Cation radicals of xanthophylls

Mary Grace Ignacio Galinato, Dariusz Niedzwiedzki, Cailin Deal, Robert R. Birge, Harry A. Frank

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

Carotenes and xanthophylls are well known to act as electron donors in redox processes. This ability is thought to be associated with the inhibition of oxidative reactions in reaction centers and light-harvesting pigment-protein complexes of photosystem II (PSII). In this work, cation radicals of neoxanthin, violaxanthin, lutein, zeaxanthin, β-cryptoxanthin, β-carotene, and lycopene were generated in solution using ferric chloride as an oxidant and then studied by absorption spectroscopy. The investigation provides a view toward understanding the molecular features that determine the spectral properties of cation radicals of carotenoids. The absorption spectral data reveal a shift to longer wavelength with increasing π-chain length. However, zeaxanthin and β-cryptoxanthin exhibit cation radical spectra blue-shifted compared to that of β-carotene, despite all of these molecules having 11 conjugated carbon-carbon double bonds. CIS molecular orbital theory quantum computations interpret this effect as due to the hydroxyl groups in the terminal rings selectively stabilizing the highest occupied molecular orbitals of preferentially populated s-trans-isomers. The data are expected to be useful in the analysis of spectral results from PSII pigment-protein complexes seeking to understand the role of carotene and xanthophyll cation radicals in regulating excited state energy flow, in protecting PSII reaction centers against photoinhibition, and in dissipating excess light energy absorbed by photosynthetic organisms but not used for photosynthesis.

Original languageEnglish (US)
Pages (from-to)67-78
Number of pages12
JournalPhotosynthesis research
Volume94
Issue number1
DOIs
StatePublished - Oct 1 2007

Fingerprint

Xanthophylls
xanthophylls
Carotenoids
carotenes
Cations
cations
Photosystem II Protein Complex
photosystem II
zeaxanthin
lutein
spectral analysis
Molecular orbitals
Pigments
pigments
neoxanthin
Light-Harvesting Protein Complexes
Carbon
Quantum Theory
violaxanthin
carbon

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Plant Science
  • Cell Biology

Cite this

Galinato, M. G. I., Niedzwiedzki, D., Deal, C., Birge, R. R., & Frank, H. A. (2007). Cation radicals of xanthophylls. Photosynthesis research, 94(1), 67-78. https://doi.org/10.1007/s11120-007-9218-5
Galinato, Mary Grace Ignacio ; Niedzwiedzki, Dariusz ; Deal, Cailin ; Birge, Robert R. ; Frank, Harry A. / Cation radicals of xanthophylls. In: Photosynthesis research. 2007 ; Vol. 94, No. 1. pp. 67-78.
@article{f76db5cf60a444b38601eba2034274f3,
title = "Cation radicals of xanthophylls",
abstract = "Carotenes and xanthophylls are well known to act as electron donors in redox processes. This ability is thought to be associated with the inhibition of oxidative reactions in reaction centers and light-harvesting pigment-protein complexes of photosystem II (PSII). In this work, cation radicals of neoxanthin, violaxanthin, lutein, zeaxanthin, β-cryptoxanthin, β-carotene, and lycopene were generated in solution using ferric chloride as an oxidant and then studied by absorption spectroscopy. The investigation provides a view toward understanding the molecular features that determine the spectral properties of cation radicals of carotenoids. The absorption spectral data reveal a shift to longer wavelength with increasing π-chain length. However, zeaxanthin and β-cryptoxanthin exhibit cation radical spectra blue-shifted compared to that of β-carotene, despite all of these molecules having 11 conjugated carbon-carbon double bonds. CIS molecular orbital theory quantum computations interpret this effect as due to the hydroxyl groups in the terminal rings selectively stabilizing the highest occupied molecular orbitals of preferentially populated s-trans-isomers. The data are expected to be useful in the analysis of spectral results from PSII pigment-protein complexes seeking to understand the role of carotene and xanthophyll cation radicals in regulating excited state energy flow, in protecting PSII reaction centers against photoinhibition, and in dissipating excess light energy absorbed by photosynthetic organisms but not used for photosynthesis.",
author = "Galinato, {Mary Grace Ignacio} and Dariusz Niedzwiedzki and Cailin Deal and Birge, {Robert R.} and Frank, {Harry A.}",
year = "2007",
month = "10",
day = "1",
doi = "10.1007/s11120-007-9218-5",
language = "English (US)",
volume = "94",
pages = "67--78",
journal = "Photosynthesis Research",
issn = "0166-8595",
publisher = "Springer Netherlands",
number = "1",

}

Galinato, MGI, Niedzwiedzki, D, Deal, C, Birge, RR & Frank, HA 2007, 'Cation radicals of xanthophylls', Photosynthesis research, vol. 94, no. 1, pp. 67-78. https://doi.org/10.1007/s11120-007-9218-5

Cation radicals of xanthophylls. / Galinato, Mary Grace Ignacio; Niedzwiedzki, Dariusz; Deal, Cailin; Birge, Robert R.; Frank, Harry A.

