Stark spectroscopy of the light-harvesting complex II in different oligomerisation states

M.A. Palacios, R.N. Frese, C.C. Gradinaru, I.H.M. van Stokkum, L.L. Premvardhan, P. Horton, A.V. Ruban, R. van Grondelle, H. van Amerongen

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Abstract

The electric field-induced absorption changes (Stark effect) of light-harvesting complex 11 (LHCII) in different oligomerisation states-monomeric, trimeric and aggregated-have been probed at 77 K. All the chlorophyll (Chl) a molecules exhibit electro-optic properties in the Q(y) absorption region characterized by a change in dipole moment \Delta(μ) over right arrow \ = 0.6+/-0.06 D/f and polarizability, Tr(Delta(α) over tilde) similar to 55 +/- 5 Delta(3)/f(2) upon electronic excitation, which are similar to those of unbound monomeric Chl a, indicating the absence of strong delocaliz.ation of the excitations which would be expected in the presence of strong excitonic interactions. The Stark effect in the Chl b absorption region is significantly bigger with \Delta(μ) over right arrow \ values of the order of 2.0 +/- 0.2 D/f and it is attributed to strong interactions with neoxanthin molecules. Clear oligomerisation-dependent differences are observed in the carotenoid region, mainly due to the appearance of a new xanthophyll absorption band at 509 in the spectra of trimers and oligomers. It is ascribed to some lutein molecules, in agreement with previous experimental observations. The electro-optic properties of these lutein molecules are significantly different from those of the other xanthophylls in LHCII, which do not exhibit such a big change in dipole moment upon electronic excitation (\Delta(μ) over right arrow \ = 14.6 +/- 2.0 D/f). Upon aggregation of LHCII some extra absorption appears on the red side of the main Chl a Q(y) absorption band. In contrast to an earlier suggestion [J. Phys. Chem., A 103 (1999) 2422], no indications are found for the charge-transfer character of the corresponding band. The assignments of the S-2 electronic transitions of neoxanthin and lutein in LHCII and possible origins of the Stark effect are discussed. (C) 2003 Elsevier B.V. All rights reserved.
Original languageEnglish
Pages (from-to)83-95
JournalBiochimica et Biophysica Acta. B, Bioenergetics
Volume1605
DOIs
Publication statusPublished - 2003

Fingerprint

Oligomerization
Stark effect
Lutein
Spectrum Analysis
Spectroscopy
Xanthophylls
Light
Molecules
Dipole moment
Electrooptical effects
Absorption spectra
A 103
Carotenoids
Oligomers
Charge transfer
Agglomeration
Electric fields
chlorophyll a
neoxanthin

Keywords

  • carotenoid-binding-sites
  • higher-plants
  • photosystem-ii
  • green plants
  • energy-transfer
  • lhc-ii
  • antenna complex
  • chlorophyll fluorescence
  • electron crystallography
  • chloroplast membranes

Cite this

Palacios, M.A. ; Frese, R.N. ; Gradinaru, C.C. ; van Stokkum, I.H.M. ; Premvardhan, L.L. ; Horton, P. ; Ruban, A.V. ; van Grondelle, R. ; van Amerongen, H. / Stark spectroscopy of the light-harvesting complex II in different oligomerisation states. In: Biochimica et Biophysica Acta. B, Bioenergetics. 2003 ; Vol. 1605. pp. 83-95.
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abstract = "The electric field-induced absorption changes (Stark effect) of light-harvesting complex 11 (LHCII) in different oligomerisation states-monomeric, trimeric and aggregated-have been probed at 77 K. All the chlorophyll (Chl) a molecules exhibit electro-optic properties in the Q(y) absorption region characterized by a change in dipole moment \Delta(μ) over right arrow \ = 0.6+/-0.06 D/f and polarizability, Tr(Delta(α) over tilde) similar to 55 +/- 5 Delta(3)/f(2) upon electronic excitation, which are similar to those of unbound monomeric Chl a, indicating the absence of strong delocaliz.ation of the excitations which would be expected in the presence of strong excitonic interactions. The Stark effect in the Chl b absorption region is significantly bigger with \Delta(μ) over right arrow \ values of the order of 2.0 +/- 0.2 D/f and it is attributed to strong interactions with neoxanthin molecules. Clear oligomerisation-dependent differences are observed in the carotenoid region, mainly due to the appearance of a new xanthophyll absorption band at 509 in the spectra of trimers and oligomers. It is ascribed to some lutein molecules, in agreement with previous experimental observations. The electro-optic properties of these lutein molecules are significantly different from those of the other xanthophylls in LHCII, which do not exhibit such a big change in dipole moment upon electronic excitation (\Delta(μ) over right arrow \ = 14.6 +/- 2.0 D/f). Upon aggregation of LHCII some extra absorption appears on the red side of the main Chl a Q(y) absorption band. In contrast to an earlier suggestion [J. Phys. Chem., A 103 (1999) 2422], no indications are found for the charge-transfer character of the corresponding band. The assignments of the S-2 electronic transitions of neoxanthin and lutein in LHCII and possible origins of the Stark effect are discussed. (C) 2003 Elsevier B.V. All rights reserved.",
keywords = "carotenoid-binding-sites, higher-plants, photosystem-ii, green plants, energy-transfer, lhc-ii, antenna complex, chlorophyll fluorescence, electron crystallography, chloroplast membranes",
author = "M.A. Palacios and R.N. Frese and C.C. Gradinaru and {van Stokkum}, I.H.M. and L.L. Premvardhan and P. Horton and A.V. Ruban and {van Grondelle}, R. and {van Amerongen}, H.",
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doi = "10.1016/S0005-2728(03)00080-X",
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Palacios, MA, Frese, RN, Gradinaru, CC, van Stokkum, IHM, Premvardhan, LL, Horton, P, Ruban, AV, van Grondelle, R & van Amerongen, H 2003, 'Stark spectroscopy of the light-harvesting complex II in different oligomerisation states' Biochimica et Biophysica Acta. B, Bioenergetics, vol. 1605, pp. 83-95. https://doi.org/10.1016/S0005-2728(03)00080-X

Stark spectroscopy of the light-harvesting complex II in different oligomerisation states. / Palacios, M.A.; Frese, R.N.; Gradinaru, C.C.; van Stokkum, I.H.M.; Premvardhan, L.L.; Horton, P.; Ruban, A.V.; van Grondelle, R.; van Amerongen, H.

