The functional evaluation of waste yuzu (Citrus junos) seeds.

We have succeeded in extracting a large amount of expensive limonoids and the high total antioxidant capability yuzu seed oil from waste yuzu seed by simple methods. Yuzu seeds contain higher amounts of fat-soluble limonoid aglycone (330.6 mg g(-1) of dry seed), water-soluble limonoid glycoside (452.0 mg g(-1) of dry seed), and oil (40 mg g(-1) of green seed) than other citrus fruits. The antioxidant activities of yuzu seed aglycone, glycoside, and seed oil were evaluated in vitro. The potential antioxidant activity in oil solution, diphenylpicrylhydrazyl radical-scavenging activity, and hydrogen peroxide-scavenging activity effects of the seed extracts were also investigated. The antioxidant activity of yuzu seed oil was two times that of grapefruit seed oil, which has high activity. Yuzu glycoside produced the same high antioxidant activity as Luo Han Guo glycoside.

Amidation of alcohols with nitriles under solvent-free conditions using molecular iodine as a catalyst.

The reactions of alcohols with nitriles under solvent-free conditions, using molecular iodine as a catalyst, were investigated. The reaction of 1-phenylethanol with propanenitrile produced the amide N-(1-phenylethyl)propanamide, by dehydration and tautomerization, in 71% yield, under the following conditions: temperature=90°C, alcohol:iodine molar ratio=1:0.2, alcohol:nitrile molar ratio=1:5, and reaction time=5 h. The amidation reactivity depended on the stability of the cationic intermediate formed from the alcohol. The reaction of (-)-borneol with benzonitrile produced a racemic amide in 83% yield.

Synthesis of cinnamyl ethers from α-vinylbenzyl alcohol using iodine as catalyst.

Reactions of α-vinylbenzyl alcohol with other alcohols using iodine as a catalyst were investigated. The corresponding cinnamyl ethers were obtained as products. This suggested that α-vinylbenzyl alcohol was converted to cinnamyl ethers via 1-phenylallyl cation. Cinnamyl ethyl ether was obtained in 75% yield by the reaction of α-vinylbenzyl alcohol and ethanol in acetonitrile with iodine under the following conditions: temperature = 50 °C, molar ratio of α-vinylbenzyl alcohol:ethanol:iodine = 1:3.0:0.2, and time period = 6 h. Generally, the yields of the reactions using primary alcohols were higher than those using secondary and tertiary alcohols. Ether interchange also occurred by the reaction of α-vinylbenzyl alcohol and iodine, but proceeded smoothly only when an allyl group was used as the other substituent of the starting ether.

Inhibitory effect of galectin-3 on the cytokine-inducing activity of periodontopathic Aggregatibacter actinomycetemcomitans endotoxin in splenocytes derived from mice.

Galectins, a family of animal lectins, are involved not only in development and differentiation but also in immunoregulation and host-pathogen interactions. Galectin-3 interacts with lipopolysaccharides in gram-negative bacteria such as Escherichia coli, Salmonella minnesota and Pseudomonas aeruginosa. The present study investigated whether galectin-3 inhibited the cytokine-inducing activity of periodontopathic bacterial lipopolysaccharides using splenocytes derived from mice of different ages. Lipopolysaccharides were extracted from Aggregatibacter actinomycetemcomitans Y4 and Porphyromonas gingivalis ATCC 33277, and then purified. Enzyme-linked immunosorbent assay (ELISA) analysis revealed that galectin-3 adhered to A. actinomycetemcomitans lipopolysaccharides, but not to the lipopolysaccharides of P. gingivalis. Splenocytes were prepared from 1- or 7-month-old C57BL/6 mice. Either A. actinomycetemcomitans lipopolysaccharides (200 ng mL(-1)) alone or lipopolysaccharides and murine galectin-3 (10 microg mL(-1)) were added to culture solutions, and the release of interleukin-6 (IL-6) and interferon-gamma (IFNgamma) from splenocytes was measured by ELISA after a 17-h incubation. In all mice tested, A. actinomycetemcomitans lipopolysaccharide stimulation significantly increased the production of IL-6 and IFNgamma (P<0.01). Murine galectin-3 suppressed lipopolysaccharide-induced cytokine production in the splenocytes of the 1-month-old mice (P<0.02 for IL-6; P<0.05 for IFNgamma), but not in the splenocytes of the 7-month-old mice. This suggests that responses change with age.

Iodine-catalyzed synthesis of five-membered cyclic ethers from 1,3-diols under solvent-free conditions.

Intramolecular etherification of 1,3-diols was investigated using iodine as a catalyst under solvent-free conditions. The reaction proceeded to completion in a heterogeneous system. Five-membered cyclic ethers were obtained by intramolecular cyclization of 1,3-diols with dehydration. A propella ether (11-oxatricyclo[4.4.3.0(1,6)]tridecane) was conveniently synthesized from a 1,3-diol (6-(2-hydroxyethyl)spiro[4.5]decan-6-ol) in 86% yield with carbon skeleton rearrangement under the following conditions: a temperature of 60 degrees C, a molar ratio of 1,3-diol:iodine = 1:0.2, and a time period of 3 h. Bicyclic ethers were also obtained from the corresponding 1,3-diols, but spiro ethers were obtained in lower yield. Terpenic cyclic ethers were efficiently synthesized from the corresponding 1,3-diols, derived from (+)-camphor and (-)-fenchone. In the case of etherification with a mechanism of carbon skeleton rearrangement, the yield of the solvent-free reaction was as high as that of the corresponding reaction in solution. Etherification reactions with carbon skeleton rearrangement proceeded more smoothly than those with hydride shift.

On-line preconcentration of phosphate onto molybdate form anion exchange column.

In this paper, we describe an automated flow injection system for measuring the concentration of phosphate based on a fluorescence quenching reaction between Rhoadamine 6G and phosphomolybdate with a preconcentration column, which was packed with a molybdate-form ion exchange resin to collect and preconcentrate the phosphate in the sample solution. Rhodamine 6G was chosen because the reaction with phosphomolybdate was fast and did not require heat. For the construction of a stable flow injection system, an aqueous methanol solution was used as the cleaning reagent to overcome the precipitation of ion-associated complexes between Rhodamine 6G and phosphomolybdate or Rhodamine 6G and molybdate. For the preconcentration and collection of the phosphate ions in a water sample, a preconcentration column, which was packed with a molybdate-form ion exchange resin, was combined with the proposed flow injection system and applied to natural water samples containing low concentrations of phosphate.