We investigated the effect of hydrogen bonding on the dynamics and kinetics of single polymer growth using magnetic tweezers. In the previous study, it was found that, during single polymer growth, nonequilibrium polymer entanglements were formed and unraveled due to the intra-chain van der Waals force, and the microstructure of the entanglements was found to affect the apparent chain propagation rate. To demonstrate how the intra-chain interactions affect the chain propagation rate, we introduced hydroxyl-functionalized monomers and studied the effect of the hydrogen bonding on the chain propagation rate. Based on the previous study, it was expected that higher ratio of hydroxyl-functionalized monomers should slow down the chain propagation rate. However, our results showed that the chain propagation rate first decrease and then increase with increasing hydroxyl-functionalized monomer ratio unexpectedly. This phenomenon can be explained by the competition between the intra-chain hydrogen bond and the inter-molecular hydrogen bond between polymer and free monomers in solution. To verify the hypothesis, we solely increased the inter-molecular hydrogen bond by adding the inert molecules that contain the hydroxyl group. The result showed that the chain propagation rate was increased by adding the inert molecules, which is consistent with the hypothesis.

Effect of intra- and inter-molecular forces on single polymer growth

ACS Fall 2021

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