journal = {J. Phys. Chem. B},
issn = {1089-5647},
number = 8 ; Feb. 28, 2002,
volume = 106,
place = {United States},
year = {Thu Feb 28 00:00:00 EST 2002},
month = {Thu Feb 28 00:00:00 EST 2002}
}