Star‐shaped polypeptide/glycopolymer biohybrids: Synthesis, self‐assembly, biomolecular recognition, and controlled drug release behavior

Abstract

Star-shaped polypeptide/glycopolymer biohybrids composed of poly(cbenzyl L-glutamate) and poly(D-gluconamidoethyl methacrylate), exhibiting controlled molecular weights and low polydispersities, were synthesized by the combination of ring-opening polymerization of c-benzyl-L-glutamate N-carboxyanhydride and the direct atom transfer radical polymerization of unprotected D-gluconamidoethyl methacrylate glycomonomer. These biohybrids were characterized in detail by means of FTIR, 1 H NMR, gel permeation chromatography, differential scanning calorimetry, and wide angle X-ray diffraction. Independent of weight fraction of hydrophilic glycopolymer segment, the biohybrids self-assembled into large spherical micelles in aqueous solution, which had a helical polypeptide core surrounded by a multivalent glycopolymer shell. The deprotected poly(L-glutamate)/glycopolymer hybrid exhibited a pH-sensitive self-assembly behavior, and the average size of the nanoparticles decreased gradually over the aqueous pH value. Moreover, whatever these biohybrids existed in unimolecular level or glycopolymer-surfaced nanoparticles, they had specific biomolecular recognition with Concanavalin A compared with bovine serum albumin. Furthermore, star-shaped biohybrids showed a higher doxorubicin loading efficiency and longer drug-release time than linear analogues. This potentially provides a platform for fabricating targeted anticancer drug delivery system and studying glycoprotein functions in vitro.

Surface hydrophilic modification with a sugar moiety for a uniform-sized polymer molecularly imprinted for phenobarbital in serum

“…The synthesis and application of glycopolymers have attracted a great deal of attention from researchers in recent years due to their highly hydrophilic characteristics and with their innate biocompatibility [20][21][22][23][24][25][26]. They were widely applied in various fields of biomedicine, including bioseparation, tissue engineering and cell recognition.…”

Water-soluble starlike poly(acrylic acid) graft polymer: preparation and application as templates for silver nanoclusters

“…Recently, they have been widely investigated in terms of micellar aggregation in solution because of their well-defined macromolecular architecture [27,28]. In addition, the aggregates of star polymers which have amino groups, hydroxyl groups or carboxylic acid groups in the side chains have versatile applications in medicine and biology [29][30][31], catalytical chemistry [32][33][34], and nanotechnology [35,36]. For example, Kumacheva's group recently reported fast photoactivated synthesis of stable fluorescent silver nanoclusters [37] and other semiconductor or magnetic nanoparticles [38] by employing polymer microgels with concentrated carboxyl groups as templates.…”

Synthesis of star-glycopolymers by Cu(0)-mediated radical polymerisation in the absence and presence of oxygen

“…29,38 The tolerance to oxygen and shorter polymerisation time guarantee our approach more possibilities in complex systems.…”

“…28,29 However, there are disadvantages such as easily coupling between star molecules, producing linear by-product and needing high reaction temperature. Cu(0)-mediated Living Radical Polymerisation (LRP) possesses many advantages, [30][31][32][33][34][35] although the mechanism is under debate.…”