Diblock copolymers consisting of a water-soluble nonionic block and either an anionic or cationic block were prepared from sodium 2-(acrylamido)-2-methylpropanesulfonate (AMPS) or (3-(methacryloylamino)propyl)trimethylammonium chloride (MAPTAC) via reversible addition-fragmentation chain transfer (RAFT)controlled radical polymerization using poly(ethylene glycol) (PEG)-based chain transfer agent (PEG-CTA) in water. The RAFT polymerization proceeded in a living fashion, as suggested by the observation that the numberaverage molecular weight (M n ) increased linearly with the monomer conversion (up to conversions of 30% for MAPTAC and 50% for AMPS), whereas the polydispersity (M w /M n ) remained nearly constant (M w /M n < 1.05 for MAPTAC and <1.2 for AMPS) independent of the conversion. The mixing of aqueous solutions of the oppositely charged diblock copolymers, PEG-b-PAMPS and PEG-b-PMAPTAC, led to the spontaneous formation of polyion complex (PIC) micelles. The PIC micelles were characterized by 1 H NMR spin-spin relaxation time, static light scattering (SLS), dynamic light scattering (DLS), and scanning electron microscopy (SEM) techniques. The hydrodynamic size of the micelle depended on the mixing ratio of PEG-b-PAMPS and PEG-b-PMAPTAC with the size maximizing at the mixing ratio of stoichiometric charge neutralization. The mixing of the oppositely charged diblock copolymers with shorter charged blocks formed a core-shell PIC micelle. In contrast, a complicated aggregate was formed from a pair of longer blocks. The exact structure of the aggregate is still an open question, but it is speculated to be a multicore intermicellar aggregate on the basis of various characterization data.

An asymmetric triblock copolymer, poly(styrene-b-acrylic acid-b-ethylene glycol) (PS-b-PAA-b-PEG), was synthesized via reversible addition-fragmentation chain transfer controlled radical polymerization. Micelles of PS-b-PAA-b-PEG with PS core, PAA shell, and PEG corona were then prepared in aqueous solutions, followed by extensive characterization based on dynamic light scattering, zeta-potential, and transmission electron microscopy (TEM) measurements. The well-characterized micelles were used to fabricate hollow nanospheres of CaCO(3) as a template. It was elucidated from TEM measurements that the hollow nanospheres have a uniform size with cavity diameters of ca. 20 nm. The X-ray diffraction analysis revealed a high purity and crystallinity of the hollow nanospheres. The hollow CaCO(3) nanospheres thus obtained have been used for the controlled release of an anti-inflammatory drug, naproxen. The significance of this study is that we have overcome a previous difficulty in the synthesis of hollow CaCO(3) nanospheres. After mixing of Ca(2+) and CO(3)(2-) ions, the growth of CaCO(3) is generally quite rapid to induce large crystal, which prevented us from obtaining hollow CaCO(3) nanospheres with controlled structure. However, we could solve this issue by using micelles of PS-b-PAA-b-PEG as a template. The PS core acts as a template that can be removed to form a cavity of hollow CaCO(3) nanospheres, the PAA shell is beneficial for arresting Ca(2+) ions to produce CaCO(3), and the PEG corona stabilizes the CaCO(3)/micelle nanocomposite to prevent secondary aggregate formation.

Hollow barium sulfate (BaSO 4 ) nanospheres were synthesized by templating a polymeric micelle of a triblock copolymer poly(styrene-b-acrylic acid-b-ethylene glycol) (PS-b-PAA-b-PEG). This polymer is known to form a micelle with a PS core, a PAA shell and a PEG corona in aqueous solutions. Barium chloride and sodium sulfate were used as precursors of BaSO 4 . In the synthesis, the PS core acts as a template for cavities of the hollow particles, the PAA shell is beneficial for arresting Ba 2+ ions to produce BaSO 4 , and the PEG corona stabilizes the BaSO 4 /polymer nanocomposite to prevent secondary aggregate formation. Hollow BaSO 4 nanospheres were obtained by removing the polymeric template from the BaSO 4 /polymer nanocomposite by calcination. The hollow BaSO 4 nanospheres thus fabricated were characterized by various techniques including transmission electron microscopy and X-ray diffraction analysis. The average diameter of the spheres is around 25 nm and the average cavity diameter is around 16 nm. The significance of the present method is that it can avoid formation of large crystals which is generally unavoidable in other methods.

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