In: Photosynthesis research, Vol. 94, No. 1, 01.10.2007, p. 67-78.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Cation radicals of xanthophylls

AU - Galinato, Mary Grace Ignacio

AU - Niedzwiedzki, Dariusz

AU - Deal, Cailin

AU - Birge, Robert R.

AU - Frank, Harry A.

PY - 2007/10/1

Y1 - 2007/10/1

N2 - Carotenes and xanthophylls are well known to act as electron donors in redox processes. This ability is thought to be associated with the inhibition of oxidative reactions in reaction centers and light-harvesting pigment-protein complexes of photosystem II (PSII). In this work, cation radicals of neoxanthin, violaxanthin, lutein, zeaxanthin, β-cryptoxanthin, β-carotene, and lycopene were generated in solution using ferric chloride as an oxidant and then studied by absorption spectroscopy. The investigation provides a view toward understanding the molecular features that determine the spectral properties of cation radicals of carotenoids. The absorption spectral data reveal a shift to longer wavelength with increasing π-chain length. However, zeaxanthin and β-cryptoxanthin exhibit cation radical spectra blue-shifted compared to that of β-carotene, despite all of these molecules having 11 conjugated carbon-carbon double bonds. CIS molecular orbital theory quantum computations interpret this effect as due to the hydroxyl groups in the terminal rings selectively stabilizing the highest occupied molecular orbitals of preferentially populated s-trans-isomers. The data are expected to be useful in the analysis of spectral results from PSII pigment-protein complexes seeking to understand the role of carotene and xanthophyll cation radicals in regulating excited state energy flow, in protecting PSII reaction centers against photoinhibition, and in dissipating excess light energy absorbed by photosynthetic organisms but not used for photosynthesis.

AB - Carotenes and xanthophylls are well known to act as electron donors in redox processes. This ability is thought to be associated with the inhibition of oxidative reactions in reaction centers and light-harvesting pigment-protein complexes of photosystem II (PSII). In this work, cation radicals of neoxanthin, violaxanthin, lutein, zeaxanthin, β-cryptoxanthin, β-carotene, and lycopene were generated in solution using ferric chloride as an oxidant and then studied by absorption spectroscopy. The investigation provides a view toward understanding the molecular features that determine the spectral properties of cation radicals of carotenoids. The absorption spectral data reveal a shift to longer wavelength with increasing π-chain length. However, zeaxanthin and β-cryptoxanthin exhibit cation radical spectra blue-shifted compared to that of β-carotene, despite all of these molecules having 11 conjugated carbon-carbon double bonds. CIS molecular orbital theory quantum computations interpret this effect as due to the hydroxyl groups in the terminal rings selectively stabilizing the highest occupied molecular orbitals of preferentially populated s-trans-isomers. The data are expected to be useful in the analysis of spectral results from PSII pigment-protein complexes seeking to understand the role of carotene and xanthophyll cation radicals in regulating excited state energy flow, in protecting PSII reaction centers against photoinhibition, and in dissipating excess light energy absorbed by photosynthetic organisms but not used for photosynthesis.

UR - http://www.scopus.com/inward/record.url?scp=34548192056&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=34548192056&partnerID=8YFLogxK

U2 - 10.1007/s11120-007-9218-5

DO - 10.1007/s11120-007-9218-5

M3 - Article

C2 - 17638112

AN - SCOPUS:34548192056

VL - 94

SP - 67

EP - 78

JO - Photosynthesis Research

JF - Photosynthesis Research

SN - 0166-8595

IS - 1

ER -

Galinato MGI, Niedzwiedzki D, Deal C, Birge RR, Frank HA. Cation radicals of xanthophylls. Photosynthesis research. 2007 Oct 1;94(1):67-78. https://doi.org/10.1007/s11120-007-9218-5