Polymer-Chlorosome Nanocomposites Consisting of Non-Native Combinations of Self-Assembling Bacteriochlorophylls
- Orf, Gregory S. [ Washington Univ, Dept Chem, St Louis, MO 63130 USA ] [ Washington Univ, Dept Biol, Campus Box 1137, St Louis, MO 63130 USA ]
- Collins, Aaron M. [ Los Alamos Natl Lab, Ctr Integrated Nanotechnol, Los Alamos, NM 87545 USA ]
- Niedzwiedzki, Dariusz M. [ Washington Univ, PARC, St Louis, MO 63130 USA ]
- Tank, Marcus [ Penn State Univ, Dept Biochem & Mol Biol, University Pk, PA 16802 USA ] [ Tokyo Metropolitan Univ, Dept Biol Sci, Tokyo 1920397, Japan ]
- Thiel, Vera [ Tokyo Metropolitan Univ, Dept Biol Sci, Tokyo 1920397, Japan ] [ Penn State Univ, Dept Biochem & Mol Biol, University Pk, PA 16802 USA ]
- Kell, Adam [ Kansas State Univ, Dept Chem, Manhattan, KS 66506 USA ]
- Bryant, Donald A. [ Montana State University: Chemistry & Biochemistry ] [ Penn State Univ, Dept Biochem & Mol Biol, University Pk, PA 16802 USA ]
- Montano, Gabriel A. [ Los Alamos Natl Lab, Ctr Integrated Nanotechnol, Los Alamos, NM 87545 USA ]
- Blankenship, Robert E. [ Washington Univ, Dept Biol, Campus Box 1137, St Louis, MO 63130 USA ] [ Washington Univ, Dept Chem, St Louis, MO 63130 USA ] [ Washington Univ, PARC, St Louis, MO 63130 USA ]
Chlorosomes are one of the characteristic light-harvesting antennas from green sulfur bacteria. These complexes represent a unique paradigm: self-assembly of bacteriochlorophyll pigments within a lipid monolayer without the influence of protein. Because of their large size and reduced complexity, they have been targeted as models for the development of bioinspired light-harvesting arrays. We report the production of biohybrid light-harvesting nanocomposites mimicking chlorosomes, composed of amphiphilic diblock copolymer membrane bodies that incorporate thousands of natural self-assembling bacterio-chlorophyll molecules derived from green sulfur bacteria. The driving force behind the assembly of these polymer-chlorosome nanocomposites is the transfer of the mixed raw materials from the organic to the aqueous phase. We incorporated up to five different self-assembling pigment types into single nanocomposites that mimic chlorosome morphology. We establish that the copolymer-BChl self-assembly process works smoothly even when non-native combinations of BChl homologues are included. Spectroscopic characterization revealed that the different types of self-assembling pigments participate in ultrafast energy transfer, expanding beyond single chromophore constraints of the natural chlorosome system. This study further demonstrates the utility of flexible short-chain, diblock copolymers for building scalable, tunable light-harvesting arrays for technological use and allows for an in vitro analysis of the flexibility of natural self-assembling chromophores in unique and controlled combinations.