Total synthesis of 3,5-O-dicaffeoylquinic acid and its derivatives

We report the first total synthesis of 3,5-O-dicaffeoylquinic acid and its derivatives, 3,5-O-diferuloylquinic acid and 3,5-(3,4-dimethoxycinnamyl)quinic acid, in a nine-step sequence. The key step involves Knoevenagel condensations between vanillin, 3,4-dimethoxybenzaldehyde or 4-hydroxy-3-methoxybenzaldehyde and the dimalonate ester of quinic acid.     

Efficient asymmetric synthesis of novel gastrin receptor antagonist AG-041R via highly stereoselective alkylation of oxindole enolates

An efficient method for asymmetric synthesis of the potent Gastrin/CCK-B receptor antagonist AG-041R was developed. Core oxindole stereochemistry was established by asymmetric alkylation of oxindole enolates with bromoacetic acid esters, using l-menthol as a chiral auxiliary. The key alkylation reaction of the oxindole enolates generated tetrasubstituted chiral intermediates with high diastereoselectivity. The stereoselective alkylation reactions are described in detail.     

Irciniasulfonic acid B, a novel taurine conjugated fatty acid derivative from a Japanese marine sponge, Ircinia sp.

Irciniasulfonic acid B (1) was obtained from a marine sponge, Ircinia sp., together with a known multi-drug resistance modulator irciniasulfonic acid (2). Spectroscopic and chemical analyses revealed structure consisting of common unsaturated fatty acids, a novel unsaturated branched fatty acid, and a taurine. Final separation of irciniasulfonic acid B (1) was achieved with its methylated derivatives. Irciniasulfonic acid B (1) reversed the multi-drug resistance in the same way as irciniasulfonic acid.     

Amphimelibiosides A-F, six new ceramide dihexosides isolated from a Japanese marine sponge Amphimedon sp

Six new ceramide dihexosides, amphimelibiosides A-F (1-6), were isolated from a Japanese marine sponge Amphimedon sp. The structure of amphimelibioside C (3), which is a major component of amphimelibiosides, was determined by 2D NMR techniques, chemical degradation, and a semisynthetic method to be 1-O-[beta-D-glucopyranosyl-(1-->6)-alpha-D-galactopyranosyl]-(2S,3S,4R,6E)-2-[(2'R)-2-hydroxydocosanoyl]-2-amino-6-octadecene-1,3,4-triol. The structures of the other constituents were elucidated by a combination of mass spectra, (1)H NMR, and GC-MS analysis.     

Observation of a dip-bump structure in differential cross section for pp → nn in the 700–760 MeV/c momentum range

Based on a sample of about 3500 events, we have measured the total and differential cross sections of $\text{p}\text{p}\text{→}\text{n}\text{n}$ in the 700–760 MeV/c incident momentum region. It is found that σ_CE = 10.7 ± 0.2 mb at the average momentum of 730 MeV/c. The differential angular distribution is characterised by a sharp peak and a dip in the forward direction followed by a secondary maximum. The position of the dip corresponds to |t| ≈ m_π². These results are compared with the predictions of the model of Bryan-Phillips. On the other hand, this dip-bump structure can be well understood on a simple picture involving a π exchange and a constant background (for |t| ? 3 m_π²).     

Characterization of hydrogen production by the co-culture of dark-fermentative and photosynthetic bacteria

Apprehension over exhaustion of fossil fuels and global warming, due to increasing amounts of CO₂, has generated a lot of attention for the subject of renewable energy. Renewable energy has an intermittency problem and its output fluctuates depending on natural conditions. Biohydrogen is one of the promising renewable energy sources. Hydrogen produced by photosynthetic bacteria depends on the intensity of light irradiation and also fluctuates with the daily variation of sunlight. The co-culture system of dark-fermentative and photosynthetic bacteria is one solution for reducing the dependency of hydrogen production on light intensity. Because these two strains of bacteria have different processes of hydrogen production, it is possible to combine different outputs so far as the co-culture system works well. This study performed hydrogen production by the co-culture system composed of agar gels embedded with both dark-fermentative bacteria, Clostridium butyricum MIYAIRI, and photosynthetic bacteria, Rhodobacter sphaeroides RV, under a fluctuating light-irradiation. The time-course of hydrogen production was determined for the different conditions of co-culture in the mixing ratios of the two bacterial strains and light-irradiation patterns. As a result, the co-culture system succeeded in producing hydrogen exceeding that in the case of a single culture system and improved its stability against light fluctuation. Hydrogen production by the co-culture system would be applicable to the reduction of intermittency in renewable energies.     

Unexpected Cyclization of Dipyridyl-glycoluril in the Presence of Formaldehyde and Strong Acid: A New Scaffold with a Potential as an Anion Receptor

In an attempted synthesis of peripherally pyridine-substituted cucurbituril, an unexpected cyclized product was obtained. A careful NMR analysis followed by mass spectrometry and preliminary crystallographic analyses, helped us in resolving the structure. The structure has two quaternized pyridine functionalities and a groove suitable as a potential receptor site. In addition, just like the parent glycoluril structure, two remaining urea-derived nitrogens can be alkylated by alkyl halides. Thus, we believe this high yielding reaction may become an entry point to a new class of anion receptors.