Abstract

Bio-hybrid nanomaterials have great potential for combining the most desirable aspects of biomolecules and the contemporary concepts of nanotechnology to create highly efficient light-harvesting materials. Light-harvesting proteins are optimized to absorb and transfer solar energy with remarkable efficiency but have a spectral range that is limited by their natural pigment complement. Herein, we present the development of model membranes ("proteoliposomes") in which the absorption range of the membrane protein Light-Harvesting Complex II (LHCII) is effectively enhanced by the addition of lipid-tethered Texas Red (TR) chromophores. Energy transfer from TR to LHCII is observed with up to 94% efficiency and increased LHCII fluorescence of up to three-fold when excited in the region of lowest natural absorption. The new self-assembly procedure offers the modularity to control the concentrations incorporated of TR and LHCII, allowing energy transfer and fluorescence to be tuned. Fluorescence Lifetime Imaging Microscopy provides single-proteoliposome-level quantification of energy transfer efficiency and confirms that functionality is retained on surfaces. Designer proteoliposomes could act as a controllable light-harvesting nanomaterial and are a promising step in the development of bio-hybrid light-harvesting systems.

Highlights

  • Biological systems are a source of inspiration in solar energy and nanotechnology research,[1,2,3,4,5,6] because the early stages of energy absorption and transfer in photosynthesis have an 16284 | Nanoscale, 2019, 11, 16284–16292Communication tration, (iv) membranes allow the potential to coassemble other components to make for a modular system.Solution-based fluorescence spectroscopy is typically used to assess Förster Resonance Energy Transfer (FRET) in ensemble measurements

  • Light-Harvesting Complex II (LHCII) protein was extracted from spinach leaves and biochemically purified using the detergent α-DDM, as previously described.[30]

  • We chose the small organic chromophore Texas Red (TR)[32] as an ideal candidate for an energy donor to LHCII in membranes because of its complementary spectral properties and its amenability to assembly into lipid bilayers by tethering it to a lipid headgroup (TR-DHPE, as purchased).[33]

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Summary

Introduction

Biological systems are a source of inspiration in solar energy and nanotechnology research,[1,2,3,4,5,6] because the early stages of energy absorption and transfer in photosynthesis have an 16284 | Nanoscale, 2019, 11, 16284–16292Communication tration (or type), (iv) membranes allow the potential to coassemble other components to make for a modular system (e.g. other photosynthetic proteins or any small amphiphiles).Solution-based fluorescence spectroscopy is typically used to assess FRET in ensemble measurements.

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