Abstract
The distinct photochemical and electrochemical properties of single-walled carbon nanotubes (SWCNTs) boosted the research interest in nanomaterial utilization in different in vivo and in vitro photosynthetic biohybrid setups. Aiming to unravel the yet not fully understood energetic interactions between the nanotubes and photosynthetic pigment–protein assemblies in an aqueous milieu, we studied SWCNT effects on the photochemical reactions of isolated thylakoid membranes (TMs), Photosystem II (PSII)-enriched membrane fragments and light-harvesting complexes (LHCII). The SWCNTs induced quenching of the steady-state chlorophyll fluorescence in the TM-biohybrid systems with a corresponding shortening of the average fluorescence lifetimes. The effect was not related to changes in the integrity and macroorganization of the photosynthetic membranes. Moreover, we found no evidence for direct excitation energy exchange between the SWCNTs and pigment–protein complexes, since neither the steady-state nor time-resolved fluorescence of LHCII-biohybrid systems differed from the corresponding controls. The attenuation of the fluorescence signal in the TM-biohybrid systems indicates possible leakage of photosynthetic electrons toward the nanotubes that most probably occurs at the level of the PSII acceptor site. Although it is too early to speculate on the nature of the involved electron donors and intermediate states, the observed energetic interaction could be exploited to increase the photoelectron capture efficiency of natural biohybrid systems for solar energy conversion.
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Acknowledgements
The authors thank Dr. András Kincses for carrying out electrokinetic mobility measurements on SWCNTs.
Funding
This work was partially funded by the Short Term Mobility program of CNR supporting the visit of M.D.L. to the Laboratory of Photosynthetic Membranes, BRC, Hungary. M.D.L. acknowledges financial support from the Bilateral Scientific and Technological Cooperation CNR-RFBR Italy/Russia within the Joint Research Project Lambreva/Rubin, 2015–2017. This work was supported by grants from the National Research Development and Innovation Fund Hungary (FK-139067 to P.A. and PD-138498 to G.S.) and the Eötvös Loránd Research Network (SA-76/2021 to P.A.).
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MDL, PA and PHL performed the experiments and analyzed data; PA was responsible for TM, BBY and LHCII sample preparation; MDL and AM performed SWCNT functionalization; G.S. performed electrochromic shift spectroscopy; MDL and PHL conceived the study, conceptualized data and drafted the original manuscript. All the authors read, edited, and approved the final manuscript.
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Lambreva, M.D., Akhtar, P., Sipka, G. et al. Fluorescence quenching in thylakoid membranes induced by single-walled carbon nanotubes. Photochem Photobiol Sci 22, 1625–1635 (2023). https://doi.org/10.1007/s43630-023-00403-7
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DOI: https://doi.org/10.1007/s43630-023-00403-7