Efficient Synthesis of Hydrolytically Degradable Block Copolymer Nanoparticles via Reverse Sequence Polymerization-Induced Self-Assembly in Aqueous Media.

Autor: Farmer MAH; Department of Chemistry, The University of Sheffield, Brook Hill, S3 7HF, Sheffield, South Yorkshire, UK., Musa OM; Ashland Specialty Ingredients, 1005 US 202/206, 08807, Bridgewater, NJ, USA., Armes SP; Department of Chemistry, The University of Sheffield, Brook Hill, S3 7HF, Sheffield, South Yorkshire, UK.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2023 Sep 18; Vol. 62 (38), pp. e202309526. Date of Electronic Publication: 2023 Aug 10.
DOI: 10.1002/anie.202309526
Abstrakt: Hydrolytically degradable block copolymer nanoparticles are prepared via reverse sequence polymerization-induced self-assembly (PISA) in aqueous media. This efficient protocol involves the reversible addition-fragmentation chain transfer (RAFT) polymerization of N,N'-dimethylacrylamide (DMAC) using a monofunctional or bifunctional trithiocarbonate-capped poly(ϵ-caprolactone) (PCL) precursor. DMAC monomer is employed as a co-solvent to solubilize the hydrophobic PCL chains. At an intermediate DMAC conversion of 20-60 %, the reaction mixture is diluted with water to 10-25 % w/w solids. The growing amphiphilic block copolymer chains undergo nucleation to form sterically-stabilized PCL-core nanoparticles with PDMAC coronas. 1 H NMR studies confirm more than 99 % DMAC conversion while gel permeation chromatography (GPC) studies indicate well-controlled RAFT polymerizations (M w /M n ≤1.30). Transmission electron microscopy (TEM) and dynamic light scattering (DLS) indicate spheres of 20-120 nm diameter. As expected, hydrolytic degradation occurs within days at 37 °C in either acidic or alkaline solution. Degradation is also observed in phosphate-buffered saline (PBS) (pH 7.4) at 37 °C. However, no degradation is detected over a three-month period when these nanoparticles are stored at 20 °C in deionized water (pH 6.7). Finally, PDMAC 30 -PCL 16 -PDMAC 30 nanoparticles are briefly evaluated as a dispersant for an agrochemical formulation based on a broad-spectrum fungicide (azoxystrobin).
(© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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