Molecular interactions of photosystem I and ZIF-8 in bio-nanohybrid materials

Bio-nanohybrid devices featuring natural photocatalysts bound to a nanostructure hold great promise in the search for sustainable energy conversion. One of the major challenges of integrating biological systems is protecting them against harsh environmental conditions while retaining, or ideally enhancing their photophysical properties. In this mainly computational work we investigate an assembly of cyanobacterial photosystem I (PS I) embedded in a metal-organic framework (MOF), namely the zeolitic imidazolate framework ZIF-8. This complex has been reported experimentally [Bennett et al., Nanoscale Adv., 2019, 1, 94] but so far the molecular interactions between PS I and the MOF remained elusive. We show via absorption spectroscopy that PS I remains intact throughout the encapsulation-release cycle. Molecular dynamics (MD) simulations further confirm that the encapsulation has no noticeable structural impact on the photosystem. However, the MOF building blocks frequently coordinate to the Mg²⁺ ions of chlorophylls in the periphery of the antenna complex. High-level quantum mechanical calculations reveal charge-transfer interactions, which affect the excitonic network and thereby may reversibly change the fluorescence properties of PS I. Nevertheless, our results highlight the stability of PS I in the MOF, as the reaction center remains unimpeded by the heterogeneous environment, paving the way for applications in the foreseeable future.