Novel Glycopolymer Brushes via ATRP: 1. Synthesis and Characterization

Abstract

The synthesis and characterization of a series of glycopolymer brushes with P(methyl 6-O -methacryloyl-α -D -glucoside) (P(6-O -MMAGIc)) side chains (SCs) is reported. The formation of well-defi ned glycopolymer brushes is confi rmed by 1 H NMR spectroscopy and size exclusion chromatography (SEC) with a MALLS detector. Four multifunctional macroinitiators with different topologies and molar masses are prepared. The P(6-O -MMAGIc) SCs are cleaved from the backbone and analyzed by 1 H NMR and SEC-MALLS, which further confi rmed the synthesis of well-defi ned glycopolymer brushes. The grafting efficiency of P(6-O -MMAGIc) from the different macroinitiators are determined to be in the range 0.37 < f < 0.55.

Tunable, biodegradable grafting-from glycopolypeptide bottlebrush polymers

“…However, this method typically suffers from low graft density and incomplete functionalization. Although much beautiful work has been done to optimize grafting-from systems utilizing controlled radical, ring-opening metathesis, and NCA polymerizations 13 , 16 , 20 – 22 , there are few reports on the use of glyco-monomers and prior work has focused exclusively on reversible deactivation radical polymerization 23 – 28 . This method yields hydrocarbon backbone polymers incapable of the hydrogen bonds crucial to protein conformation and function, requires non-native glycan structures, and, to date, initiation inefficiency has limited the grafting density, as only low MW sidechains were produced.…”

“…S10 ). Previously reported atom transfer radical polymerization grafting-from glycobrushes suffered from inefficient initiation ranging from 23% to 38%, necessitated monomer conversions of <11%, and used non-native glycans and polymer backbones 23 – 26 . Our system overcomes these challenges offering quantitative initiation and conversion, up to 100% graft density, complete tunability in chain length, glycan identity and density, native components, and MWs on par with native proteoglycan and glycoprotein structures.…”

Glycopolymer Brushes by Reversible Deactivation Radical Polymerization: Preparation, Applications, and Future Challenges

“…In most of the cases, this assumption could be very far from reality. N -methyl- d -glucamine and different glucose- and glucosamine-based acrylamide or (meth)acrylate monomers [ 30 , 33 , 43 , 45 , 46 , 47 , 48 , 49 , 50 , 51 ], ( Figure 4 ), either in their linear or ring form, have been synthesized and used for the preparation of well-defined polymer brushes by RDRP methods. The resultant materials have been extensively studied mainly for the specific binding and recognition by lectins [ 22 , 24 , 25 , 38 , 39 , 41 , 48 , 49 , 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 ].…”

Synthesis of Glycopolymer Architectures by Reversible-Deactivation Radical Polymerization

“…Klumperman et al [129,148,149] described the synthesis of a series of cylindrical brushes carrying α-methylglucoside-functionalized graft chains and investigated their thermal and mechanical properties (Entry 101-104, Table 2). To this end, four macroinitiators based on HEMA (M33), MMA (M15), 4-vinylbenzyl chloride (M58), and maleic anhydride (MAnh) were synthesized by ATRP or RAFT copolymerization, followed by chemical modification with 2-bromo-2-methylpropionyl bromide as needed.…”