Analysis of glycosaminoglycan monosaccharides by capillary electrophoresis using indirect laser-induced fluorescence detection

Two methods for monosaccharide analysis by capillary electrophoresis (CE) using counterelectroosmotic and coelectroosmotic modes with indirect laser-induced fluorescence detection were optimised and compared. A mixture of seven glycosaminoglycan-derived hexoses was separated in alkaline fluorescein-based electrolytes and detected in both counterelectroosmotic and coelectroosmotic conditions. The fluorescein concentration and pH of the background electrolyte, and the influence of the reversal of electroosmotic flow by addition of hexadimethrine bromide on the separation were studied. Coelectroosmotic CE conditions provided better resolution and limits of detection. A 10(-6) M fluorescein solution at pH 12.25 containing 0.0005% (w/v) hexadimethrine bromide was used as background electrolyte. Quality parameters such as run-to-run, day-to-day precision and limits of detection were calculated, and better figures of merit were obtained for the coelectrooosmotic conditions than for the counterelectroosmotic mode. The coelectroosmotic method was applied to the quantitation of the hexosamine contents in glycosaminoglycans after acid hydrolysis. The method proved to be suitable for the determination of dermatan sulfate in heparin down to 2% (w/w).     

Synthesis of 3-epi-6,7-dideoxyxestobergsterol A

3-Epi-6,7-dideoxyxestobergsterol A (2), an analogue of xestobergsterol A, has been synthesized from dehydroepiandrosterone (3) in 15 steps. The key synthetic intermediate, 15beta,16alpha-dioxypregn-17(20)E-ene derivative 8, was prepared from the corresponding 15beta,16beta-epoxide 6 by treating with acetic acid and titanium tetraisopropoxide. The 23-oxo side chain was constructed stereoselectively by orthoester Claisen rearrangement of 8 followed by introduction of an isobutyl group. Basic treatment of the 15,23-diketone 12 followed by deprotection gave the title compound 2.     

Steroidal glycosides from the aerial part of Asclepias incarnata L. II

Thirty new steroidal glycosides were obtained from the aerial part of Asclepias incarnata L. (Asclepiadaceae). These glycosides were confirmed to have lineolon, isolineolon, 12-O-acetyllineolon, 12-O-(Z)-cinnamoyllineolon, metaplexigenin, 15 beta-hydroxylineolon, 15 beta-hydroxyisolineolon, 16 alpha-hydroxyisolineolon, 12-O-tigloyl-16 alpha-hydroxyisolineolon as the aglycone and 2,6-dideoxyhexopyranose as the sugar sequence by spectroscopic methods and chemical evidence.     

The toxic effect of aluminium in vines

The split-root technique was used to study the effect of varying the growth media on the elemental content of nutrient elements in the roots of grape vines. The varieties 2-1 (R99 x Jacquez) and Sauvignon blanc (Vitis vinifera) were grown in Hoagland water culture with and without added aluminium. The elemental concentrations of Mg, Al, Si, P. S, Cl, K and Ca in the dried roots were determined by PIXE. Roots grown in Al-rich media were deficient in Mg and Ca, but enriched in Al. There was a correlation between Al and Si but the uptake differed in the two varieties.     

Study of the formation of polyimide from complexes of benzophenonetetracarboxylic acid diester with different diamines. 2. Features of thermal imidization of the molecular complex of benzophenonetetracarboxylic acid diester with 2,6-diaminopyridine

H-bond complexes of benzophenonetetracarboxylic acid dimethyl ester with 2,6-diaminopyridine (BZPE·DAP) have a dimeric structure in which one of the amino groups of the diaminopyridine participates in the formation of an H bond and the other does not form strong intermolecular bonds. During thermal imidization, the relative reactivity of the free amino group is lower than the reactivity of the group bound in the complex. In the BZPE·DAP system, 10% of the free amino groups remain after completion of imidization and they disappear at a high temperature. It is hypothesized that they can participate in the formation of interchain imide bonds.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 530–533, March, 1990.     

New rearrangement in the 3-indolinone series

In an aqueous alcohol solution of hydrogen chloride 1-(2-propionylphenyl)amino-2-alkoxy-2-methyl-3-indolinone undergoes rearrangement to 2-(2-acetylcarbonyl)phenyl-3-ethylindazole. The structure of the rearrangement product was investigated by x-ray diffraction analysis.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 929–932, July, 1991.