Two new tryptamine derivatives, leptoclinidamide and (-)-leptoclinidamine B, from an Indonesian ascidian Leptoclinides dubius.

Two new tryptamine-derived alkaloids, named as leptoclinidamide (1) and (-)-leptoclinidamine B (2), were isolated from an Indonesian ascidian Leptoclinides dubius together with C²-α-D-mannosylpyranosyl-L-tryptophan (3). The structure of 1 was assigned on the basis of spectroscopic data for 1 and its N-acetyl derivative (4). Compound 1 was an amide of tryptamine with two ß-alanine units. Although the planar structure of 2 is identical to that of the known compound (+)-leptoclinidamine B (5), compound 2 was determined to be the enantiomer of 5 based on amino acid analysis using HPLC methods. Compounds 1 to 4 were evaluated for cytotoxicity against two human cancer cell lines, HCT-15 (colon) and Jurkat (T-cell lymphoma) cells, but none of the compounds showed activity.

Development of a chemical strategy to produce rare aldohexoses from ketohexoses using 2-aminopyridine.

Rare sugars are monosaccharides that are found in relatively low abundance in nature. Herein, we describe a strategy for producing rare aldohexoses from ketohexoses using the classical Lobry de Bruyn-Alberda van Ekenstein transformation. Upon Schiff-base formation of keto sugars, a fluorescence-labeling reagent, 2-aminopyridine (2-AP), was used. While acting as a base catalyst, 2-AP efficiently promoted the ketose-to-aldose transformation, and acting as a Schiff-base reagent, it effectively froze the ketose-aldose equilibrium. We could also separate a mixture of Sor, Gul, and Ido in their Schiff-base forms using a normal-phase HPLC separation system. Although Gul and Ido represent the most unstable aldohexoses, our method provides a practical way to rapidly obtain these rare aldohexoses as needed.

In situ product removal of ketoses by immobilized 3-amino phenyl boronic acid: effect of immobilization method on pH profile.

The use of polymeric derivatives of phenylboronic acid (PBA) as an effective means for specific in situ product removal of ketoses from aldose-containing reaction mixtures, strongly depends on the retention of selective binding of ketoses exhibited by soluble PBA and 3-amino PBA, by their polymeric, water insoluble analogs. In this communication we demonstrate that immobilization chemistry has a strong effect on ketose preferred binding by polymeric PBA derivatives. Our results indicate that for the preparation of an effective and more specific adsorbent, 3-amino PBA should be coupled to the polymeric carrier via alkylamino chemistry and not via the commonly employed amido derivative. Immobilized alkylamino-PBA exhibited selective fructose and xylulose binding throughout glucose and xylose isomerization processes at the pH range of 7.0-8.0.

Isolation of ketoses or nonreducing sugars from a sugar mixture containing aldoses by aniline treatment.

A method for the isolation of ketoses and nonreducing sugars from sugar mixtures by the addition of aniline, in the presence of acetic acid as a catalyst, is described. The aldoses react readily to form aniline derivatives, which are then removed using standard procedures: extraction with organic solvents, and treatment with activated charcoal and with a cation-exchange resin. The ketoses and nonreducing sugars are retained in aqueous solution.

Characterization of lipopolysaccharide of Haemophilus influenzae.

Lipopolysaccharide from strains of Haemophilus influenzae was extracted and isolated by the hot phenol-water procedure. The preparations were relatively insoluble in water but could be solubilized with surface-active agents. The preparations contained carbohydrate (30%), fatty acid (29%), and phosphate (4.7%); protein content was less than 1%. Thin-layer chromatography, gas-liquid chromatography, and colorimetric assays detected glucose, galactose, glucosamine, heptose, and a 2-keto-3-deoxy-octonate-like molecule (less than 1%). Neither methylpentose nor dideoxyhexose was detected. The lipid portion was composed of fatty acids common to lipopolysaccharide of Salmonella. The preparations provoked positive dermal Shwartzman reactions and biphasic febrile responses in rabbits, responses typical of endotoxic activity. The 50% lethal dose for mice was decreased from 16.5 microgram/g to 0.015 microgram/g by concomitant administration of actinomycin D. The preparations were shown to be polyclonal activators of bone marrow-derived (B) cells. Limulus lysate gelation was seen with 8.0 ng of lipopolysaccharide. Preliminary hemagglutination data suggested at least three different antigenic factors associated with the lipopolysaccharide of H. influenzae type b. The H. influenzae lipopolysaccharide appeared biologically similar to that of enterobacteria but chemically different.