Spectroscopic studies on self-aggregation of bacteriochlorophyll-e in nonpolar organic solvents: effects of stereoisomeric configuration at the 3(1)-position and alkyl substituents at the 8(1)-position.

Self-aggregation of naturally occurring bacteriochlorophyll (BChl)-e in nonpolar organic solvents was investigated by visible absorption, fluorescence emission and circular dichroism spectra. Cultured brown-colored photosynthetic bacteria have several BChl-e as light-harvesting antenna pigments. Three major BChl-e homologs were separated from the extracts of the culture by reverse-phase high-performance liquid chromatography (HPLC) and characterized by 1H-NMR and fast-atom bombardment mass spectroscopy: 8-ethyl-12-ethyl ([E,E])-, 8-propyl-12-ethyl- and 8-isobutyl-12-ethyl-BChl-e farnesyl esters. All the homologs consisted of a mixture of the 3(1)-epimers, and epimerically pure BChl-e were also given by HPLC separation. All the separated BChl-e epimers, the epimeric mixtures and the homologous mixtures formed self-aggregates in 2% dichloromethane/hexane, giving visible absorption spectra similar to that of the whole cells, which showed two peaks (or shoulders) around 430-450 and 520 nm at the Soret region as well as a red-shifted Qy band relative to the monomeric. The spectral properties of the Soret band were basically unchanged among the epimers or epimeric/homologous mixtures. In contrast, the Qy band of aggregates of epimeric mixtures (except [E,E]) and homologous mixtures red-shifted and broadened compared with the epimerically pure. The red-shift and broadening of the Qy band are advantageous for efficient energy transfer from BChl-e aggregates to BChl-a in a baseplate in chlorosomes because their spectral overlap increases.

Supramolecular structure of self-assembled synthetic zinc-13(1)-oxo-chlorins possessing a primary, secondary or tertiary alcoholic 3(1)-hydroxyl group: visible spectroscopic and molecular modeling studies.

Zinc-chlorin 3 (see Fig. 2 in text) possessing a tertiary 3(1)-hydroxyl group and a 13-keto group was synthesized as a model for the antenna chlorophylls of green bacteria. Self-aggregation of 3 in nonpolar organic media was examined and compared to 1 and 2 possessing a primary and secondary 3(1)-hydroxyl group, respectively. Zinc-chlorin 3 self-aggregated in 1 vol% CH2Cl2-hexane to form oligomers and showed a red-shifted Qy maximum at 704 nm compared to the monomer (648 nm in CH2Cl2). This red-shift is larger than that of 2S (648-->697 nm) and comparable to that of 2R (648-->705 nm), but smaller than that of 1 (648-->740 nm), indicating that while a single 3(1)-methyl group (prim-OH-->sec-OH) suppressed close and/or higher aggregation, the additional 3(1)-methyl group (sec-OH-->tert-OH) did not further suppress aggregation. The relative stability of the aggregates was in the order 1 > 2R-3 > 2S as determined by visible spectral analyses. Molecular modeling calculations on dodecamers of zinc-chlorins 1, 2R and 3 gave similar well-ordered energy-minimized structures, while 1 stacked more tightly than 2R and 3. In contrast, 2S gave a relatively disordered (twisted) structure. The calculated dodecameric structures could explain the visible spectral data of 1-3 in nonpolar organic media.

Specific recognition of chiral amino alcohols via lanthanide coordination chemistry: structural optimization of lanthanide tris(beta-diketonates) toward effective circular dichroism/fluorescence probing.

Lanthanide tris(beta-diketonates) formed stable, 1:1 highly coordinated complexes with amino alcohols, and the resulting complexes exhibited large enhanced fluorescence and intense induced circular dichroism (CD) signals. The stability constants of the highly coordinated complexes were determined for various combinations of lanthanide centers, beta-diketonate ligands, and organic substrates. These revealed that amino alcohol coordinated with the lanthanide center much more strongly than monoamine, monoalcohol, or diol derivative. On the basis of the highly coordinated complexation, several lanthanide tris(beta-diketonates) acted as CD/fluorescence probes specific for amino alcohols. Tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octadionato)europium(III) showed enhanced fluorescence in the presence of amino alcohols, while the corresponding ytterbium complex exhibited chirality-dependent CD signals for amino alcohols. In particular, the observed CD spectral profiles related well with the absolute configuration and optical purity of the bound amino alcohol, indicating that the structural optimization of lanthanide tris(beta-diketonates) offered specific sensing of amino alcohols and precise determination of their enantiomer excess percentages.

Pure and scrambled self-aggregates prepared with zinc analogues of bacteriochlorophylls c and d.

