Imperial College London
Alternate

Professor Bill Rutherford FRS

Faculty of Natural Sciences, Department of Life Sciences

Chair in Biochemistry of Solar Energy
 
 
 
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Contact

 

+44 (0)20 7594 5329a.rutherford Website

 
 
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Location

 

702Sir Ernst Chain BuildingSouth Kensington Campus

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Summary

 

Publications

Citation

BibTex format

@article{Zamzam:2020:10.1073/pnas.2006016117,
author = {Zamzam, N and Rakowski, R and Kaucikas, M and Dorlhiac, G and Viola, S and Nurnberg, D and Fantuzzi, A and Rutherford, A and van, Thor J},
doi = {10.1073/pnas.2006016117},
journal = {Proceedings of the National Academy of Sciences of USA},
pages = {1--7},
title = {Femtosecond visible transient absorption spectroscopy of chlorophyll f- containing Photosystem II},
url = {http://dx.doi.org/10.1073/pnas.2006016117},
volume = {117},
year = {2020}
}
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RIS format (EndNote, RefMan)

TY  - JOUR
AB  - 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.
AU  - Zamzam,N
AU  - Rakowski,R
AU  - Kaucikas,M
AU  - Dorlhiac,G
AU  - Viola,S
AU  - Nurnberg,D
AU  - Fantuzzi,A
AU  - Rutherford,A
AU  - van,Thor J
DO  - 10.1073/pnas.2006016117
EP  - 7
PY  - 2020///
SN  - 0027-8424
SP  - 1
TI  - Femtosecond visible transient absorption spectroscopy of chlorophyll f- containing Photosystem II
T2  - Proceedings of the National Academy of Sciences of USA
UR  - http://dx.doi.org/10.1073/pnas.2006016117
UR  - https://www.pnas.org/content/117/37/23158/tab-article-info
UR  - http://hdl.handle.net/10044/1/82099
VL  - 117
ER  -
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