Nanotubes of Biomimetic Supramolecules Constructed by Synthetic Metal Chlorophyll Derivatives

Various supramolecular nanotubes have recently been built up by lipids, peptides, and other organic molecules. Major light-harvesting (LH) antenna systems in a filamentous anoxygenic phototroph, Chloroflexus (Cfl.) aurantiacus, are called chlorosomes and contain photofunctional single-wall supramolecular nanotubes with approximately 5 nm in their diameter. Chlorosomal supramolecular nanotubes of Cfl. aurantiacus are constructed by a large amount of bacteriochlorophyll(BChl)-c molecules. Such a pigment self-assembles in a chlorosome without any assistance from the peptides, which is in sharp contrast to the other natural photosynthetic LH antennas. To mimic chlorosomal supramolecular nanotubes, synthetic models were prepared by the modification of naturally occurring chlorophyll(Chl)-a molecule. Metal complexes (magnesium, zinc, and cadmium) of the Chl derivative were synthesized as models of natural chlorosomal BChls. These metal Chl derivatives self-assembled in hydrophobic environments, and their supramolecules were analyzed by spectroscopic and microscopic techniques. Cryo-transmission electron microscopic images showed that the zinc and cadmium Chl derivatives could form single-wall supramolecular nanotubes and their outer and inner diameters were approximately 5 and 3 nm, respectively. Atomic force microscopic images suggested that the magnesium Chl derivative formed similar nanotubes to those of the corresponding zinc and cadmium complexes. Three chlorosomal single-wall supramolecular nanotubes of the metal Chl derivatives were prepared in the solid state and would be useful as photofunctional materials.