Structure of a single polymer chain confined in a dense array of nanoposts

Control of polymer conformations in heterogeneous confinement plays an important role in natural and engineering processes. We present a simulation study on the conformational structure and dynamics of a single, flexible polymer in a dense array of nanoposts with different sizes and separations, especially, when the volume of the interstitial space formed between four nanoposts is less than the size of the polymer chain. When a polymer is placed in the array of nanoposts, the size of polymer increases compared with that in the absence of nanoposts due to the confinement effect. It is shown that when a polymer is confined in the array of nanoposts the chain is elongated in the direction parallel to the nanoposts. As the interstitial volume between four nanoposts decreases either by increasing the nanopost diameter or by decreasing the separation between nanoposts, the chain elongation becomes more pronounced. On the contrary, the polymer size varies in a non-monotonic fashion, with an initial elongation followed by a chain contraction, as the interstitial volume is reduced both by increasing the nanopost diameter and decreasing the separation at the same time while keeping constant the width of the passageway between two nanoposts. The simulation analysis shows that the non-monotonic dependence of polymer size is determined by interplay between the chain alignment along the nanoposts in each interstitial volume and the chain spreading through passageways over several interstitial volume.