Synthesis ofArsenocholine-Type Polycation Brush andIts Hydration Structure in Aqueous Solution

Arsenocholine-containing methacrylate (MTAsB) inspired by marine organisms was synthesized by the reaction of 2-bromoethyl methacrylate and trimethylarsine to investigate its polymerization behavior and the fundamental properties of the resulting polymer. Controlled radical polymerization of MTAsB proceeded in the presence of a copper catalyst and imidazolium chloride at 60 °C for 8 h to give a water-soluble polycation with a 94% yield. The smaller amount of nonfreezing water and intermediate water of poly­(MTAsB) was observed compared with that of the ammonium-containing polycations. A poly­(MTAsB) brush was also prepared on a silicon substrate to investigate its swelling structure in aqueous salt solution by scanning probe microscopy and neutron reflectivity measurements. The brush chains adopted a relatively extended conformation in pure water because of the Coulombic repulsion among the arsenic cation groups of the polyelectrolyte, while the brush formed a collapsed structure in aqueous solutions of Hofmeister series anions as a result of the screening effect by salt ions. In particular, thiocyanate ions induced a significant reduction in the swollen thickness of the brush, probably caused by the attractive interaction between arsenic cations and chaotropic thiocyanate ions. The salt concentration dependency of the poly­(MTAsB) brush was similar to that of the ammonium-cation-type polyelectrolyte brushes.