ABSTRACT
Deuteron spin-lattice relaxation times of specifically labelled methyl N-acetyl-D-glucosaminides associated to lysozyme were measured from 1H and 2H NMR spectra through bandshape analysis and FT inversion-recovery technique, respectively. Model calculations were carried out in order to assess the limits of the extreme narrowing approximation for the systems studied. Rotational correlation times of the acetamido methyl groups were analyzed in terms of anisotropic overall reorientation combined with internal rotation. The acetamido methyl group undergoes fast internal rotation in the alpha-glycoside complex about an axis nearly parallel with the major ellipsodial axis of lysozyme. More rotational freedom is likely to occur in the beta-glycoside complex.
Subject(s)
Acetylglucosamine/analogs & derivatives , Glucosamine/analogs & derivatives , Muramidase/metabolism , Acetylglucosamine/metabolism , Chemical Phenomena , Chemistry , Chemistry, Physical , Deuterium , Kinetics , Magnetic Resonance Spectroscopy , Mathematics , Molecular Conformation , Spin Labels , Time FactorsABSTRACT
The chlorinated organic compounds are very important from the point of view of the chemical industry and environmental protection, and therefore the gas chromatographic analysis of these compounds is very interesting for analytical chemists. In this paper we studied the relationship between the molecular structure and gas chromatographic retention on several stationary phases having different polarity and at several temperatures of benzene and 12 chlorobenzene compounds as model compounds. A coding system involving primary (mosaic increments) and secondary (bond increments)calculation methods was developed. The retention indices of benzene and the chlorobenzenes calculated on HP-5 at 120 degrees C shows a better performance of the mosaic increments (average absolute deviation delta of 1.7 retention index units) compared with the bond increments (delta = 11.7 retention index units). Retention factors, k, calculated with mosaic increments for chlorobenzenes on SPB-1 and WAX-10, at 140 degrees C, yield average relative errors of epsilon = 0.9 and 3.5%, respectively. Therefore, the presented paper provides a new possibility for precalculation of the retention data.
Subject(s)
Chlorobenzenes/analysis , Chromatography, Gas/methodsABSTRACT
A definitive synthesis of the propyl glycoside (1) of ristotetraose, the heterotetrasaccharide component of the antibiotic ristomycin A (ristocetin A) is described.
Subject(s)
Glycosides/chemical synthesis , Oligosaccharides/chemical synthesis , Carbohydrate Conformation , Carbohydrate Sequence , Magnetic Resonance Spectroscopy , Molecular Sequence Data , Molecular StructureABSTRACT
The oligosaccharide components, 3-O-Me-beta-D-Glcp-(1----3)-beta-D-Glcp-(1----4)-beta-D-Glcp-(1----6)- alpha-D-Glcp-(1----1)-alpha-D-Glcp (1) and beta-D-Glcp-(1----4)-beta-D-Glcp-(1----6)-alpha-D-Glcp-(1----1)-alpha-D- Glcp, of the glycolipid-type antigens isolated from M. smegmatis have been synthesised from 2,3,4,2',3',4',6'-hepta-O-acetyl-alpha,alpha-trehalose and the appropriate glycosyl bromides under Helferich conditions with Hg(CN)2 as the promoter. Condensation of the trisaccharide glycosyl bromide 27 gave an orthoester derivative (28) which could be rearranged, using HgBr2 or boron trifluoride etherate, into the acetylated derivative (29) of 1. The model compound beta-D-Glcp-(1----6)-alpha-D-Glcp-(1----1)-alpha-D-Glcp has also been synthesised.
Subject(s)
Antigens, Bacterial , Disaccharides , Glycolipids/chemical synthesis , Mycobacterium/immunology , Oligosaccharides/chemical synthesis , Trehalose , Carbohydrate Conformation , Carbohydrate Sequence , Glycosides , Indicators and Reagents , Magnetic Resonance Spectroscopy , Optical Rotation , Structure-Activity RelationshipABSTRACT
One-pot acetylation and subsequent partial acetolysis of alpha-, beta- and gamma-cyclodextrins resulted in crystalline peracetylated malto-hexaose, -heptaose, and -octaose, respectively. Prolonged acetolysis of beta-cyclodextrin gave a mixture of acetylated maltooligosaccharides, from which peracetylated malto-triose, -tetraose, and -pentaose were isolated. The acetylated oligosaccharides were converted into alpha-acetobromo derivatives, and then transformed into 4-nitrophenyl and 2-chloro-4-nitrophenyl beta-glycosides. From the 4-nitrophenyl glycosides 4,6-O-benzylidene derivatives were prepared, which were used together with the free glycosides as substrates of porcine pancreatic alpha-amylase.
Subject(s)
Cyclodextrins/metabolism , alpha-Amylases/metabolism , Acetylation , Carbohydrate Sequence , Chromatography, High Pressure Liquid , Crystallization , Humans , Models, Chemical , Molecular Sequence Data , Pancreas/enzymology , TolueneABSTRACT
The title tetrasaccharide having the structure 3-O-Me-beta-L-Xylp-(1----4)- alpha-L-Rhap-(1----4)-alpha-L-Rhap-(1----2)-L-Rhap was obtained by reaction of the alpha-acetobromo derivative of 4-O-(3-O-methyl-beta-L-xylopyranosyl)-L-rhamnopyranose and benzyl 3,4-di-O-benzyl-2-O-(2,3-O-isopropylidene-alpha-L-rhamnopyranosyl)- alpha-L-rhamnopyranoside, followed by removal of the protecting groups. The synthesised compounds were characterised on the basis of n.m.r. data.
Subject(s)
Lipopolysaccharides/chemical synthesis , Oligosaccharides/chemical synthesis , Pseudomonas/immunology , Carbohydrate Sequence , Chromatography, Thin Layer , Indicators and Reagents , Lipopolysaccharides/isolation & purification , Magnetic Resonance SpectroscopyABSTRACT
Diapulmon (Chinoin) which comprise camphor, 1-menthol, eucalyptus oil and quinine dissolved in sunflower oil (Oleum helianthi) is marketed in ampoules of 2 ml but utilized almost exclusively for inhalation therapy. Complexing the active ingredients of Diapulmon with beta-cyclodextrin (beta-CD) a stable non hygroscopic microcrystalline substance is obtained. When this powder sprinkled on hot water, the included volatile compounds are gradually released and the desired pharmacological effect can be brought about.