A simple artificial light-harvesting dyad as a model for excess energy dissipation in oxygenic photosynthesis

R. Berera, C. Herrero, L.H.M. van Stokkum, M. Vengris, G. Kodis, R.E. Palacios, H. van Amerongen, R. van Grondelle, D. Gust, T.A. Moore, A.L. Moore, J.T.M. Kennis

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

Under excess illumination, plant photosystem II dissipates excess energy through the quenching of chlorophyll fluorescence, a process known as nonphotochemical quenching. Activation of non-photochemical quenching has been linked to the conversion of a carotenoid with a conjugation length of nine double bonds (violaxanthin) into an 11-double-bond carotenoid (zeaxanthin). It has been suggested that the increase in the conjugation length turns the carotenoid from a nonquencher into a quencher of chlorophyll singlet excited states, but unequivocal evidence is lacking. Here, we present a transient absorption spectroscopic study on a model system made up of a zinc phthalocyanine (Pc) molecule covalently linked to carotenoids with 9, 10, or 11 conjugated carbon-carbon double bonds. We show that a carotenoid can act as an acceptor of Pc excitation energy, thereby shortening its singlet excited-state lifetime. The conjugation length of the carotenoid is critical to the quenching process. Remarkably, the addition of only one double bond can turn the carotenoid from a nonquencher into a very strong quencher. By studying the solvent polarity dependence of the quenching using target analysis of the time-resolved data, we show that the quenching proceeds through energy transfer from the excited Pc to the optically forbidden S
Original languageEnglish
Pages (from-to)5343-5348
JournalProceedings of the National Academy of Sciences of the United States of America
Volume103
Issue number14
DOIs
Publication statusPublished - 2006

Fingerprint

Photosynthesis
Carotenoids
Energy dissipation
Quenching
Chlorophyll
Excited states
Carbon
Photosystem II Protein Complex
Excitation energy
Energy transfer
Lighting
Fluorescence
Chemical activation
Molecules

Bibliographical note

A simple artificial light-harvesting dyad as a model for excess energy dissipation in oxygenic photosynthesis

Cite this

Berera, R. ; Herrero, C. ; van Stokkum, L.H.M. ; Vengris, M. ; Kodis, G. ; Palacios, R.E. ; van Amerongen, H. ; van Grondelle, R. ; Gust, D. ; Moore, T.A. ; Moore, A.L. ; Kennis, J.T.M. / A simple artificial light-harvesting dyad as a model for excess energy dissipation in oxygenic photosynthesis. In: Proceedings of the National Academy of Sciences of the United States of America. 2006 ; Vol. 103, No. 14. pp. 5343-5348.
@article{2b3626326b024145b6b9370d4eb0f3e1,
title = "A simple artificial light-harvesting dyad as a model for excess energy dissipation in oxygenic photosynthesis",
abstract = "Under excess illumination, plant photosystem II dissipates excess energy through the quenching of chlorophyll fluorescence, a process known as nonphotochemical quenching. Activation of non-photochemical quenching has been linked to the conversion of a carotenoid with a conjugation length of nine double bonds (violaxanthin) into an 11-double-bond carotenoid (zeaxanthin). It has been suggested that the increase in the conjugation length turns the carotenoid from a nonquencher into a quencher of chlorophyll singlet excited states, but unequivocal evidence is lacking. Here, we present a transient absorption spectroscopic study on a model system made up of a zinc phthalocyanine (Pc) molecule covalently linked to carotenoids with 9, 10, or 11 conjugated carbon-carbon double bonds. We show that a carotenoid can act as an acceptor of Pc excitation energy, thereby shortening its singlet excited-state lifetime. The conjugation length of the carotenoid is critical to the quenching process. Remarkably, the addition of only one double bond can turn the carotenoid from a nonquencher into a very strong quencher. By studying the solvent polarity dependence of the quenching using target analysis of the time-resolved data, we show that the quenching proceeds through energy transfer from the excited Pc to the optically forbidden S",
author = "R. Berera and C. Herrero and {van Stokkum}, L.H.M. and M. Vengris and G. Kodis and R.E. Palacios and {van Amerongen}, H. and {van Grondelle}, R. and D. Gust and T.A. Moore and A.L. Moore and J.T.M. Kennis",
note = "A simple artificial light-harvesting dyad as a model for excess energy dissipation in oxygenic photosynthesis",
year = "2006",
doi = "10.1073/pnas.0508530103",
language = "English",
volume = "103",
pages = "5343--5348",
journal = "Proceedings of the National Academy of Sciences of the United States of America",
issn = "0027-8424",
publisher = "National Acad Sciences",
number = "14",

