Biohybrid photosynthetic antenna complexes for enhanced light-harvesting

Joseph W. Springer, Pamela S Parkes-Loach, Kanumuri Ramesh Reddy, Michael Krayer, Jieying Jiao, Gregory M. Lee, Dariusz M. Niedzwiedzki, Michelle A. Harris, Christine Kirmaier, David F. Bocian*, Jonathan S. Lindsey, Dewey Holten, Paul A Loach

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

65 Scopus citations

Abstract

Biohybrid antenna systems have been constructed that contain synthetic chromophores attached to 31mer analogues of the bacterial photosynthetic core light-harvesting (LH1) β-polypeptide. The peptides are engineered with a Cys site for bioconjugation with maleimide-terminated chromophores, which include synthetic bacteriochlorins (BC1, BC2) with strong near-infrared absorption and commercial dyes Oregon green (OGR) and rhodamine red (RR) with strong absorption in the blue-green to yellow-orange regions. The peptides place the Cys 14 (or 6) residues before a native His site that binds bacteriochlorophyll a (BChl-a) and, like the native LH proteins, have high helical content as probed by single-reflection IR spectroscopy. The His residue associates with BChl-a as in the native LH1 β-polypeptide to form dimeric ββ-subunit complexes [31mer( - 14Cys)X/BChl] 2, where X is one of the synthetic chromophores. The native-like BChl-a dimer has Q y absorption at 820 nm and serves as the acceptor for energy from light absorbed by the appended synthetic chromophore. The energy-transfer characteristics of biohybrid complexes have been characterized by steady-state and time-resolved fluorescence and absorption measurements. The quantum yields of energy transfer from a synthetic chromophore located 14 residues from the BChl-coordinating His site are as follows: OGR (0.30) < RR (0.60) < BC2 (0.90). Oligomeric assemblies of the subunit complexes [31mer( - 14Cys)X/BChl] n are accompanied by a bathochromic shift of the Q y absorption of the BChl-a oligomer as far as the 850-nm position found in cyclic native photosynthetic LH2 complexes. Room-temperature stabilized oligomeric biohybrids have energy-transfer quantum yields comparable to those of the dimeric subunit complexes as follows: OGR (0.20) < RR (0.80) < BC1 (0.90). Thus, the new biohybrid antennas retain the energy-transfer and self-assembly characteristics of the native antenna complexes, offer enhanced coverage of the solar spectrum, and illustrate a versatile paradigm for the construction of artificial LH systems.

Original languageEnglish (US)
Pages (from-to)4589-4599
Number of pages11
JournalJournal of the American Chemical Society
Volume134
Issue number10
DOIs
StatePublished - Mar 14 2012

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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