The chlorosomal light-harvesting antennae of green phototrophic bacteria consist of large supramolecular aggregates of bacteriochlorophyll c (BChl c). The supramolecular structure of (31-R/S)-BChl c on highly oriented pyrolytic graphite (HOPG) and molybdenum disulfide (MoS2) has been investigated by scanning tunneling microscopy (STM). On MoS2, we observed single BChl c molecules, dimers or tetramers, depending on the polarity of the solvent. On HOPG, we observed extensive self-assembly of the dimers and tetramers. We propose C=O · · · H–O · · · Mg bonding networks for the observed dimer chains, in agreement with former ultraviolet–visible and infrared spectroscopic work. The BChl c moieties in the tetramers are probably linked by four C=O · · · H–O hydrogen bonds to form a circle and further stabilized by Mg · · · O–H bondings to underlying BChl c layers. The tetramers form highly ordered, distinct chains and extended two-dimensional networks. We investigated semisynthetic chlorins for comparison by STM but observed that only BChl c self-assembles to well-structured large aggregates on HOPG. The results on the synthetic chlorins support our structure proposition.
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1 June 2002
Self-assembly of [Et,Et]-Bacteriochlorophyll cF on Highly Oriented Pyrolytic Graphite Revealed by Scanning Tunneling Microscopy
H. Möltgen,
K. Kleinermanns,
A. Jesorka,
K. Schaffner,
A. R. Holzwarth
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Photochemistry and Photobiology
Vol. 75 • No. 6
June 2002
Vol. 75 • No. 6
June 2002