Analysis of the internal motions of thermoresponsive polymers and single chain nanoparticles

Data-driven techniques, such as proper orthogonal decomposition (POD) and uniform manifold approximation & projection (UMAP), are powerful methods for understanding polymer behavior in complex systems that extend beyond ideal conditions. They are based on the principle that low-dimensional behaviors are often embedded within the structure and dynamics of complex systems. Here, the internal motions of a thermoresponsive, LCST polymer are investigated for two cases: (1) the coil-to-globule transition that occurs as the system is heated above its critical temperature and (2) intramolecularly crosslinked, single chain nanoparticles (SCNPs) both above and below the critical temperature (T_C). Our results demonstrate that POD can successfully extract the key features of the dynamics for both polymer globules and SCNPs. In the globular state, our results show that the relaxation modes are distorted relative to the coil state and relaxation times decrease upon chain collapse. After randomly crosslinking a globule to produce a SCNP, we observe a further distortion of the relaxation modes that depends strongly upon the particular set of monomers that are crosslinked. Yet, different sets of crosslinked monomers produce similar relaxation times for the SCNP. We observe that for SCNPs below the critical temperature, the relaxation times decrease with increasing crosslink density while above the critical temperature, they increase as crosslink density increases. Finally, using UMAP we categorize the local structure of SCNPs and examine the influence of the local structure on SCNP relaxation dynamics.