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Synthesis of linoleoyl disaccharides through lipase-catalyzed condensation and their surface activities.

Monolinoleoyl trehalose, maltose and cellobiose were synthesized by Candida antarctica lipase-catalyzed condensation in an organic solvent with a low water content. The use of a mixture of pyridine and tert-butanol as the reaction medium resulted in a high product concentration on the order of mmol/l for the synthesis of linoleoyl trehalose and maltose. The highest product concentration was achieved with the 0.4 volumetric fraction of pyridine. Linoleoyl cellobiose was also synthesized although its concentration was approximately one tenth the concentrations of linoleoyl trehalose and maltose. The surfactant properties of linoleoyl trehalose, maltose and cellobiose were measured. Among the esters, linoleoyl trehalose showed the strongest surface activity.

Biotechnology↗

Synthesis and structure analysis of novel disaccharides containing D-psicose produced by endo-1,4-beta-D-xylanase from Aspergillus sojae.

Xylosylpsicoses (XPs) were synthesized by transglycosylation (TG) with arabinoxylan (AX) and D-psicose (D-psi) using endo-1,4-beta-D-xylanase (EC 3.2.1.8) from Aspergillus sojae. The structures of XPs were analyzed by HPLC to determine sugar composition and molecular mass, by methylation analysis using GC-MS to determine linkage, and by 1H- and 13C-NMR spectrometries to obtain the anomeric configuration of glycosidic linkage. By chemical analysis, it was found that the structures of XPs are Xylp beta1-4Psip, Xylp beta1-5Psip, Xylp beta1-1Psif and Xylp beta1-6Psif.

Aspergillus↗

(S)-linalyl, 2-phenylethyl, and benzyl disaccharide glycosides isolated as aroma precursors from oolong tea leaves.

Three glycosides, 6-O-beta-D-xylopyranosyl-beta-D-glucopyranosides (beta-primeverosides) of the aroma constituents, linalool, 2-phenylethanol, and benzyl alcohol, were isolated as aroma precursors from the tea leaves (Camellia sinensis var. sinensis cv. Shuixian and Maoxie, cultivars for oolong tea). The isolation was guided by acid or enzymatic hydrolysis, and subsequent GC and GC-MS analyses. The linalyl glycoside is the first example of naturally occurring (S)-linalyl beta-primeveroside.

Benzyl Alcohols↗

Structural analysis of disaccharides synthesized by beta-D-glucosidase of Bifidobacterium breve clb and their assimilation by Bifidobacteria.

Circulation of a solution of 1 M D-fucose and 1 M D-glucose through a reaction system consisting of serial columns of immobilized recombinant beta-D-glucosidase of Bifidobacterium breve clb and activated charcoal gave two oligosaccharides. Structural analysis identified these oligosaccharides as D-fucosylglucose (6-O-beta-D-Fucopyranosyl-D-glucose) and gentiobiose (6-O-beta-D-Glucopyranosyl-D-glucose). The D-fucosylglucose obtained was well assimilated by many Bifidobacteria but not by the other intestinal bacteria tested.

Animals↗

Alterations of rat intestinal disaccharide absorption by bile or conjugated bile acids.

Taurocholate showed different effects on the jejunal sucrose absorption, depending on the concentration of the bile acid: 3 mmol/l taurocholate inhibited to a small extent (-7%), 10 mmol/l taurocholate had no effect and 30 mmol/l taurocholate increased the sucrose absorption by 17%. The sucrose hydrolysis was augmented by 20% in the presence of 30 mmol/l taurocholate. 2 mmol/l taurochenodeoxycholate caused an increase of sucrose hydrolysis(+ 37%) as well as of sucrose absorption (+ 12%) in the jejunum. Pooled rat bile induced a 21% inhibition of the sucrose hydrolysis, while the sucrose absorption was unchanged. The jejunal maltose hydrolysis was unaffected by 3 mmol/l taurocholate, whereas 10 or 30 mmol/l caused a minimal increase (+ 3%). The absorption of the resulting glucose was reduced to 84--92%. In the ileum 10 mmol/l taurocholate did not change the sucrose hydrolysis and absorption, whereas 2 mmol/l taurochenodeoxycholate induced a 30% decrease. The investigated bile acids had no effect on the microscopic structure of the small intestinal mucosa. Hypertonic solutions caused an accumulation and exfoliation of PAS-positive material at the top of the villi, independent of the presence or absence of bile acids.

