Biohybrid Photosynthetic Antenna Complexes for Enhanced Light-Harvesting

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• 作者：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
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：March 14, 2012
• 年：2012
• 卷：134
• 期：10
• 页码：4589-4599
• 全文大小：631K
• 年卷期：v.134,no.10(March 14, 2012)
• ISSN：1520-5126

文摘

Biohybrid antenna systems have been constructed that contain synthetic chromophores attached to 31mer analogues of the bacterial photosynthetic core light-harvesting (LH1) 尾-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 尾-polypeptide to form dimeric 尾尾-subunit complexes [31mer(鈭?4Cys)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(鈭?4Cys)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.