Synthesis of aryl azide chain-end functionalized N-linked glycan polymers and their photo-labelling of specific protein

Abstract

We report a straightforward synthesis of aryl azide chain-end functionalized N-linked glycan polymers and its application for affinity-assisted photo-labelling of specific protein.

Carbohydrate- and Chain Length-Controlled Complexation of Carbon Nanotubes by Glycopolymers

“…Biomimetic glycopolymers with monosaccharide and disaccharide groups were synthesized via the cyanoxyl-free-radical-mediated polymerization scheme in one-pot fashion, as previously reported. 30,31 In essence, cyanoxyl radicals were generated by an electron−transfer reaction between cyanate anions from a sodium cyanate aqueous solution and aryl-diazonium salts, which were prepared in situ through a diazotization reaction of arylamine in water. Cyanoxyl persistent radicals and aryl-type active radicals were simultaneously produced, where only the latter species was capable of initiating chain growth, thus facilitating the copolymerization of N-acryloyl-glycosylamine glycomonomers (Glyco-AM) and free acrylamide (AM).…”

“…Cyanoxyl persistent radicals and aryl-type active radicals were simultaneously produced, where only the latter species was capable of initiating chain growth, thus facilitating the copolymerization of N-acryloyl-glycosylamine glycomonomers (Glyco-AM) and free acrylamide (AM). 30,31 Particularly, glycocopolymers (i.e., AM/Glyco-AM) expressing different densities of carbohydrate ligands (i.e., y/x) were synthesized by varying the ratios between N-acryloyl-glycosylamine glycomonomers and free AM. Lact-homopolymers of various chain lengths n were synthesized by varying the amount of N-lactosylacrylamide monomers without inclusion of free AM.…”

“…Glycopolymers, namely, polymers with carbohydrate pendant groups, have been extensively used as glycoconjugate mimetics for different biological applications. − It is generally accepted that synthetic glycopolymers can mimic the functions of naturally occurring glycoconjugates , and have been employed for biosensor and drug delivery applications and biofunctionalization of nanomaterials of different interests. , Noncovalent complexation of SWCNTs by glycopolymers is of interest because of the potential of polymer backbone to form a wrapping structure on the nanotube surface, while hydrophilic groups are exposed to water for entropic stabilization of polymer–SWCNT complexes. Synthetic glycopolymers also provide greater structural tunability compared to natural glycoconjugates.…”

Glycopolymer-Wrapped Carbon Nanotubes Show Distinct Interaction of Carbohydrates With Lectins

“…CoMoCAT SWCNT powder (SG65i-L39, CHASM Advanced Materials), that is enriched in small diameter (6,5) chirality species, was dispersed in a total volume of 1 ml aqueous solutions of synthetic glycopolymers by probe tip sonication (model VCX 130, Sonics and Materials, Inc.) in an ice bath at a power level of 8 W. Disaccharide ß -lactose (Lact)-containing homopolymers were synthesized from lactosylacrylamide (i.e., Lact-AM) monomer using cyanoxyl free radical-mediated polymerization (CFRMP) scheme in one-pot fashion as previously reported ( Tang et al, 2017 ; Chan et al, 2020 ). The polymer chain lengths of Lact-homopolymers utilized here are 400 and 415 (i.e., Lact-AM 400 and Lact-AM 415), respectively.…”

“…We have previously reported the creation of stable and water-soluble glycopolymer-wrapped single-wall carbon nanotubes (Glyco-SWCNTs) through the noncovalent complexation of nanotubes with polymers, where the interaction of glycopolymers with SWCNTs is strongly dependent on the carbohydrate identity, ligand density, and the polymer chain length ( Cantwell et al, 2020 ). Synthetic glycopolymers with highly tunable carbohydrate structures are chemically stable and can be used as glycoconjugate mimetics for many biological applications ( Sun 2018 ; Chan et al, 2020 ). The multivalency of glycopolymers together with the tunability in polymer chain length, ligand composition and density, flexibility, and conformation promotes strong carbohydrate-mediated interactions with lectins ( Kumar et al, 2011 ; Narla et al, 2012 ; Miura et al, 2016 ; Tang et al, 2017 ).…”