Generation of well-defined clickable glycopolymers from aqueous RAFT polymerization of isomaltulose-derived acrylamides (original) (raw)
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Biomacromolecules, 2006
Well-defined linear poly(acryloyl glucosamine) (PAGA) exhibiting molar masses ranging from 3 to 120 K and low polydispersities have been prepared via reversible addition-fragmentation chain transfer polymerization (RAFT) in aqueous solution without recourse to protecting group chemistry. The livingness of the process was further demonstrated by successfully chain-extending one of these polymers with N-isopropylacrylamide affording narrow dispersed thermosensitive diblocks. This strategy of polymerization was finally extended to the preparation of glycopolymer stars from Z designed non-water-soluble trifunctional RAFT agent. After the growth of very short blocks of poly(hydroxyethyl acrylate) (DP nbranch) 10), AGA was polymerized in aqueous solution in a controlled manner affording well-defined 3-arm glycopolymer stars.
Journal of visualized experiments : JoVE, 2015
Synthetic glycopolymers are instrumental and versatile tools used in various biochemical and biomedical research fields. An example of a facile and efficient synthesis of well-controlled fluorescent statistical glycopolymers using reversible addition-fragmentation chain-transfer (RAFT)-based polymerization is demonstrated. The synthesis starts with the preparation of β-galactose-containing glycomonomer 2-lactobionamidoethyl methacrylamide obtained by reaction of lactobionolactone and N-(2-aminoethyl) methacrylamide (AEMA). 2-Gluconamidoethyl methacrylamide (GAEMA) is used as a structural analog lacking a terminal β-galactoside. The following RAFT-mediated copolymerization reaction involves three different monomers: N-(2-hydroxyethyl) acrylamide as spacer, AEMA as target for further fluorescence labeling, and the glycomonomers. Tolerant of aqueous systems, the RAFT agent used in the reaction is (4-cyanopentanoic acid)-4-dithiobenzoate. Low dispersities (≤1.32), predictable copolymer ...
Macromolecules, 2007
We report a detailed kinetic study of the RAFT polymerization of methyl 6-O-methacryloyl-R-D-glucoside (a methacrylic ester-type glycomonomer) with the chain transfer agent (CTA) (4-cyanopentanoic acid)-4-dithiobenzoate and initiator 4,4′-azobis(4-cyanopentanoic acid) in homogeneous aqueous media. The influence of temperature, initiator and CTA concentration, molar mass of the CTA radical leaving group, and the presence of residual oxygen on the polymerization kinetics were investigated in comparison with corresponding conventional free radical polymerizations (i.e., with no CTA present). RAFT processes were characterized by an initial non-steady-state period, the length of which depended inversely on the radical flux in the system, and were found to proceed at a significantly slower rate than the corresponding conventional free radical polymerizations. Also, attainment of the steady-state coincided with complete consumption of the initial CTA. The use of a macromolecular CTA reduced the length of the non-steady-state period but, interestingly, did not eliminate it, and the duration of this period was still shown to depend inversely on the initial CTA to initiator ratio. To our knowledge, this is the first time that a non-steady-state period has been observed in a RAFT polymerization initiated by a macromolecular CTA. Finally, the results of this investigation were used as a guide for the preparation of a series of well-defined living glyco-oligomers (DP n ) 15-66, PDI ) 1.05-1.12) in high yield.
Macromolecules, 2007
We report a detailed kinetic study of the RAFT polymerization of methyl 6-O-methacryloyl-R-D-glucoside (a methacrylic ester-type glycomonomer) with the chain transfer agent (CTA) (4-cyanopentanoic acid)-4-dithiobenzoate and initiator 4,4′-azobis(4-cyanopentanoic acid) in homogeneous aqueous media. The influence of temperature, initiator and CTA concentration, molar mass of the CTA radical leaving group, and the presence of residual oxygen on the polymerization kinetics were investigated in comparison with corresponding conventional free radical polymerizations (i.e., with no CTA present). RAFT processes were characterized by an initial non-steady-state period, the length of which depended inversely on the radical flux in the system, and were found to proceed at a significantly slower rate than the corresponding conventional free radical polymerizations. Also, attainment of the steady-state coincided with complete consumption of the initial CTA. The use of a macromolecular CTA reduced the length of the non-steady-state period but, interestingly, did not eliminate it, and the duration of this period was still shown to depend inversely on the initial CTA to initiator ratio. To our knowledge, this is the first time that a non-steady-state period has been observed in a RAFT polymerization initiated by a macromolecular CTA. Finally, the results of this investigation were used as a guide for the preparation of a series of well-defined living glyco-oligomers (DP n ) 15-66, PDI ) 1.05-1.12) in high yield.
