Synthesis of glycosyl amino acids by light-induced coupling of photoreactive amino acids with glycosylamines and 1-C-aminomethyl glycosides.

The glycosylamines of O-acetyl-protected GlcNAc and chitobiose, as well as two partially unprotected 1-C-aminomethyl glucosides, were photochemically coupled with orthogonally protected N-aspartyl-5-bromo-7-nitroindoline derivatives. The reactions proceeded under neutral conditions by irradiation with near-UV light. The glycosyl asparagines with N- or C-glycosyl linkages were afforded in 60-85% yield on a 10-70 mg scale. Moreover, the ability of a highly photoreactive N-glutamyl-4-methoxy-7-nitroindoline derivative to acylate amino saccharides was tested. Upon irradiation in the presence of a dimeric 1-C-aminomethyl glycoside, or a glycosylamine, the corresponding glycosyl glutamines were obtained in 50% and 30% yield, respectively. Preparations of the photoreactive aspartates and the 1-C-aminomethyl glycosides are also described.

Wavelength-tunable ultraviolet photodissociation (UVPD) of heparin-derived disaccharides in a linear ion trap.

A set of three heparin-derived disaccharide deprotonated ions was isolated in a linear ion trap and subjected to UV laser irradiation in the 220-290 nm wavelength range. The dissociation yields of the deprotonated molecular ions were recorded as a function of laser wavelength. They revealed maximum absorption at 220 nm for the nonsulfated disaccharide, but centered at 240 nm for the sulfated species. The comparison of the fragmentation patterns between ultraviolet photodissociation (UVPD) at 240 nm and CID modes showed roughly the same distribution of fragment ions resulting from glycosidic bond cleavages. Interestingly, UVPD favored additional cross ring cleavages of A and X type ion series enabling easier sulfate group location. It also reduced small neutral losses (H(2)O).

Radiolysis of alpha, alpha-trehalose in concentrated aqueous solution; the effect of co-irradiated proteins and lipids.

gamma-Radiolysis (dose-rate: 0 X 89 Gy/s) or electron (e)-radiolysis (dose-rate: 5 X 10(7) Gy/s) of unbuffered aqueous solutions of alpha, alpha-trehalose (concentration: 60 mg/ml, radiation dose: 20 kGy) at 0 degree C yielded glucose (Ggamma = 1 X 7; Ge = 0 X 63) and 5-deoxyxylohexodialdose (Ggamma = 0 X 21; Ge = 0 X 05). Buffering at pH-values of 5 X 0 or 5 X 5 and irradiation caused increased formation of these monomeric products, particularly of the deoxy-compound. On addition of increasing amounts of bovine serum albumin or ovalbumin (10-30 mg/ml) and irradiation the yields of products were markedly reduced. The decrease in glucose formation was less pronounced when sperm whale myoglobin was present during gamma- or electron-irradiation. The G-values of 5-deoxyxylohexodialdose, however, were increased by 45 per cent (gamma-irradiation) and 70 per cent (electron-irradiation) at approximately 10 mg/ml of admixed myoglobin. Further increase in myoglobin concentration led to a gradual decrease in the yields of the deoxy-product. The observed effects are explained by scavenging of water radicals and by interactions of the added substrates with sugar radicals. Emulsified lipids (palmitic acid methylester or trilinoleic glycerol) did not affect the radiation-induced formation of products from trehalose.