“Click Chemistry” as a Facile Approach to the Synthesis of Polyphosphazene Glycopolymers

Abstract

A versatile approach based on click chemistry to synthesize polyphosphazene glycopolymers is presented. The glucose‐substituted polyphosphazene was synthesized by nucleophilic substitution of poly(dichlorophosphazene) with propargylamine and the subsequent azide/alkyne “click” reaction of poly[di(propargylamine)phosphazene] (PDPAP) with azidosugar. The relative proportion of the glucose substituent can be easily controlled over a broad range by varying the amount of azidoglucose used in the azide/alkyne “click” reaction. magnified image

Glycosylation of Polyphosphazene Nanofibrous Membrane by Click Chemistry for Protein Recognition

“…As an extension to this concept, surface “click” chemistry has been established as a robust series of transformations for the effective modification of materials without destroying their bulk properties 39. However, PDPAP is an elastomer with a glass transition temperature ( T g ) value of −4.0 °C,31 making its nanofibrous membrane susceptible to deformation. Therefore, the glycosylated polyphosphazene was fabricated into nanofibrous membrane via a two‐step process combined with coaxial electrospinning and surface alkyne–azide “click” chemistry, where PAN served as a backbone due to its good thermal stability as the existing high polarity of the nitrile groups in the polymer chains to improve the stability of the glycolpolyphosphazene nanofibers.…”

“…Poly(dichlorophosphazene) was synthesized via ring‐opening polymerization of hexachlorocyclotriphosphazene in a sealed Pyrex tube at 250 °C under vacuum. Poly[di(propargylamine)phosphazene] (PDPAP) was obtained by macromolecular substitution between poly(dichlorophosphazene) and propargylamine and purified according to the procedures reported in our previous study 31. The M n , M w , and polydispersity index D ( M w / M n ) of PDPAP were 8.06 × 10 5 g mol −1 , 1.15 × 10 6 g mol −1 , and 1.43, respectively, according to gel permeation chromatography (GPC) analysis using DMF as the solvent with a flow rate of 1.0 mL min −1 at 60 °C, with poly(methyl methacrylate) standards.…”

“…Glycosylated polyphosphazene nanofibrous membrane was prepared via alkyne–azide click reaction according to the procedure reported in our previous work 31, 35, 36. The PDPAP nanofibrous membrane was incubated for 4 h in a mixture of ethanol and H 2 O (1:1, v/v) containing 0.1 M azido sugar, 1 × 10 −3 M CuSO 4 and 5 × 10 −3 M sodium ascorbate, and subsequently washed with ethanol and water.…”

“…Our previous work suggested that a variety of different polyphosphazene glycopolymers can be synthesized using “click” chemistry 31–33. Taking into account the advantage of nanofibers mentioned above, the purpose of the current work was to fabricate nanofibers with clickable surface.…”

Facile Modification of Silica Substrates Provides a Platform for Direct‐Writing Surface Click Chemistry

“…Recently, both Huisgen's and the copper(I)‐catalyzed cycloaddition were applied for surface modification, as click reaction of monolayers was proven successfully on gold8, 9, 10 and silica11, 12 surfaces. They were considered very useful for the synthesis and modification of polymers,13–16 hydrogels,17 or bioactive surfaces,18 and for surface‐patterning techniques like microcontact printing,19–22 microarray fabrication,23 or dip‐pen nanolithography 24–26. In order to perform the click reaction, the presence of two functional groups is necessary: an alkyne group and an azide group.…”