Facile Synthesis of Chain-End Functionalized Glycopolymers for Site-Specific Bioconjugation (original) (raw)
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α-Functional glycopolymers: New materials for (poly)peptide conjugation
Polymer, 2005
The synthesis and characterization of a number of N-(hydroxy)succinimidyl ester-terminated glycopolymers obtained via copper(I)catalysed living radical polymerisation have been described. Monomers employed were based on protected glucose and galactose, glucofuranoside monomer (1) and galactopyranoside monomer . The corresponding polymers featured a relatively narrow molecular weight distribution (PDIZ1.10-1.31) and M n between 4.5 and 10.2 kDa. The protecting groups were removed by treatment with formic acid. Analogous fluorescent polymers have been synthesized by copolymerisation of a monomer which fluoresces in the visible, the fluorescent behaviour of these materials has been investigated. Preliminary experiments have also shown that the terminally functional sugar polymers can react with molecules containing primary amino groups and some triblock ABA copolymers have been prepared. q Polymer 46 8536-8545 www.elsevier.com/locate/polymer 0032-3861/$ -see front matter q
Synthesis of Glycopolymer Architectures by Reversible-Deactivation Radical Polymerization
Polymers, 2013
This review summarizes the state of the art in the synthesis of well-defined glycopolymers by Reversible-Deactivation Radical Polymerization (RDRP) from its inception in 1998 until August 2012. Glycopolymers architectures have been successfully synthesized with four major RDRP techniques: Nitroxide-mediated radical polymerization (NMP), cyanoxyl-mediated radical polymerization (CMRP), atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT) polymerization. Over 140 publications were analyzed and their results summarized according to the technique used and the type of monomer(s) and carbohydrates involved. Particular emphasis was placed on the experimental conditions used, the structure obtained (comonomer distribution, topology), the degree of control achieved and the (potential) applications sought. A list of representative examples for each polymerization process can be found in tables placed at the beginning of each section covering a particular RDRP technique.
Synthetic glycopolymers: an overview
European Polymer Journal, 2004
Glycopolymers, synthetic sugar-containing macromolecules, are attracting ever-increasing interest from the chemistry community due to their role as biomimetic analogues and their potential for commercial applications. Recent developments in polymerisation techniques have enabled the synthesis of glycopolymers featuring a wide range of controlled architectures and functionalities. This review covers the syntheses of pendant carbohydrate-carrying linear polymers and their subsequent properties.
Ting, S. R. S. et al., Synthesis of glycopolymers, Polym. Chem.,
Synthetic carbohydrate ligands -also widely known as glycopolymers -are known to undergo numerous recognition events when interacting with their corresponding lectins. Interactions are greatly enhanced due to the multivalent character displayed by the large number of repeating carbohydrate units along the polymers (pendant glycopolymers); therefore, resulting what is called the ''glycocluster effect''. Moreover, the strength and the availability of these multivalent recognitions can be tuned via the architecture of the glycopolymers. Hence, understanding the mechanistic interactions between the types of lectins (plant, animal, toxin and bacteria) with their synthetic ligands is crucial. This review focuses on the synthesis of pendant glycopolymers via various synthetic pathways (free radical polymerization, NMP, RAFT, ATRP, cyanoxyl mediated polymerization, ROP, ROMP and post-polymerization modification) and their interactions with their respectively lectins.
Journal of Polymer Science Part A-polymer Chemistry, 2009
We describe here the direct synthesis of novel gluconamidoalkyl methacrylamides by reacting D-gluconolactone with aminoalkyl methacrylamides. The glycomonomers were then successfully polymerized via the reversible addition-fragmentation chain transfer process (RAFT) using 4-cyanopentanoic acid dithiobenzoate (CTP) as chain transfer agent and 4,4′-azobis(4-cyanovaleric acid) (ACVA) as the initiator in aqueous media. Well-defined polymers were obtained as revealed by gel permeation chromatography. Diblock copolymers were then synthesized by the macro-CTA approach. The cationic glycopolymers were subsequently used in the formation of nanostructures via the complexation with plasmid DNA. As noted by dynamic light scattering, monodisperse nanoparticles were obtained via the electrostatic interaction of the cationic glycopolymer with DNA. The sizes of the nanoparticles formed were found to be stable and independent of pH. In vitro cell viability studies of the glycopolymers were carried out using HELA cell lines. The RAFT synthesized glycopolymers and cationic glyco-copolymers revealed to be nontoxic. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 614–627, 2009
Journal of Polymer Science Part A: Polymer Chemistry, 2011
In this work the synthesis of poly(butyl acrylate)-bpoly(2-{[(D-glucosamin-2-N-yl)carbonyl]oxy}ethyl methacrylate) (PBA-b-PHEMAGl) diblock glycopolymer and poly(2-{[(D-glucosamin-2-N-yl)carbonyl]oxy}ethyl methacrylate)-b-poly(butyl acrylate)-b-poly(2-{[(D-glucosamin-2-N-yl)carbonyl]oxy}ethyl methacrylate) (PHEMAGl-b-PBA-b-PHEMAGl) was performed via atom transfer radical polymerization. Monofunctional and difunctional poly(butyl acrylate) macroinitiators were used to synthesize the well-defined diblock and triblock glycopolymers by chain extension reaction with the glycomonomer HEMAGl.
