Ionic, Core-Corona Polymer Microsphere-Immobilized MacMillan Catalyst for Asymmetric Diels-Alder Reaction

The improvement of the catalytic activity of a heterogeneous chiral catalyst is one of the most critical issues, as are its recovery and reuse. The design of a heterogeneous chiral catalyst, including the immobilization method and the support polymer, is of significance for the catalytic activity in asymmetric reactions. An ionic, core-corona polymer microsphere-immobilized MacMillan catalyst (ICCC) was successfully synthesized by the neutralization reaction of sulfonic acid functionalized core-corona polymer microsphere (CCM–SO3H) with a chiral imidazolidinone precursor. We selected the core-corona polymer microsphere as the polymer support for the improvement of catalytic activity and recovery. The MacMillan catalyst was immobilized onto the pendant position of the corona with ionic bonding. ICCC exhibited excellent enantioselectivity up to 92% enantiomeric excess (ee) (exo) and >99% ee (endo) in the asymmetric Diels-Alder (DA) reaction of (E)-cinnamaldehyde and 1,3-cyclopentadiene. ICCC was quantitatively recovered by centrifugation because of the microsphere structure. The recovered ICCC was reused without significant loss of the enantioselectivity.

Phosphorescent and semiconductive fiber-like micelles formed by platinum(ii) complexes and block copolymers

The electrostatic self-assembly of cationic platinum(ii) complexes with negatively charged block copolymers in water leads to the formation of fiber-like micelles with a platinum(ii)-based ionic core surrounded by a poly(ethylene oxide) corona, which exhibit intense phosphorescent emissions and appreciable conductivity.

Modeling Equilibrium Swelling of a Dual pH- and Temperature-Responsive Core/Shell Hydrogel

The equilibrium swelling of a dual stimuli-responsive core/shell hydrogel is studied by a thermodynamic model. This hydrogel shows thermo-sensitivity as well as pH-sensitivity. The model captures the inhomogeneous swelling of core/shell hydrogels and also, accounts for temperature and pH sensitivity. The predictions of this model are verified with the swelling experiments of a core/shell microgel comprising poly N-isopropyl acrylamide (pNIPAM) and acrylic acid (AAc). The model calculates the equilibrium swelling within the ionic core and the neutral shell. Simulation results can reproduce the equilibrium swelling-temperature curves of this microgel at different pH values considering the delay in the volume phase transition temperature (VPTT) of the ionic polymer gel (pNIPAM-co-AAc) in the core. Two transition points are found in the equilibrium swelling behavior of the hydrogel akin to the VPTTs of the core and shell domains at high pH values of bath solutions. Likewise, the degree of ionization in the core domain is predicted to have a two-step transition behavior corresponding to the VPTTs of the core and shell domains at high pH values of bath solutions. It is shown that the equilibrium swelling of the ionic core is mainly influenced by the electrostatic repulsion between bound charges rather than the ionic pressure. Furthermore, it is determined that the maximum radial stress occurs at the core/shell interface and reaches its maximum value about the VPTT of the core.