Zinc analogues of bacteriochlorophylls c and d self-assembled in aqueous media with phospholipids. A methanol solution of zinc chlorin and alpha-lecithin was put in a cellulose tube and the inner methanol solvent was gradually replaced with water by dialysis to form the self-assembled oligomers. Visible absorption spectra of the aqueous solution showed that zinc chlorins formed J-aggregates within the hydrophobic core of alpha-lecithin assemblies and that the supramolecular structure of the aggregates depended upon the stereochemistry at the 3(1)-position and the alkyl substituents at the 8-, 12-, and 17(4)-positions of the zinc chlorin. When the aqueous aggregates were prepared with a mixture of 3(1)-epimers and/or 8-, 12-, or 17(4)-homologues of zinc 3(1)-hydroxy-13(1)-oxochlorins, the structurally distinct components coaggregated to make scrambled oligomers. However, during the dialysis, zinc 3(1)-hydroxy- and 7(1)-hydroxy-13(1)-oxochlorins slowly individually aggregated to give two structurally different oligomer units in the cellulose tube. In contrast, if the two zinc chlorin components rapidly self-assembled in an aqueous medium, these components coaggregated to form scrambled oligomers. The present study shows that both the molecular structure of the pigments and the speed of the oligomerization determine the molecular arrangement in chlorosome-type self-assembled oligomers.

Self-aggregates of a synthetic cadmium chlorin in solid film as a photosynthetic antenna model.

Self-aggregates of a synthetic cadmium chlorin possessing 3(1)-hydroxyl and 13-carbonyl groups were prepared in dried thin film. The solid film was characterized by visible and infrared absorption spectroscopies at both transmission and reflection modes. The spectra given by the two different modes were essentially the same and resembled those in the extramembranous antennas of green photosynthetic bacteria. The circular dichroism and resonance Raman spectra also supported the similarity between the artificial self-aggregates and the natural systems. Electron diffraction of the aggregated film by transmission electron microscopy indicated the presence of an orderly structure with a 6.4-A interval, which was estimated for the close Cd-Cd distance of the stacking in the self-aggregates. The in vitro self-assembly in the solid state is a good structural model for the in vivo antenna.

A novel approach toward bacteriochlorophylls-e and f.

Methyl bacteriopheophorbide-f was prepared from methyl bacteriopheophorbide-d with retention of the 3(1)-chirality. The transformation of the methyl to the formyl group at the 7-position of the chlorin moiety will provide an alternative route for the synthesis of bacteriochlorophylls-e and f.

Photoinduced electron transfer from synthetic chlorophyll analogue to fullerene C60 on carbon paste electrode. Preparation of a novel solar cell.

Upon a carbon paste electrode, fullerene C60 and successively methyl pyropheophorbide-a (chlorin) were casted to prepare a chlorin-fullerene modified carbon paste electrode (CFE). Photocurrents on the CFE were produced by irradiating of visible lights (> 510 nm) in an aqueous solution of 0.05 M ethylenediaminetetraacetic acid and 0.1 M Na2SO4 at pH 6.7. Larger anodic photocurrent was induced by the CFE than by the carbon paste electrodes modified with either the fullerene or the chlorin. In addition, the photocurrent of the CFE was dependent upon the amount of fullerene casted. The photocurrent action spectra of the CFE (at 300 mV vs. Ag/Ag+) showed that photoinduced electron transfer occurred from the excited state of the chlorin to the fullerene and/or from the chlorin to the photoexcited fullerene, and the electron of the fullerene anion radical produced was then shifted to the carbon paste. Upon irradiation of > 375 nm lights, the anodic photocurrent of the CFE was enhanced by increase in the illuminated light power and reached 0.03 mA cm-2 in the present system.

Synthetic zinc tetrapyrroles complexing with pyridine as a single axial ligand.

Zinc chlorins were prepared from chlorophyll-a. Visible spectra in benzene showed that synthetic zinc chlorins complexed with pyridine as an axial ligand to form the monopyridine adducts. The equilibrium constants for the complexation were dependent upon the chlorin structure: substitution of electron-withdrawing groups at the peripheral position enhanced the coordinated ability of the central zinc. 1H NMR spectra in benzene-d6 also indicated that single pyridine coordinated to the central zinc. Comparison of the equilibrium constant in a zinc chlorin with those of the corresponding zinc bacteriochlorin (7,8-dihydrochlorin) and porphyrin (17,18-dedihydrochlorin) led to an increase in the saturation and flexibility of the tetrapyrrole pi-plane ligands making the central zinc more axial-ligated. All the zinc tetrapyrroles in benzene complexed with pyridine to form 5-coordinated (1:1) complexes, not 6-coordinated bisadducts. The observed equilibrium constants were consistent with the energy changes of the complexation calculated from molecular modeling.

Dimerization of synthetic zinc aminochlorins in non-polar organic solvents.

UV-visible spectra of synthetic zinc aminochlorins were measured in 99:1 (v/v) cyclohexane-dichloromethane solution. The compounds formed anti-parallel dimers with mutual coordination of the central zinc in one molecule to the amino nitrogen in the other (Qy band red-shift of about 500 cm(-1)). Such a dimer arrangement appears to be too stable to form far-red (> 1500 cm(-1)) shifted oligomers which have been observed with bacteriochlorophylls-c (possessing a hydroxy group and a central magnesium) and with their model compounds (with a hydroxy group and a central zinc) in non-polar organic solvents.