Green Synthesis of Glycopolymers Using an Enzymatic Approach
Macromolecular Chemistry and Physics
brush systems, [7-11] polystyrene rod-coil systems, [12,13] and modified surfaces. [14] This work was extended in recent years to continue the efforts of the Stadler group. [15-29] The synthesis of glycopolymers was summarized comprehensively in recent years-showing a wide range of possible synthetic methods with the majority of reports applying chain-growth polymerization mechanism either in controlled or uncontrolled fashion. [30-32] To the best of our knowledge, none of these reports utilized enzymes as alternative catalysts to synthesize glycopolymers. The role of enzymes was so far limited to the preparation of sugar-based monomers to avoid tedious protection steps of the saccharide-hydroxyl groups in conventional synthetic reactions. [33-40] In an effort to achieve complete green and sustainable processes in glycopolymer synthesis, enzymes are ideal candidates as a catalyst for the polymerization since they are nontoxic, obtained from renewable materials, and typically work under mild reaction conditions. [41-47] Horseradish peroxidase (HRP) is one of the oxidoreductase enzymes that have been widely reported in mediating enzymatic polymerization of vinyl monomers [48-50] and the polymerization of phenol and aniline derivatives via oxidative couplings. [51] The active site of HRP contains an iron-porphyrin complex to generate free radicals in the presence of hydrogen peroxide substrates. While the versatility of HRP was demonstrated with different polymerizable groups, the polymerization of vinyl monomers derived from natural resources is rarely reported. For example, Singh and Kaplan studied HRP-mediated free radical polymerization (FRP) of the enzymatically synthesized ascorbate-based methacrylate/styrene monomers. [52,53] However, toxic trifluoroethanol was generated during the monomer synthesis which provides a disadvantage of this system in terms of eco-friendliness. In this report, we present an HRP-mediated synthesis of glycopolymers at room temperature in aqueous solution. The glycopolymers consist of poly(2-(β-glucosyloxy)ethyl acrylate) (PGEA), poly(2-(β-glucosyloxy)ethyl methacrylate) (PGEMA), and poly(4-(β-glucosyloxy)butyl acrylate) (PGBA). The used glycomonomers (GEA, GEMA, and GBA) were synthesized by β-glucosidase in the thermodynamically controlled reverse hydrolysis reactions as previously reported by us. [40] Hence, the synthesis of the reported glycopolymers is achieved through a fully enzymatic pathway in the course of preparation of both the monomers as Biocatalysis β-Glucosidase and horseradish peroxidase (HRP) are used as biocatalysts in aqueous solution for the enzymatic synthesis of glycomonomers and the respective enzymatic polymerization toward glycopolymers. The biocatalytically synthesized monomers contain (meth)acrylate functionalities that are able to be polymerized by an enzyme-initiated polymerization using an HRP/hydrogen peroxide/acetylacetone ternary system. The structure of the glycomonomers and the respective glycopolymers as well as the monomer conversion after the reaction are determined by 1 H NMR spectroscopy. The synthesized glycopolymers have a dispersity and a number-average molecular weight up to 5.8 and 297 kg mol −1 , respectively. Thermal and degradation properties of the glycopolymers are studied by differential scanning calorimetry and thermogravimetric analysis. In addition, preparation of glycopolymers via conventional free radical polymerization is performed and the properties of the obtained polymers are compared with the enzymatically synthesized glycopolymers.
Glycopolymer-Based Materials: Synthesis, Properties, and Biosensing Applications
Topics in Current Chemistry
Glycopolymer materials have emerged as a significant biopolymer class that has piqued the scientific community's attention due to their potential applications. Recently, they have been found to be a unique synthetic biomaterial; glycopolymer materials have also been used for various applications, including direct therapeutic methods, medical adhesives, drug/gene delivery systems, and biosensor applications. Therefore, for the next stage of biomaterial research, it is essential to understand current breakthroughs in glycopolymer-based materials research. This review discusses the most widely utilized synthetic methodologies for glycopolymer-based materials, their properties based on structure-function interactions, and the significance of these materials in biosensing applications, among other topics. When creating glycopolymer materials, contemporary polymerization methods allow precise control over molecular weight, molecular weight distribution, chemical activity, and polymer architecture. This review concludes with a discussion of the challenges and complexities of glycopolymer-based biosensors, in addition to their potential applications in the future.
Recent advances in the synthesis of well-defined glycopolymers
Journal of Polymer Science Part A: Polymer Chemistry, 2007
Glycopolymers are receiving increasing interest due to their application in areas, such as glycomics, medicine, biotechnology, sensors, and separation science. Consequently, new methods for their synthesis are constantly being developed, with an increasing emphasis on the preparation of well-defined polymers and on the production of complex macromolecular architectures such as stars. This review cov-