Materials Research, 2014
Poly(2-(dimethylamino)ethylmethacrylate-b-methymethacrylate) (PDMAEMA-b-PMMA) poly(2-(dimethylamino)ethylmethacrylate-b-vinylcaprolactam-b-(2-(dimethylamino)ethyl methacrylate) (PDMAEMA-b-PVCL-b-PDMAEMA) and poly(vinylcaprolactam-b-(2-(dimethylamino) ethylmethacrylate-b-vinylcaprolactam) (PVCL-b-PDMAEMA-b-PVCL) block copolymers were obtained by reversible addition-fragmentation chain transfer (RAFT) polymerization, and the effect of the solution pH on the particle size was investigated. In the case of PDMAEMA-b-PMMA, PDMAEMA was first synthesized using 2-cyanoprop-2-yl dithiobenzoate (CPDB) as a chain transfer agent (CTA), which was subsequently used for the RAFT polymerization of MMA. The triblock copolymers were obtained using PDMAEMA or PVCL as macro-CTAs prepared using dibenzyl trithiocarbonate (DBTTC) as a bifunctional RAFT agent. The structure and formation of the copolymers was confirmed through 1 H NMR and SEC analysis. The particle size varied considerably depending on the pH of the aqueous solutions of copolymers indicating that these materials could be potential candidates for biomedical applications.
Macromolecules, 2010
We report a new strategy to synthesize densely functionalized highly and hyperbranched glycopolymers. Our methodology combines living radical polymerization and click chemistry. Hyperbranched "clickable" scaffolds synthesized via RAFT polymerization are functionalized with carbohydrate groups using an array of "click" chemistry reactions, namely Cu(I)-catalyzed Huisgen 1,3-cycloaddition of azides and alkynes (CuAAC), thiol-ene addition, and thiol-yne addition. This simple and flexible method yields glycopolymers of unique structures, which are potential candidates for biomedical applications.
2008
The controlled synthesis and characterization of a range of stimuli responsive cationic terpolymers containing varying amounts of N-isopropylacrylamide (NIPAM), 3-(methylacryloylamino)propyl trimethylammonium chloride (MAPTAC), and poly(ethylene glycol)monomethyl methacrylate (PEGMA) is presented. The terpolymers were synthesized using reversible addition-fragmentation chain transfer (RAFT) polymerization. Compositions of the terpolymers determined using 1 H NMR were in close agreement to the theoretical values determined from the monomer feed ratios. GPC-MALLS was used to analyze the molecular weight characteristics of the polymers, which were found to have low polydispersities (M w /M n 1.1-1.4). The phase transitions were studied as a function of PEGMA and NIPAM content using temperature controlled 1 H NMR and turbidity measurements (UV-Vis). The relationship between thermal stability and the comonomer ratio of the polymers was measured using thermogravimetric analysis (TGA). Protein interaction studies were performed to determine the suitability of the polymers for biological applications. V V C 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4021-4029, 2008
Facile Synthesis of Chain-End Functionalized Glycopolymers for Site-Specific Bioconjugation
Bioconjugate Chemistry, 2004
A series of derivatized arylamine initiators were used to generate chain-end functionalized glycopolymers by cyanoxyl-mediated free-radical polymerization. Significant features of this strategy include the capacity to produce polymers of low polydispersity (PDI < 1.5) under aqueous conditions using unprotected monomers bearing a wide range of functional groups. In addition, the presence of a phenyl ring simplifies calculation of polymer saccharide content and molar mass by 1 H NMR. It is particularly noteworthy, however, that derivatized arylamine initiators in conjunction with the presence of a terminal cyanate group provide a convenient approach for synthesizing polymers with a variety of distinct functional groups at R and ω chain ends. In the process, the capacity to label glycopolymers or otherwise conjugate them to proteins or other molecules is greatly enhanced.
One-pot synthesis of hyperbranched glycopolymers by RAFT polymerization
Journal of Polymer Science Part A: Polymer Chemistry, 2012
Soluble hyperbranched glycopolymers were prepared by copolymerization of glycan monomers with RAFT inimers in a simple one-pot reaction. Two novel RAFT inimers, 2-(methacryloyloxy)ethyl 4-cyano-4-(phenylcarbonothioylthio)pentanoate (MAE-CPP) and 2-(3-(benzylthiocarbonothioylthio)propanoyloxy)ethyl acrylate (BCP-EA) were synthesized and used to prepare hyperbranched glycopolymers. Two types of galactose-based saccharide monomers, 6-O-methacryloyl-1,2:3,4-di-Oisopropylidene-D-galactopyranose (proGal-M) and 6-O-(2'-acrylamido-2'methylpropanoate)-1,2:3,4-di-O-isopropylidene-D-galactopyranose (proGal-A), containing a methacrylate and an acrylamide group, respectively, were also synthesized and polymerized under the mediation of the MAE-CPP and BCP-EA inimers, respectively. In addition, hyperbranched poly(proGal-M), linear poly(proGal-A) and hyperbranched poly(proGal-A) were generated and their polymerization kinetics were studied and compared. An unusual phenomenon was observed in the kinetics between the two monomers during polymerization. The relationship between polymerization rate and concentration of inimer was totally opposite in different monomer-inimer systems. Branching analysis was conducted by using degree of branching (DB) as the measurement parameter. A higher degree of branching occurred with increased inimer content. Furthermore, these polymers were readily
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.