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

Journal Article · Tue Jan 01 00:00:00 EST 2013 · Chemical Science

DOI:https://doi.org/10.1039/c3sc51518d· OSTI ID:1089678

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

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.

• Research Organization: Washington Univ., St. Louis, MO (United States); Energy Frontier Research Centers (EFRC) (United States). Photosynthetic Antenna Research Center (PARC)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES)
• DOE Contract Number: SC0001035
• OSTI ID: 1089678
• Report Number(s): DE-SC0001035-86
• Journal Information: Chemical Science, Vol. 4, Issue 10; ISSN 2041-6520
• Publisher: Royal Society of Chemistry
• Country of Publication: United States
• Language: English

Related Subjects

14 SOLAR ENERGY