Comb copolymer cylindrical brushes containing semiflexible side chains: a Monte Carlo study

The off-lattice Monte Carlo method is applied to investigate the equilibrium conformations of isolated comb copolymer cylindrical brushes in an athermal solution. The molecules considered consist of a flexible backbone, which is densely grafted with semiflexible side chains. The study focuses on the influence of the degree of intrinsic stiffness, λside, of the side chains on the conformational behavior of the molecules. It is demonstrated that with a fixed side chain length, M, the local length scale conformational fluctuations of the backbone increase as a function of λside. However, the persistence length, λ, of the cylindrical brush increases considerably with the side chain stiffness, indicating that the backbone becomes more extended at the large length scale. Moreover, as a function of λside, there is an increase in the ratio λ/D of the persistence length and the diameter, D, of the brush. This behavior is in good agreement with recent theoretical predictions and provides important new insight in the latest experimental observations.