Synthesis of biomimetic poly (2-(methacryloyloxy) ethyl phosphorylcholine) nanolatexes via atom transfer radical dispersion polymerization in alcohol/water mixtures
Abstract
Poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC) exhibits a phenomenon known as co-nonsolvency in certain alcohol/water binary mixtures. We have exploited this phenomenon to prepare a series of sterically stabilized PMPC nanolatexes by atom transfer radical polymerization (ATRP) under dispersion polymerization conditions using a near-monodisperse poly(ethylene oxide) (PEO) macroinitiator in a 9:1 isopropanol/water mixture. The as-synthesized nanolatex particles comprised nonsolvated PMPC cores and solvated PEO shells, as determined by 1 H NMR spectroscopy. In our preliminary experiments linear core-forming PMPC chains were targeted, but alternatively either ethylene glycol dimethacrylate or bisphenol A dimethacrylate can be used as comonomers (at up to 10 mol % based on MPC) in order to prepare cross-linked PMPC particles that acquire swollen microgel character when dialyzed against pure water. Low levels of cross-linker (e.g., 4 mol %) lead to bimodal microgel size distributions as judged by dynamic light scattering. However, higher levels of cross-linker (e.g., 10 mol %) lead to narrow unimodal microgel size distributions, since all the core-forming PMPC chains become cross-linked. The final nanolatex/microgel dimensions are dictated by the target block compositions and initial MPC concentration used in these ATRP syntheses. A PEO 113 - b -PMPC 50 formulation synthesized at 30 wt % solids produced nanolatex/microgel particles that were 5−6 times larger than those observed for the same block composition prepared at 10 wt % solids. TEM and SEM studies confirm that these new sterically stabilized particles have uniform spherical morphologies. Cross-linked PEO- b -PMPC particles were analyzed by X-ray photoelectron spectroscopy after dialysis against water. The surface coverage of the PEO stabilizer chains was estimated to be 54−61%. Aqueous electrophoresis studies confirmed that the PEO- b -PMPC microgels exhibited almost zero net charge, and the addition of electrolyte had little effect on their dimensions and colloidal stability due to the anti-polyelectrolyte behavior expected for the zwitterionic PMPC chains.
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Armes and coworkers synthesized zwitterionic PMPC-based block copolymers by a dispersion ATRP process.
“Armes and coworkers synthesized zwitterionic PMPC-based block copolymers by a dispersion ATRP process [29].”
From Block Copolymers: Synthesis, Self-Assembly, and Applications (2017) · cites this paper as [29]
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Block Copolymers: Synthesis, Self-Assembly, and Applications
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“Armes and coworkers synthesized zwitterionic PMPC-based block copolymers by a dispersion ATRP process [29].”
Method
- Authors
- Sugihara, S., Sugihara (nee Nishikawa), K., Armes, S. P., Ahmad, H., & Lewis, A. L.
- Affiliations
- University of Fukui (JP)
- Department of Chemistry, University of Sheffield, Brook Hill, Sheffield, South Yorkshire S3 7HF, U.K.
- University of Sheffield (GB)
- University of Rajshahi (BD)
- Biocompatibles (United Kingdom) (GB)
- Corresponding author
- Sugihara, Shinji
- Armes, Steven P.
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2010-07-12
- Volume
- 43
- Issue
- 15
- Pages
- 6321-6329
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W1971509973
- Cited by
- 72
- References
- 68
- Citations by year
- 2024: 2 · 2023: 3 · 2022: 4 · 2021: 7 · 2020: 4 · 2019: 8 · 2018: 6 · 2017: 7 · 2016: 8 · 2015: 4 · 2014: 4 · 2013: 3 · 2012: 5
- FWCI
- 2.38
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Physical Sciences › Materials Science › Biomaterials › Hydrogels: synthesis, properties, applications
- Physical Sciences › Materials Science › Surfaces, Coatings and Films › Polymer Surface Interaction Studies
- Keywords
- alcohol-water mixtures, microgels, crosslinking, ethylene glycol dimethacrylate, bisphenol A dimethacrylate, zwitterionic polymers, colloidal stability
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