Elsevier

Carbohydrate Research

Volume 307, Issues 3–4, February 1998, Pages 361-369
Carbohydrate Research

Note
The synthesis of 16-mercaptohexadecanyl glycosides for biosensor applications

https://doi.org/10.1016/S0008-6215(98)00053-6Get rights and content

Abstract

The Pk trisaccharide and the central disaccharide element of asialo GM1 activated as their trichloroacetimidates were each used to glycosylate 16-(p-toluensulfonyloxy)hexadecanol 1. Displacement of the tosyl group by thiocyanate followed by sodium borohydride reduction and saponification afforded oligosaccharide 16-mercaptohexadecanyl glycosides that were isolated as the corresponding disulfides 6 and 17 unless oxygen was rigorously excluded from the solvents used for work-up. Dithiothreitol reduction of disulfides and subsequent isolation under an inert atmosphere with degassed solvents gave the thiols 7 and 18. Chemisorption of ω-glycosyl alkanethiols and alkanethiols onto gold electrodes produces self-assembled monolayers that can act as amperometric biosensors for the detection of proteins that bind to the immobilized oligosaccharide epitope.

Section snippets

General methods

Optical rotations were measured on a Perkin-Elmer 241 polarimeter in a 1 dm cell at ambient temperature (22±2 °C). Analytical thin-layer chromatography (TLC) was performed on Silica Gel 60-F254 (Merck) with detection by quenching of fluorescence and/or by charring with 10% H2SO4 in ethanol solution followed by heating at 180 °C. Millex-HV (0.45 μM) filter units were from Millipore (Missisuaga, ON). Column chromatography was performed on Silica Gel 60 (Merck, 40–60 μm), and solvents were distilled

Acknowledgements

This work was supported by the Protein Engineering (PENCE) and Canadian Bacterial Diseases (CBDN) Network Centers of Excellence. The authors thank Dr Elena Kitova for assistance in the analysis and purification of thiol and disulfide products.

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