A series of light-activatable perfluorophenylazide (PFPA)-conjugated carbohydrate structures have been synthesized and applied to glycoarray fabrication. The glycoconjugates were structurally varied with respect to anomeric attachment, S-, and O-linked carbohydrates, respectively, as well as linker structure and length. Efficient stereoselective synthetic routes were developed, leading to the formation of the PFPA-conjugated structures in good yields over few steps. The use of glycosyl thiols as donors proved especially efficient and provided the final compounds in up to 70% total yield with high anomeric purities. PFPA-based photochemistry was subsequently used to generate carbohydrate arrays on a polymeric surface, and surface plasmon resonance imaging (SPRi) was applied for evaluation of carbohydrate-protein interactions using the plant lectin Concanavalin A (Con A) as a probe. The results indicate better performance and equal efficiency of S- and O-linked structures with intermediate linker length.

The mechanism involved in the photochemical immobilization of poly(4‐vinylphenol) (PVP) thin films was investigated. The films were fabricated by a simple procedure of UV irradiation and solvent extraction. A combination of ellipsometry, IR, and high‐resolution X‐ray photoelectron spectroscopy (XPS) was used to provide detailed and quantitative analysis of the composition of the photochemical reaction products. Upon irradiation at 260 nm, benzyl and phenoxy radicals are generated in the polymer. In the absence of oxygen, PVP films crosslinked via the combination of the benzyl radicals or phenoxy radicals. At lower irradiation doses, the photochemical process was dominated by crosslinking of the polymer backbone via the combination of benzyl radicals. At higher exposure doses, crosslinked quinoid structures were generated, and the concentration increased with the irradiation time. No oxidation or degradation products were observed. In the presence of oxygen, additional reactions of oxidation and degradation occurred. At lower doses, oxidation at the benzyl position produced the ketone structure evidenced by the drastic increase in the O content in the irradiated films. As the irradiation doses increased, further oxidation at the methylene position occurred, and in addition, volatile and degradation products were also generated. This photochemical process was successfully employed to fabricate patterned PVP structures.magnified image

The use of thioglycosides and other glycan derivatives with anomeric sulfur linkages is gaining increasing interest, both in synthesis and in various biological contexts. Herein, we demonstrate the occurrence and circumvention of anomerization during 1-S-glycosylation reactions, and present highly efficient and stereocontrolled syntheses of a series of photoprobe-thiosaccharide conjugates. Mutarotation of glycosyl thiols proved to be the origin of the anomeric mixtures formed, and kinetic effects could be used to circumvent anomerization. The synthesized carbohydrate conjugates were then evaluated by both solution- and solid-phase-based techniques. Both binding results showed that the S-linked glyco-sides interact with their cognate lectins comparably to the corresponding O-analogs in the present cases, thus demonstrating the reliability of the solid-support platform built upon our photo-initiated carbohydrate immobilization method for probing protein bindings, and showing the potential of combining these two means for studying carbohydrate–protein interactions.

Covalently immobilized poly(4-vinylphenol) (PVP) monolayer films were fabricated by spin coating PVP on perfluorophenyl azide (PFPA)-functionalized surface followed by UV irradiation. The pH-responsive behavior of these PVP ultrathin films was evaluated by ellipsometry, quartz crystal microbalance (QCM) and surface plasmon resonance (SPR). By monitoring the responses of these films to pH in situ, the ionization constant of the monolayer thin films was obtained. The apparent pKa value of these covalently immobilized PVP monolayers, 13.4 by SPR, was 3 units higher than that of the free polymer in aqueous solution.