Dataset Information

Construction of Highly Ordered Glyco-Inside Nano-Assemblies through RAFT Dispersion Polymerization of Galactose-Decorated Monomer.

ABSTRACT: Glyco-assemblies derived from amphiphilic sugar-decorated block copolymers (ASBCs) have emerged prominently due to their wide application, for example, in biomedicine and as drug carriers. However, to efficiently construct these glyco-assemblies is still a challenge. Herein, we report an efficient technology for the synthesis of glyco-inside nano-assemblies by utilizing RAFT polymerization of a galactose-decorated methacrylate for polymerization-induced self-assembly (PISA). Using this approach, a series of highly ordered glyco-inside nano-assemblies containing intermediate morphologies were fabricated by adjusting the length of the hydrophobic glycoblock and the polymerization solids content. A specific morphology of complex vesicles was captured during the PISA process and the formation mechanism is explained by the morphology of its precursor and intermediate. Thus, this method establishes a powerful route to fabricate glyco-assemblies with tunable morphologies and variable sizes, which is significant to enable the large-scale fabrication and wide application of glyco-assemblies.

SUBMITTER: Qiu L

PROVIDER: S-EPMC8252037 | biostudies-literature | 2021 May

REPOSITORIES: biostudies-literature

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Construction of Highly Ordered Glyco-Inside Nano-Assemblies through RAFT Dispersion Polymerization of Galactose-Decorated Monomer.

Qiu Liang L Zhang Haoran H Bick Thomas T Martin Johannes J Wendler Petra P Böker Alexander A Glebe Ulrich U Xing Chengfen C

Angewandte Chemie (International ed. in English) 20210325 20

Glyco-assemblies derived from amphiphilic sugar-decorated block copolymers (ASBCs) have emerged prominently due to their wide application, for example, in biomedicine and as drug carriers. However, to efficiently construct these glyco-assemblies is still a challenge. Herein, we report an efficient technology for the synthesis of glyco-inside nano-assemblies by utilizing RAFT polymerization of a galactose-decorated methacrylate for polymerization-induced self-assembly (PISA). Using this approach, ...[more]

PMID: 33565244

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Project description:A poly(2-(dimethylamino)ethyl methacrylate) (PDMA) chain transfer agent (CTA) is used for the reversible addition-fragmentation chain transfer (RAFT) alcoholic dispersion polymerization of benzyl methacrylate (BzMA) in ethanol at 70 °C. THF GPC analysis indicated a well-controlled polymerization with molecular weight increasing linearly with conversion. GPC traces also showed high blocking efficiency with no homopolymer contamination apparent and Mw/Mn values below 1.35 in all cases. 1H NMR studies confirmed greater than 98% BzMA conversion for a target PBzMA degree of polymerization (DP) of up to 600. The PBzMA block becomes insoluble as it grows, leading to the in situ formation of sterically stabilized diblock copolymer nanoparticles via polymerization-induced self-assembly (PISA). Fixing the mean DP of the PDMA stabilizer block at 94 units and systematically varying the DP of the PBzMA block enabled a series of spherical nanoparticles of tunable diameter to be obtained. These nanoparticles were characterized by TEM, DLS, MALLS, and SAXS, with mean diameters ranging from 35 to 100 nm. The latter technique was particularly informative: data fits to a spherical micelle model enabled calculation of the core diameter, surface area occupied per copolymer chain, and the mean aggregation number (Nagg). The scaling exponent derived from a double-logarithmic plot of core diameter vs PBzMA DP suggests that the conformation of the PBzMA chains is intermediate between the collapsed and fully extended state. This is in good agreement with 1H NMR studies, which suggest that only 5-13% of the BzMA residues of the core-forming chains are solvated. The Nagg values calculated from SAXS and MALLS are in good agreement and scale approximately linearly with PBzMA DP. This suggests that spherical micelles grow in size not only as a result of the increase in copolymer molecular weight during the PISA synthesis but also by exchange of individual copolymer chains between micelles and/or by sphere-sphere fusion events.

Project description:Synthesis of cationic polyacrylamides (CPAMs) by introducing cationic polymer precursors followed by chain extension of acrylamide (AM) homopolymer blocks via RAFT polymerization is a promising approach for engineering high-performance CPAMs. However, the aqueous solution polymerization of AM usually leads to high viscosity, thus limiting the solid content in the polymerization system. Herein a novel approach is introduced that uses a random copolymer of AM and methacryloxyethyltrimethyl ammonium chloride (DMC) as a macro RAFT chain transfer agent (mCTA) and stabilizer for aqueous RAFT dispersion polymerization of AM. The AM/DMC random copolymers synthesized by RAFT solution polymerization, having narrow dispersities (Đ s) at different molecular weights and cationic degrees (C s), could serve as the mCTA, which was confirmed by mCTA chain extension in aqueous solution polymerization of AM under different C s, solid contents, AM addition contents, extended PAM block lengths, and mCTA chain lengths. The block CPAMs had a Đ value of less than 1.2. A model was developed using the method of moments with consideration of the diffusion control effect, for further understanding the chain extension kinetics. Predicted polymerization kinetics provided an accurate fit of the experimental data. The AM/DMC random copolymers were further used for aqueous RAFT dispersion polymerization of AM under different polymerization temperatures, C s, and mCTA chain lengths. The resulting products had a milky appearance, and the block copolymers had Đ s of less than 1.3. Higher C s and longer chain lengths on mCTAs were beneficial for stabilizing the polymerization systems and produced smaller particle sizes and less particle aggregation. The products remained stable at room temperature storage for more than a month. The results indicate that aqueous RAFT dispersion polymerization using random copolymers of AM and DMC at moderate cationic degrees as a stabilizer and mCTA is a suitable approach for synthesizing CPAM block precursors at an elevated solid content.

Dataset Information

Construction of Highly Ordered Glyco-Inside Nano-Assemblies through RAFT Dispersion Polymerization of Galactose-Decorated Monomer.

Publications

Construction of Highly Ordered Glyco-Inside Nano-Assemblies through RAFT Dispersion Polymerization of Galactose-Decorated Monomer.

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