Integration of multiple chromophores with native photosynthetic antennas to enhance solar energy capture and delivery

Michelle A. Harris, Pamela S. Parkes-Loach, Joseph W. Springer, Jianbing Jiang, Elizabeth C. Martin, Pu Qian, Jieying Jiao, Dariusz M. Niedzwiedzki, Christine Kirmaier, John D. Olsen, David F. Bocian, Dewey Holten, C. Neil Hunter, Jonathan S. Lindsey, Paul A. Loach*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

28 Scopus citations

Abstract

Native length bacterial light-harvesting peptides carrying covalently attached designer chromophores have been created that self-assemble with native bacteriochlorophyll a (BChl a) to afford stable antennas with enhanced spectral coverage. Native (or native-like) α- and β-peptides interact with each other and BChl a to form a heterodimeric (αβ-dyad) unit that can then oligomerize to form biohybrid analogs of the bacterial core light-harvesting complex (LH1). Pairs of distinct synthetic chromophores were incorporated in αβ-dyads at selected distances from the BChl a target site (position 0). Two designs were explored. One design used green-yellow absorbing/emitting Oregon Green at the −34 position (toward the N-terminus relative to the BChl a coordination site) of β and orange-red absorbing/emitting Rhodamine Red at the −20 position of α, which combine with BChl a to give homogeneous oligomers. A second design used two different β-peptide conjugates, one with Oregon Green at the −34 position and the second with a near-infrared absorbing/emitting synthetic bacteriochlorin at the −14 position, which combine with α and BChl a to give a heterogeneous mixture of oligomers. The designs afford antennas with ∼45 to ∼60 pigments, provide enhanced spectral coverage across the visible and near-infrared regions relative to native antennas, and accommodate pigments at remote sites that contribute to solar light harvesting via an energy-transfer cascade. The efficiencies of energy-transfer to the BChl a target in the biohybrid antennas are comparable to native antennas, as revealed by static and time-resolved absorption and emission studies. The results show that the biohybrid approach, where designer chromophores are integrated via semisynthesis with native-like scaffolding, constitutes a versatile platform technology for rapid prototyping of antennas for solar energy capture without the laborious synthesis typically required for creating artificial photosynthetic light-harvesting architectures.

Original languageEnglish (US)
Pages (from-to)3924-3933
Number of pages10
JournalChemical Science
Volume4
Issue number10
DOIs
StatePublished - Aug 26 2013

ASJC Scopus subject areas

  • Chemistry(all)

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