Novel Conjugates of 1,3-Diacylglycerol and Lipoic Acid: Synthesis, DPPH Assay, and RP-LC-MS-APCI Analysis.

1,3-Diacylglycerol is known to reduce body weight and fat deposits in humans. α-Lipoic acid is a potent antioxidant and effective against many pathological conditions, including obesity and related metabolic syndromes. The present work is based on the hypothesis that the hybrid molecules of 1,3-diacylglycerol and lipoic acid possess synergistic and/or additive effects compared with the parent compounds against obesity, overweight, and related metabolic syndromes. Laboratory scale synthesis of 1,3-dioleoyl-2-lipoyl-sn-glycerol (yield 80%) and 1,3-dioleoyl-2-dihydrolipoyl-sn-glycerol (yield 70%) was performed for the first time and supported by NMR and MS data. Free radical scavenging capacity of the conjugates was assayed using DPPH test. A remarkably high in vitro free radical scavenging capacity was demonstrated for the 1,3-dioleoyl-2-dihydrolipoyl-sn-glycerol (EC(50) value 0.21). RP-HPLC-MS-APCI analysis showed satisfactory separation between the conjugates (R~1). Protonated molecular ion of the conjugates at m/z 809 and m/z at 811, respectively, and their characteristic fragment ions were abundant.

Quantitative NMR analysis of a sesamin catechol metabolite in human urine.

Sesamin, the major sesame oil lignan, is recognized for its health-promoting effects, including the lowering of cholesterol and elevation of gamma-tocopherol in rats and humans. However, little is known about the absorption and metabolism of sesamin in humans. In this study, 6 healthy volunteers took a single dose of sesame oil (508 micromol sesamin) and their urine was collected for four 12-h periods. The urine samples were treated with beta-glucuronidase/sulphatase and extracted with chloroform. The major urinary sesamin metabolite in the chloroform extract was collected using HPLC diode array detector and characterized as (1R,2S,5R,6S)-6-(3,4-dihydroxyphenyl)-2-(3,4-methylenedioxyphenyl)-3,7-dioxabicyclo-[3,3,0]octane using NMR and mass spectroscopy. A quantitative (1)H-NMR technique, based on the methylenedioxyphenyl protons signal (delta 5.91), was used for the quantification of the metabolite in the chloroform extracts of urine. The excretion of the sesamin catechol metabolite ranged from 22.2 to 38.6% (mean +/- SD, 29.3 +/- 5.6) of the ingested dose and happened mainly in the 1st 12 h after ingestion.

Characterization and analysis of sesamolinol diglucoside in sesame seeds.

A new lignan glucoside was isolated from defatted sesame seed flour and its structure was established as sesamolinol diglucoside [2-(3-methoxy-4-(O-beta-D-glucopyranosyl (1-->6)-O-beta-D-glucopyranoside)phenoxyl)-6-(3,4-methylenedioxyphenyl)-cis-3,7-dioxabicyclo-(3.3.0)-octane] by mass and nuclear magnetic resonance spectroscopy. A quantitative analysis of 65 sesame seed samples showed that this sesamolinol diglucoside ranged from <5 to 232 mg/100 g of seeds (98+/-57 mg/100 g) with no difference between white and black sesame seeds.

HPLC analysis of sesaminol glucosides in sesame seeds.

An HPLC method was developed and validated for the quantification of sesaminol triglucoside and a sesaminol diglucoside in sesame seeds. These two lignans were isolated, and their structures were characterized by mass and nuclear magnetic resonance spectroscopy. Defatted sesame flour was extracted first with 85% ethanol for 5 h followed by 70% ethanol for 10 h at room temperature using naringenin as internal standard. Analysis of 65 different samples of sesame seeds indicated that the content of sesaminol triglucoside ranged from 36 to 1560 mg/100 g of seed (mean 637 +/- 312) and that of sesaminol diglucoside ranged from 0 to 493 mg/100 g of seed (mean 75 +/- 95). No significant difference was found between sesaminol glucoside contents in black and white seeds.

Avenanthramides in oats (Avena sativa L.) and structure-antioxidant activity relationships.

Eight avenanthramides, amides of anthranilic acid (1) and 5-hydroxyanthranilic acid (2), respectively, and the four cinnamic acids p-coumaric (p), caffeic (c), ferulic (f), and sinapic (s) acid, were synthesized for identification in oat extracts and for structure-antioxidant activity studies. Three compounds (2p, 2c, and 2f) were found in oat extracts. As assessed by the reactivity toward 1,1-diphenyl-2-picrylhydrazyl (DPPH), all avenanthramides except 1p showed activity. Initially, the antioxidant activity of the avenanthramides decreased in a similar order as for the corresponding cinnamic acids, that is: sinapic > caffeic > ferulic > p-coumaric acid. The avenanthramides derived from 2 were usually slightly more active than those derived from 1. All avenanthramides inhibited azo-initiated peroxidation of linoleic acid. 1c and 1s were initially the most effective compounds. The relative order of antioxidant activities was slightly different for the DPPH and the linoleic acid assays run in methanol and chlorobenzene, respectively.