Glycopolymers via Post‐Polymerization Modification Techniques

Burns, James R.; Gibson, Matthew I.; Becer, C. Remzi

doi:10.1002/9783527655427.ch10

Cited by 5 publications

(8 citation statements)

References 117 publications

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“…75 With controlled polymerization reactions, the density of the carbohydrate ligand can be manipulated in two ways—copolymerization of a monomer bearing the carbohydrate epitope with a biologically inert monomer, or post-polymerization functionalization of a polymer with the carbohydrate ligand and a biologically inert ligand (Figure 2). 76 Using either approach, the overall length of the polymer can be kept constant, while the level of carbohydrate substitution can be varied.…”

Section: Maximizing Protein Recognition Of Glycopolymersmentioning

confidence: 99%

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Glycopolymer probes of signal transduction

2013

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Glycans are key participants in biological processes ranging from reproduction to cellular communication to infection. Revealing glycan roles and the underlying molecular mechanisms by which glycans manifest their function requires access to glycan derivatives that vary systematically. To this end, glycopolymers (polymers bearing pendant carbohydrates) have emerged as valuable glycan analogs. Because glycopolymers can readily be synthesized, their overall shape can be varied, and they can be altered systematically to dissect the structural features that underpin their activities. This review provides examples in which glycopolymers have been used to effect carbohydrate-mediated signal transduction. Our objective is to illustrate how these powerful tools can reveal the molecular mechanisms that underlie carbohydrate-mediated signal transduction.

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Section: Maximizing Protein Recognition Of Glycopolymersmentioning

confidence: 99%

“…2). 76 Using either approach, the overall length of the polymer can be kept constant, while the level of carbohydrate substitution can be varied.…”

Section: Glycopolymer Length and Functional Affinitymentioning

confidence: 99%

Glycopolymer probes of signal transduction

2013

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“…Many attempts were performed to polymerize glycomonomers in a controlled manner by anionic and cationic, controlled radical, ring‐opening, and other polymerization techniques . However, the synthesis of glycomonomers usually requires various steps and the functional groups of unprotected glycomonomers reveal incompatibility with most controlled polymerization techniques . Additionally, high molar mass polymers with a narrow distribution are still challenging to obtain by polymerizing glycomonomers.…”

Section: Introductionmentioning

confidence: 99%

“…To postmodify polymers with carbohydrates, a reactive polymer backbone is required. For this purpose, many functional groups are reported, including 4‐nitrophenyl carbonate, para ‐fluoro‐phenyl, alkinyl‐, alkenyl, and others …”

Section: Introductionmentioning

confidence: 99%

RAFT polymerization and thio‐bromo substitution: An efficient way towards well‐defined glycopolymers

Pröhl

Englert

Gottschaldt

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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Despite an increasing effort to design well-defined glycopolymers, the convenient synthesis of polymers with higher DPs (>100) and without tedious protection and deprotection steps remains a challenge. Combining the reversible addition fragmentation transfer (RAFT) polymerization and the efficient substitution of primary bromo groups by thiols, we were able to synthesize a set of well-defined glycopolymers with DPs of up to 115. With the polymerization of the highly reactive monomer (2-bromoethyl)-acrylate polymers with low dispersities were obtained that could efficiently be functionalized with various sugar thiol(ate)s. In particular, derivatives of D-glucose, D-galactose, and D-mannose gave excellent degrees of functionalization close to quantitative conversion using only a slight excess of the thiol. This atom efficient synthesis can even be applied for copolymers with acid or base labile components due to the use of unprotected sugar moieties and, hence, the lack of further deprotection steps. Binding studies with the lectin concanavalin A and the subsequent competition studies with a-D-methyl-mannopyranose (aMeMan) proved the effective binding of these derivatives and revealed a DP-and carbohydrate-dependent clustering and dissolution.

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“…63 The direct polymerization of the respective glycomonomers still remains a challenge, and thus far the most common routes are via polymerization of protected sugar monomers 64 or post modification such as using CuAAC or activate ester strategies. 14,22,65,66 Nevertheless, these attachments create additional linker groups such as triazoles that may impact on binding affinity. 67,68 The presented substitution of BEA does not create such expansive linkers.…”

Section: Scheme 2: Summary Of the Substitutionsmentioning

confidence: 99%

Poly(bromoethyl acrylate): A Reactive Precursor for the Synthesis of Functional RAFT Materials

2016

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Post-polymerization modification has become a powerful tool to create a diversity of functional materials. However, simple nucleophilic substitution reactions on halogenated monomers remains relatively unexplored. Here we report the synthesis of poly(bromoethyl acrylate) (pBEA) by reversible addition fragmentation chain transfer (RAFT) polymerization to generate a highly reactive polymer precursor for post-polymerization nucleophilic substitution. RAFT polymerization of BEA generated well-defined homopolymers and block copolymers over a range of molecular weights. The alkyl bromine containing homo-and block copolymer precursors were readily substituted by a range of nucleophiles in good to excellent conversion under mild and efficient reaction conditions without the need of additional catalysts. The broad range of nucleophilic species that are compatible with this post modification strategy enable facile synthesis of complex functionalities, from permanently charged polyanions to hydrophobic polythioethers to glycopolymers.

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Glycopolymers via Post‐Polymerization Modification Techniques

Cited by 5 publications

References 117 publications

Glycopolymer probes of signal transduction

Glycopolymer probes of signal transduction

RAFT polymerization and thio‐bromo substitution: An efficient way towards well‐defined glycopolymers

Poly(bromoethyl acrylate): A Reactive Precursor for the Synthesis of Functional RAFT Materials

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