title: Occlusion of Sulfate-Based Diblock Copolymer Nanoparticles within Calcite: Effect of Varying the Surface Density of Anionic Stabilizer Chains.
abstract: Polymerization-induced self-assembly (PISA) offers a highly versatile and efficient route to a wide range of organic nanoparticles. In this article, we demonstrate for the first time that poly(ammonium 2-sulfatoethyl methacrylate)-poly(benzyl methacrylate) [PSEM-PBzMA] diblock copolymer nanoparticles can be prepared with either a high or low PSEM stabilizer surface density using either RAFT dispersion polymerization in a 2:1 v/v ethanol/water mixture or RAFT aqueous emulsion polymerization, respectively. We then use these model nanoparticles to gain new insight into a key topic in materials chemistry: the occlusion of organic additives into inorganic crystals. Substantial differences are observed for the extent of occlusion of these two types of anionic nanoparticles into calcite (CaCO3), which serves as a suitable model host crystal. A low PSEM stabilizer surface density leads to uniform nanoparticle occlusion within calcite at up to 7.5% w/w (16% v/v), while minimal occlusion occurs when using nanoparticles with a high PSEM stabilizer surface density. This counter-intuitive observation suggests that an optimum anionic surface density is required for efficient occlusion, which provides a hitherto unexpected design rule for the incorporation of nanoparticles within crystals.
authors: Department of Chemistry, University of Sheffield , Brook Hill, Sheffield, South Yorkshire S3 7HF, U.K.
authors: Yin
authors: Y
authors: Ning
authors: Department of Chemistry, University of Sheffield , Brook Hill, Sheffield, South Yorkshire S3 7HF, U.K.|The School of Materials, University of Manchester , Oxford Road, Manchester, M13 9PL, U.K.
authors: Lee A
authors: LA
authors: Fielding
authors: Department of Chemistry, University of Sheffield , Brook Hill, Sheffield, South Yorkshire S3 7HF, U.K.
authors: Liam P D
authors: LP
authors: Ratcliffe
authors: School of Chemistry, University of Leeds , Leeds LS2 9JT, U.K.
authors: Yun-Wei
authors: YW
authors: Wang
authors: School of Chemistry, University of Leeds , Leeds LS2 9JT, U.K.
authors: Fiona C
authors: FC
authors: Meldrum
authors: Department of Chemistry, University of Sheffield , Brook Hill, Sheffield, South Yorkshire S3 7HF, U.K.
authors: Steven P
authors: SP
authors: Armes