ABSTRACT
Keratan sulfate (KS) oligomers with well-defined structures were synthesized by keratanase II (KSase II)-catalyzed transglycosylation. N-Acetyllactosamine [Galbeta(1-->4)GlcNAc; LacNAc] oxazoline derivatives with sulfate groups at the C-6 (1 a) and both the C-6 and the C-6' (1 b) were prepared as transition-state analogue substrate monomers for KSase II. Monomer 1 a was effectively oligomerized by the enzyme under weak alkaline conditions, to give alternating 6-sulfated KS oligomers (2 a) in good yields, and with total control of regioselectivity and stereochemistry. KSase II also recognized 1 b, which provided fully 6-sulfated KS oligomers (2 b) in good yields under similar conditions. Nonsulfated LacNAc oxazoline was difficult to oligomerize enzymatically. These results imply that the catalysis mechanism of KSase II involves a sugar oxazolinium ion that requires the 6-sulfate group in the GlcNAc residue not only in hydrolysis of KS chains, but also in oligomerization of oxazoline monomers. This is the first report of KSase II-catalyzed transglycosylation to form beta(1-->3)-glycosidic bond through a substrate-assisted mechanism.
Subject(s)
Acetylglucosaminidase/chemistry , Keratan Sulfate/chemistry , Oxazoles/chemistry , Amino Acid Motifs , Amino Acids/chemistry , Biochemistry/methods , Carbohydrate Conformation , Carbohydrate Sequence , Catalysis , Chromatography/methods , Hydrogen-Ion Concentration , Hydrolysis , Models, Chemical , Molecular Sequence Data , Spectrometry, Mass, Electrospray Ionization , Substrate Specificity , Time FactorsABSTRACT
The physicochemical properties of radionuclides suspended in the air are important parameters in order to evaluate internal doses due to the inhalation of the airborne radionuclides and to develop the air-monitoring system in high-energy proton accelerator facilities. This study focuses on the property of radioactive airborne chlorine (38Cl and 39Cl) and sulphur (38S) produced in Ar gas by irradiation with high-energy neutrons. As a result of the irradiation of a mixture of Ar gas and dry air, 38Cl and 39Cl existed as non-acidic gas and 38S was present as acidic gas. Furthermore, it has been found that in the high-energy neutron irradiation of aerosol containing Ar gas, the higher the amount of radioactive aerosols, the lower will be the amount of radioactive acidic gas.
