Synthesis of zinc 20-substituted bacteriochlorophyll-d analogs and their self-aggregation

Zinc complexes of methyl 3¹-demethyl-bacteriopheophorbides-d possessing a 2-(un)substituted ethynyl or ethenyl group at the 20-position were prepared through palladium-catalyzed cross-coupling of their 20-bromide with the corresponding alkyne or alkene. The synthetic zinc 20-substituted 3-hydroxymethyl-13¹-oxo-chlorins self-aggregated in an aqueous micellar solution to give similar large oligomers as self-aggregates of bacteriochlorophylls in the core part of the main light-harvesting antenna of photosynthetic green bacteria. The zinc 20-ethynyl-chlorin fully gave the self-aggregates, but its 20²-substitution disturbed the self-aggregation. The 20-(2-phenyl)ethenyl moieties induced the formation of relatively smaller oligomers as well as residual monomers due to their steric bulkiness.     

Oligonucleotide‐Based Mimetics of Hepatocyte Growth Factor

Oligonucleotide‐based hepatocyte growth factor (HGF) mimetics are described. A DNA aptamer to Met, a cognate receptor for HGF, was shown to induce Met activation when used in dimer form. The most potent aptamer dimer, ss‐0, which was composed solely of 100‐mer single‐stranded DNA, exhibited nanomolar potency. Aptamer ss‐0 reproduced HGF‐induced cellular behaviors, including migration and proliferation. The present work sheds light on oligonucleotides as a novel chemical entity for the design of growth factor mimetics.     

Contamination by butyltin compounds in harbour porpoise (Phocoena phocoena) from the Black Sea

Concentrations of butyltin compounds (BTs) were determined in harbour porpoise (Phocoena phocoena) collected from the Turkish coastal waters of the Black Sea. Total butyltin compounds (∑ BTs) in the liver were in the range of 89–219 ng/g on a wet weight basis. The dibutyltin (DBT) residues were higher than those of tributyltin (TBT), suggesting the degradation of TBT to DBT in the liver and the metabolic capacity comparable to other marine mammals. Any sex difference and age-dependent accumulation of BTs residues were not found in harbour porpoises, but residue levels increased until maturity and then remained constant. When compared with other marine mammals, the present results indicate that the Black Sea is also contaminated with butyltin compounds, but to a lesser degree than coastal waters of developed nations. The biomagnification factor in harbour porpoises was 0.8, which was comparable with pinnipeds and lower than cetaceans. Received: 23 December 1996 / Revised: 15 April 1997 / Accepted: 16 April 1997     

Synthesis of zinc 20-ethenylated bacteriochlorophyll-d analogs and their self-aggregation in an aqueous micelle solution

Zinc complexes of 3-hydroxymethyl-13¹-oxo-chlorins possessing a vinyl or its trans-substituted group at the 20-position were prepared through regioselective bromination and successive palladium-catalyzed cross-coupling reactions from naturally occurring chlorophyll-a. The synthetic zinc chlorophyll-a derivatives self-aggregated in an aqueous Triton X-100 micelle solution to give red-shifted and broadened electronic absorption bands, which were similar to those of bacteriochlorophyll-c/d self-aggregates in the main light-harvesting antenna systems of green photosynthetic bacteria. Because of the sterically demanded perpendicular orientation of the (un)substituted ethenyl group to the chlorin π-system, the present model compounds had less J-aggregation ability in a slipped π–π interaction fashion than the corresponding saturated ethyl-type analogs, while halogenations at the terminal of the 20-vinyl group enhanced the ability due to their electron-withdrawing effect.     

Organocatalytic Enantioselective Decarboxylative Reaction of Malonic Acid Half Thioesters with Cyclic N‐Sulfonyl Ketimines by Using N‐Heteroarenesulfonyl Cinchona Alkaloid Amides

The organocatalytic enantioselective decarboxylative Mannich reaction of malonic acid half thioesters (MAHTs) with cyclic N‐sulfonyl ketimines by using N‐heteroarenesulfonyl cinchona alkaloid amides afforded products with high enantioselectivity. Both enantiomers of the products could be obtained by using pseudoenantiomeric chiral catalysts. The reaction proceeds through a nucleophilic addition of the MAHTs to the ketimines prior to decarboxylation.     

Chemo‐ and Regioselective Reduction of 5,15‐Diazaporphyrins Providing Antiaromatic Azaporphyrinoids

Reagent‐controlled chemo‐ and regioselective reduction of 5,15‐diazaporphyrins has been developed. The selective reduction of carbon–carbon double bonds of diazaporphyrins provides 18 π aromatic isobacteriochlorin‐type products, whereas the reduction of carbon–nitrogen double bonds leads to selective formation of 20 π N,N′‐dihydrodiazaporphyrins in excellent yields. The distinct antiaromatic character of N,N′‐dihydrodiazaporphyrins has been revealed. The free‐base N,N′‐dihydrodiazaporphyrin exhibits slower inner NH tautomerism than that in the corresponding 18 π porphyrins.     

Magnetic field enhanced microextraction rate of europium(III) with 2-thenoyltrifluoroacetone and oxalate at dodecane-water interface.

A microscopic system for the observation of reactions at a liquid-liquid interface was established, to which strong magnetic fields (0-0.4 T) could be applied with permanent magnets. In situ observation for the interfacial extraction of fluorescent and paramagnetic Eu(III) ion with 2-thenoyltrifluoroacetone (Htta) in dodecane was carried out. In the presence of oxalate (ox2-), micro-aggregates of Eu(III)-tta-ox complexes were generated in the aqueous phase before its extraction. When the micro-aggregates diffused to the dodecane-water interface, Eu(tta)3 was extracted with excess Htta in the dodecane phase. The microextraction process of the aggregates was observed as random flashes of Eu(tta)3 fluorescence at the dodecane-water interface. The single flash contained about 10(-16)-10(-14) mol of Eu(III). An application of magnetic fields made the flash frequency increase, which corresponded to an enhancement of interfacial Eu(III) extraction rate. The enhancement effect was attributable to the magnetophoresis of the paramagnetic microaggregates to the dodecane-water interface.     

Reagent-controlled stereoselective synthesis of (±)-gallo- and (±)-epigallo-catechin gallates

Synthesis of (±)-gallocatechin and (±)-epigallocatechin gallates by electrophilic cycloarylation is reported. The precursors for cyclization were prepared by reagent-controlled stereo-selective opening of epoxide with phenol. Activation of the S-oxidized S,O-acetal enabled electrophilic cycloarylation to stereoselectively provide the acylated catechins.