In: Biochimica et Biophysica Acta. B, Bioenergetics, Vol. 1605, 2003, p. 83-95.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Stark spectroscopy of the light-harvesting complex II in different oligomerisation states

AU - Palacios, M.A.

AU - Frese, R.N.

AU - Gradinaru, C.C.

AU - van Stokkum, I.H.M.

AU - Premvardhan, L.L.

AU - Horton, P.

AU - Ruban, A.V.

AU - van Grondelle, R.

AU - van Amerongen, H.

PY - 2003

Y1 - 2003

N2 - The electric field-induced absorption changes (Stark effect) of light-harvesting complex 11 (LHCII) in different oligomerisation states-monomeric, trimeric and aggregated-have been probed at 77 K. All the chlorophyll (Chl) a molecules exhibit electro-optic properties in the Q(y) absorption region characterized by a change in dipole moment \Delta(μ) over right arrow \ = 0.6+/-0.06 D/f and polarizability, Tr(Delta(α) over tilde) similar to 55 +/- 5 Delta(3)/f(2) upon electronic excitation, which are similar to those of unbound monomeric Chl a, indicating the absence of strong delocaliz.ation of the excitations which would be expected in the presence of strong excitonic interactions. The Stark effect in the Chl b absorption region is significantly bigger with \Delta(μ) over right arrow \ values of the order of 2.0 +/- 0.2 D/f and it is attributed to strong interactions with neoxanthin molecules. Clear oligomerisation-dependent differences are observed in the carotenoid region, mainly due to the appearance of a new xanthophyll absorption band at 509 in the spectra of trimers and oligomers. It is ascribed to some lutein molecules, in agreement with previous experimental observations. The electro-optic properties of these lutein molecules are significantly different from those of the other xanthophylls in LHCII, which do not exhibit such a big change in dipole moment upon electronic excitation (\Delta(μ) over right arrow \ = 14.6 +/- 2.0 D/f). Upon aggregation of LHCII some extra absorption appears on the red side of the main Chl a Q(y) absorption band. In contrast to an earlier suggestion [J. Phys. Chem., A 103 (1999) 2422], no indications are found for the charge-transfer character of the corresponding band. The assignments of the S-2 electronic transitions of neoxanthin and lutein in LHCII and possible origins of the Stark effect are discussed. (C) 2003 Elsevier B.V. All rights reserved.

AB - The electric field-induced absorption changes (Stark effect) of light-harvesting complex 11 (LHCII) in different oligomerisation states-monomeric, trimeric and aggregated-have been probed at 77 K. All the chlorophyll (Chl) a molecules exhibit electro-optic properties in the Q(y) absorption region characterized by a change in dipole moment \Delta(μ) over right arrow \ = 0.6+/-0.06 D/f and polarizability, Tr(Delta(α) over tilde) similar to 55 +/- 5 Delta(3)/f(2) upon electronic excitation, which are similar to those of unbound monomeric Chl a, indicating the absence of strong delocaliz.ation of the excitations which would be expected in the presence of strong excitonic interactions. The Stark effect in the Chl b absorption region is significantly bigger with \Delta(μ) over right arrow \ values of the order of 2.0 +/- 0.2 D/f and it is attributed to strong interactions with neoxanthin molecules. Clear oligomerisation-dependent differences are observed in the carotenoid region, mainly due to the appearance of a new xanthophyll absorption band at 509 in the spectra of trimers and oligomers. It is ascribed to some lutein molecules, in agreement with previous experimental observations. The electro-optic properties of these lutein molecules are significantly different from those of the other xanthophylls in LHCII, which do not exhibit such a big change in dipole moment upon electronic excitation (\Delta(μ) over right arrow \ = 14.6 +/- 2.0 D/f). Upon aggregation of LHCII some extra absorption appears on the red side of the main Chl a Q(y) absorption band. In contrast to an earlier suggestion [J. Phys. Chem., A 103 (1999) 2422], no indications are found for the charge-transfer character of the corresponding band. The assignments of the S-2 electronic transitions of neoxanthin and lutein in LHCII and possible origins of the Stark effect are discussed. (C) 2003 Elsevier B.V. All rights reserved.

KW - carotenoid-binding-sites

KW - higher-plants

KW - photosystem-ii

KW - green plants

KW - energy-transfer

KW - lhc-ii

KW - antenna complex

KW - chlorophyll fluorescence

KW - electron crystallography

KW - chloroplast membranes

U2 - 10.1016/S0005-2728(03)00080-X

DO - 10.1016/S0005-2728(03)00080-X

M3 - Article

VL - 1605

SP - 83

EP - 95

JO - Biochimica et Biophysica Acta. B, Bioenergetics

JF - Biochimica et Biophysica Acta. B, Bioenergetics

SN - 0005-2728

ER -