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Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

New Perspectives on Photosystem II Reaction Centres

Jeremy Hall A , Rafael Picorel B , Nicholas Cox A , Robin Purchase A and Elmars Krausz https://orcid.org/0000-0002-8536-6890 A C
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A Research School of Chemistry, Australian National University, Canberra, ACT 2601, Australia.

B Estacion Experimental de Aula Dei (CSIC), Avda. Montañana 1005, 50059-Zaragoza, Spain.

C Corresponding author. Email: elmars.krausz@anu.edu.au

Australian Journal of Chemistry 73(8) 669-676 https://doi.org/10.1071/CH19478
Submitted: 27 September 2019  Accepted: 12 November 2019   Published: 12 March 2020

Abstract

We apply the differential optical spectroscopy techniques of circular polarisation of luminescence (CPL) and magnetic CPL (MCPL) to the study of isolated reaction centres (RCs) of photosystem II (PS II). The data and subsequent analysis provide insights into aspects of the RC chromophore site energies, exciton couplings, and heterogeneities. CPL measurements are able to identify weak luminescence associated with the unbound chlorophyll-a (Chl-a) present in the sample. The overall sign and magnitude of the CPL observed relates well to the circular dichroism (CD) of the sample. Both CD and CPL are reasonably consistent with modelling of the RC exciton structure. The MCPL observed for the free Chl-a luminescence component in the RC samples is also easily understandable, but the MCPL seen near 680 nm at 1.8 K is anomalous, appearing to have a narrow, strongly negative component. A negative sign is inconsistent with MCPL of (exciton coupled) Qy states of either Chl-a or pheophytin-a (Pheo-a). We propose that this anomaly may arise as a result of the luminescence from a transient excited state species created following photo-induced charge separation within the RC. A comparison of CD spectra and modelling of RC preparations having a different number of pigments suggests that the non-conservative nature of the CD spectra observed is associated with the ‘special pair’ pigments PD1 and PD2.


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