Hierarchical excluded volume screening in solutions of bottlebrush polymers

Polymer bottlebrushes provide intriguing features being relevant both in nature and in synthetic systems. While their presence in the articular cartilage optimizes synovial joint lubrication, bottlebrushes offer pathways for fascinating applications, such as within super-soft elastomers or for drug delivery. However, the current theoretical understanding lacks completeness, primarily due to the complicated interplay of many length scales. Herein, we develop an analytical model that demonstrates how structural properties of bottlebrushes depend on the concentration, ranging from dilute solutions to highly concentrated melts. The validity of our model is supported by data from extensive molecular dynamics simulations. We demonstrate that the hierarchical structure of bottlebrushes dictates a sequence of conformational changes as the solution concentration increases. The effect is mediated by screening of excluded volume interactions at subsequent structural parts of the bottlebrushes. Our findings provide important insights that should enable improved customization of novel materials based on the architectural design of polymer bottlebrushes.