Sunao Shoji

Construction of Chlorosomal Rod Self‐Aggregates in the Solid State on Any Substrates from Synthetic Chlorophyll Derivatives Possessing an Oligomethylene Chain at the 17‐Propionate Residue

Chlorosomes are one of the most unique natural light-harvesting antennas and their supramolecular nanostructures are still under debate. Chlorosomes contain bacteriochlorophyll (BChl)-c, d and e molecules and these pigments self-aggregate under a hydrophobic environment inside a chlorosome. The self-aggregates are mainly constructed by the following three interactions: hydrogen bonding, coordination bonding and π-π stacking. Supramolecular nanostructures of self-aggregated BChls have been widely investigated by spectroscopic and microscopic techniques. Model compounds of such chlorosomal BChl molecules have been synthesized and the effects of esterified long alkyl chains at the 17-propionate residue for their self-aggregation have been studied. Structurally simple zinc chlorophyll derivatives possessing an oligomethylene chain as the esterifying group at the 17-propionate residue were prepared as chlorosomal BChl models. The synthetic zinc BChls self-aggregated in nonpolar organic solvents to give precipitates. The resulting insoluble self-aggregated solids were investigated on a variety of substrates, including hydrophobic, neutral and hydrophilic substrates, by visible absorption, circular dichroism and polarized light absorption spectroscopies, as well as atomic force, transmission electron and scanning electron microscopies. The self-aggregates of synthetic Zn-BChls formed rods with an approximately 5 nm diameter and wires with further elongated growth of the rods (aspect ratio >200). The diameter size was consistent with that estimated for natural chlorosomal rods in a filamentous anoxygenic phototroph, Chloroflexus aurantiacus. The supramolecular formation and stability of the rod on the examined substrates depended on the length of an oligomethylene chain at the 17-propionate residue as well as on the surface properties. Especially, the number of the 5 nm rods on the substrates increased with an elongation of the chain.

Ubiquity and quantitative significance of detoxification catabolism of chlorophyll associated with protistan herbivory

Chlorophylls are essential components of the photosynthetic apparati that sustain all of the life forms that ultimately depend on solar energy. However, a drawback of the extraordinary photosensitizing efficiency of certain chlorophyll species is their ability to generate harmful singlet oxygen. Recent studies have clarified the catabolic processes involved in the detoxification of chlorophylls in land plants, but little is understood about these strategies in aquatic ecosystem. Here, we report that a variety of heterotrophic protists accumulate the chlorophyll a catabolite 132,173-cyclopheophorbide a enol (cPPB-aE) after their ingestion of algae. This chlorophyll derivative is nonfluorescent in solution, and its inability to generate singlet oxygen in vitro qualifies it as a detoxified catabolite of chlorophyll a. Using a modified analytical method, we show that cPPB-aE is ubiquitous in aquatic environments, and it is often the major chlorophyll a derivative. Our findings suggest that cPPB-aE metabolism is one of the most important, widely distributed processes in aquatic ecosystems. Therefore, the herbivorous protists that convert chlorophyll a to cPPB-aE are suggested to play more significant roles in the modern oceanic carbon flux than was previously recognized, critically linking microscopic primary producers to the macroscopic food web and carbon sequestration in the ocean.

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.

Synthesis of Zinc Chlorophyll Homo/Hetero-Dyads and their Folded Conformers with Porphyrin, Chlorin, and Bacteriochlorin π-Systems

Zinc complex of pyropheophorbide‐b, a derivative of chlorophyll‐b, was covalently dimerized through ethylene glycol diester. The synthetic homo‐dyad was axially ligated with two methanol molecules from the β‐face and both the diastereomerically coordinating methanol species were hydrogen bonded with the keto‐carbonyl groups of the neighboring chlorin in a complex. The resulting folded conformer in a solution was confirmed by visible, 1H NMR and IR spectra. All the synthetic zinc chlorin homo‐ and hetero‐dyads consisting of pyropheophorbides‐a, b and/or d took the above methanol‐locked and π–π stacked supramolecules in 1% (v/v) methanol and benzene to give redmost (Qy) electronic absorption band(s) at longer wavelengths than those of the corresponding monomeric chlorin composites. The other zinc chlorin and bacteriochlorin homo‐dyads completely formed similar folded conformers in the same solution, while zinc inverse chlorin and porphyrin homo‐dyads partially took such supramolecules. The J‐type aggregation to folded conformers and the redshift values of composite Qy bands were dependent on the electronic and steric factors of porphyrinoid moieties in dyads.

Pheophytinization kinetics of chlorophyll c under weakly acidic conditions: Effects of acrylic acid residue at the 17-position

Pheophytinization of chlorophyll (Chl) c1, which was isolated from the diatom Chaetoceros gracilis, was kinetically analyzed under weakly acidic conditions, and was compared with that of protochlorophyllide (PChlide) a and chlorophyllide (Chlide) a. Chl c1 possessing a trans-acrylic acid residue at the 17-position exhibited slower pheophytinization kinetics than PChlide a and Chlide a, both of which possessed a propionic acid residue at the same position. The difference in pheophytinization properties between Chl c1 and (P)Chlide a was ascribable to the electronegativity of the 17-substituent in Chl c1 larger than that of (P)Chlide a due to the C17(1)-C17(2) double bond with the conjugated 17(2)-carboxy group in Chl c1. Demetalation kinetics of PChlide a was slower than that of Chlide a, which originated from the effect of the π-macrocyclic structures.

Self-Assemblies of Zinc Bacteriochlorophyll-d Analogues Having Amide, Ester, and Urea Groups as Substituents at 17-Position and Observation of Lamellar Supramolecular Nanostructures

Chlorosomes are unique light-harvesting apparatuses in photosynthetic green bacteria. Single chlorosomes contain a large number of bacteriochlorophyll (BChl)-c, -d, -e, and -f molecules, which self-assemble without protein assistance. These BChl self-assemblies involving specific intermolecular interactions (Mg⋅⋅⋅O32 -H⋅⋅⋅O=C131 and π-π stacks of chlorin skeletons) in a chlorosome have been reported to be round-shaped rods (or tubes) with diameters of 5 or 10 nm, or lamellae with a layer spacing of approximately 2 nm. Herein, the self-assembly of synthetic zinc BChl-d analogues having ester, amide, and urea groups in the 17-substituent is reported. Spectroscopic analyses indicate that the zinc BChl-d analogues self-assemble in a nonpolar organic solvent in a similar manner to natural chlorosomal BChls with additional assistance by hydrogen-bonding of secondary amide (or urea) groups (CON-H⋅⋅⋅O=CNH). Microscopic analyses of the supramolecules of a zinc BChl-d analogue bearing amide and urea groups show round- or square-shaped rods with widths of about 65 nm. Cryogenic TEM shows a lamellar arrangement of the zinc chlorin with a layer spacing of 1.5 nm inside the rod. Similar thick rods are also visible in the micrographs of self-assemblies of zinc BChl-d analogues with one or two secondary amide moieties in the 17-substituent.