Using Copolymers to Design Tunable Stimuli-Reponsive Brushes

Recently, a new design for switch sensors has been proposed that exploits a conformational transition of end-grafted minority adsorption-active homopolymers in a monodisperse polymer brush [Klushin et al. Phys. Rev. Lett. 2014, 113, 068303]. The transition is sharp and first-order type if the minority chain is longer than the brush chains. However, the intrinsic nature of the system imposes a constraint on the relation between the sharpness of the transition and the height of the free energy barrier controlling the transition kinetics: The sharper the transition, the slower the transition time. Here we demonstrate that adopting diblock copolymers with the adsorption-active block anchored at the substrate as the minority chains allows a much more flexible control of the three main characteristics of the transition, i.e., the transition point, its sharpness, and the barrier height. In particular, the barrier height can be greatly reduced without compromising the sharpness. We develop an analytical theory that predicts the relevant characteristics of the transition and verify it with SCF calculations and Monte Carlo simulations. We also demonstrate that from a thermodynamic point of view the transition characteristics of a diblock copolymer are equivalent to those of the active block alone in a modified brush with the same grafting density and reduced length.