}

A simple artificial light-harvesting dyad as a model for excess energy dissipation in oxygenic photosynthesis. / Berera, R.; Herrero, C.; van Stokkum, L.H.M.; Vengris, M.; Kodis, G.; Palacios, R.E.; van Amerongen, H.; van Grondelle, R.; Gust, D.; Moore, T.A.; Moore, A.L.; Kennis, J.T.M.

In: Proceedings of the National Academy of Sciences of the United States of America, Vol. 103, No. 14, 2006, p. 5343-5348.

Research output: Contribution to JournalArticleAcademicpeer-review

TY - JOUR

T1 - A simple artificial light-harvesting dyad as a model for excess energy dissipation in oxygenic photosynthesis

AU - Berera, R.

AU - Herrero, C.

AU - van Stokkum, L.H.M.

AU - Vengris, M.

AU - Kodis, G.

AU - Palacios, R.E.

AU - van Amerongen, H.

AU - van Grondelle, R.

AU - Gust, D.

AU - Moore, T.A.

AU - Moore, A.L.

AU - Kennis, J.T.M.

N1 - A simple artificial light-harvesting dyad as a model for excess energy dissipation in oxygenic photosynthesis

PY - 2006

Y1 - 2006

N2 - Under excess illumination, plant photosystem II dissipates excess energy through the quenching of chlorophyll fluorescence, a process known as nonphotochemical quenching. Activation of non-photochemical quenching has been linked to the conversion of a carotenoid with a conjugation length of nine double bonds (violaxanthin) into an 11-double-bond carotenoid (zeaxanthin). It has been suggested that the increase in the conjugation length turns the carotenoid from a nonquencher into a quencher of chlorophyll singlet excited states, but unequivocal evidence is lacking. Here, we present a transient absorption spectroscopic study on a model system made up of a zinc phthalocyanine (Pc) molecule covalently linked to carotenoids with 9, 10, or 11 conjugated carbon-carbon double bonds. We show that a carotenoid can act as an acceptor of Pc excitation energy, thereby shortening its singlet excited-state lifetime. The conjugation length of the carotenoid is critical to the quenching process. Remarkably, the addition of only one double bond can turn the carotenoid from a nonquencher into a very strong quencher. By studying the solvent polarity dependence of the quenching using target analysis of the time-resolved data, we show that the quenching proceeds through energy transfer from the excited Pc to the optically forbidden S

AB - Under excess illumination, plant photosystem II dissipates excess energy through the quenching of chlorophyll fluorescence, a process known as nonphotochemical quenching. Activation of non-photochemical quenching has been linked to the conversion of a carotenoid with a conjugation length of nine double bonds (violaxanthin) into an 11-double-bond carotenoid (zeaxanthin). It has been suggested that the increase in the conjugation length turns the carotenoid from a nonquencher into a quencher of chlorophyll singlet excited states, but unequivocal evidence is lacking. Here, we present a transient absorption spectroscopic study on a model system made up of a zinc phthalocyanine (Pc) molecule covalently linked to carotenoids with 9, 10, or 11 conjugated carbon-carbon double bonds. We show that a carotenoid can act as an acceptor of Pc excitation energy, thereby shortening its singlet excited-state lifetime. The conjugation length of the carotenoid is critical to the quenching process. Remarkably, the addition of only one double bond can turn the carotenoid from a nonquencher into a very strong quencher. By studying the solvent polarity dependence of the quenching using target analysis of the time-resolved data, we show that the quenching proceeds through energy transfer from the excited Pc to the optically forbidden S

U2 - 10.1073/pnas.0508530103

DO - 10.1073/pnas.0508530103

M3 - Article

VL - 103

SP - 5343

EP - 5348

JO - Proceedings of the National Academy of Sciences of the United States of America

JF - Proceedings of the National Academy of Sciences of the United States of America

SN - 0027-8424

IS - 14

ER -