Animals↗

Chronic lactose intake modifies the gastric emptying of monosaccharides but not of disaccharides in weanling rats.

Ninety-six weanling male Wistar rats were fed for four weeks one of two different chows: a normal rat chow containing 55.5% (w/w) starch (control group, N = 48) or a rat chow in which starch was partially replaced by lactose, in such a way that the experimental group (N = 48) received 35.5% (w/w) starch and 20% (w/w) lactose. The gastric emptying of fluid was then studied by measuring the gastric retention of four test meals containing lactose (5% or 10%, w/v) or glucose+galactose (5% or 10%, w/v). Homogenates of the small intestine were assayed for lactase activity. The gastric retention values were obtained 15 min after orogastric infusion of the liquid meals. The median values for gastric retention of the 5% lactose solutions were 37.7% for the control group and 37.0% for the experimental group (P > 0.02). For the 10% lactose solution the median values were 51.2% and 47.9% (P > 0.02) for the control and experimental groups, respectively. However, for the 2.5% glucose +2.5% galactose meal the median gastric retention was lower (P < 0.02) in the group fed a lactose-enriched chow (38.5%) than in the control group (41.6%). For the 5% glucose +5% galactose solution the median values were not statistically different between groups, 65.0% for the control group and 58.8% for the experimental group. The median values of the specific lactase activity in the small intestine homogenate was 0.74 U/g in the control group and 0.91 U/g in the experimental group. These values were not statistically different (P > 0.05). These results suggest that the prolonged ingestion of lactose by young adult rats changes the gastric emptying of a solution containing 5% monosaccharides. This adaptation may reflect the desensitization of intestinal nutrient receptors, possibly by an osmotic effect of lactose present in the chow.

Animals↗

3-Trehalosamine, a new disaccharide antibiotic.

3-Amino-3-deoxy-alpha-D-glucopyranosyl-alpha-D-glucopyranoside (alpha, alpha--3-trehalosamine) was isolated from a culture of Nocardiopsis trehalosei sp. nov. (NRRL 12026). The structure was determined using a combination of spectroscopic techniques on derivatives of the component sugars, especially gas chromatography-mass spectrometry. The compound exhibited antibiotic activity against Gram-positive organisms at levels similar to what was found for the 2- and 4-trehalosamines.

Animals↗

Enzymatic transformations in supersaturated substrate solutions: II. Synthesis of disaccharides via transglycosylation.

Enzymatic transglycosylation in supersaturated solutions of substrates was investigated using crude glycosidase preparations from barley, snail, and coffee beans. It was shown that the use of supersaturated glycoside solutions as media for transglycosylation reactions offers considerable advantages over conventional aqueous systems. These advantages include higher yields, more efficient use of the donor glycosides and improved volumetric productivity, especially in the case of poorly water-soluble substrates. The regioselectivity of the glycosylation was not significantly affected by high concentrations of acceptor glycosides. It was also shown that the regioselectivity of transfer could be directed towards secondary hydroxyl groups by the use of methyl 6-O-acetyl-alpha-galactopyranoside as acceptor. The value of these approaches was demonstrated by the synthesis of methyl 3- and 4-O-beta-D-galactopyranosyl-alpha-D-galactopyranosides and methyl 3-O-beta-D-galactopyranosyl-alpha-L-fucopyranoside on a preparative scale.

Carbohydrate Conformation↗

Stereoselectivity in the synthesis of unnatural disaccharides.

The synthesis of branched-chain sugars with two hexose moieties linked by a -CH2- bridge in the positions (3-->3) is described. The synthesis starts from protected 3-deoxy-3-(formylmethyl)-alpha-D-allofuranose in which the original formyl group is converted in four reaction steps into a new hexopyranose of D- or L-configuration. The relative configuration of the prepared compounds was determined on the basis of coupling constants in the 1H NMR spectra whereas the absolute configuration of the newly created pyranose was unequivocally assigned by single crystal X-ray crystallography of the 3-deoxy-3-[(2R,4R,5S,6R)-2-ethoxy-5-acetoxy-6- acetoxymethyl-tetrahydropyran-4-ylmethyl]-1,2:5,6-di-O-isopropylid ene- alpha-D-allofuranose (10).

Carbohydrate Conformation↗