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Femtosecond visible transient absorption spectroscopy of chlorophyll f- containing Photosystem II

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Title: Femtosecond visible transient absorption spectroscopy of chlorophyll f- containing Photosystem II
Authors: Zamzam, N
Rakowski, R
Kaucikas, M
Dorlhiac, G
Viola, S
Nurnberg, D
Fantuzzi, A
Rutherford, A
Van Thor, J
Item Type: Journal Article
Abstract: The recently discovered, chlorophyll-f-containing, far-red photosystem II (FR-PSII) supports far-red light photosynthesis. Participation and kinetics of spectrally shifted far-red pigments are directly observable and separated from that of bulk chlorophyll-a. We present an ultrafast transient absorption study of FR-PSII, investigating energy transfer and charge separation processes. Results show a rapid subpicosecond energy transfer from chlorophyll-a to the long-wavelength chlorophylls-f/d. The data demonstrate the decay of an ∼720-nm negative feature on the picosecond-to-nanosecond timescales, coinciding with charge separation, secondary electron transfer, and stimulated emission decay. An ∼675-nm bleach attributed to the loss of chl-a absorption due to the formation of a cation radical, PD1+•, is only fully developed in the nanosecond spectra, indicating an unusually delayed formation. A major spectral feature on the nanosecond timescale at 725 nm is attributed to an electrochromic blue shift of a FR-chlorophyll among the reaction center pigments. These time-resolved observations provide direct experimental support for the model of Nürnberg et al. [D. J. Nürnberg et al., Science 360, 1210–1213 (2018)], in which the primary electron donor is a FR-chlorophyll and the secondary donor is chlorophyll-a (PD1 of the central chlorophyll pair). Efficient charge separation also occurs using selective excitation of long-wavelength chlorophylls-f/d, and the localization of the excited state on P720* points to a smaller (entropic) energy loss compared to conventional PSII, where the excited state is shared over all of the chlorin pigments. This has important repercussions on understanding the overall energetics of excitation energy transfer and charge separation reactions in FR-PSII.
Issue Date: 31-Aug-2020
Date of Acceptance: 28-Jul-2020
URI: http://hdl.handle.net/10044/1/82099
DOI: 10.1073/pnas.2006016117
ISSN: 0027-8424
Publisher: National Academy of Sciences
Start Page: 1
End Page: 7
Journal / Book Title: Proceedings of the National Academy of Sciences of USA
Volume: 117
Issue: 37
Copyright Statement: © 2020 The Author(s). Published under the PNAS license.
Sponsor/Funder: The Leverhulme Trust
The Leverhulme Trust
Funder's Grant Number: RPG-2014-126
Keywords: chlorophyll-f
photosystem II
Publication Status: Published
Online Publication Date: 2020-08-31
Appears in Collections:Faculty of Natural Sciences