Molecular Dynamics Simulation of the Effect of Carbon Space Lengths on the Antifouling Properties of Hydroxyalkyl Acrylamides.

Surface hydration has been proposed as the key antifouling mechanism of antifouling materials. However, molecular-level details of the structure, dynamics, and interactions of interfacial water around antifouling polymers still remain elusive. In this work, using all-atom molecular dynamics (MD) simulations, we studied four different acrylamides (AMs) for their interfacial water behaviors and their interactions with a protein, with special attention to the effect of carbon spacer lengths (CSLs) on the hydration properties of AMs. Collective MD simulation data revealed that although all four AMs displayed strong hydration, N-hydroxymethyl acrylamide (HMAA) and N-(2-hydroxyethyl)acrylamide (HEAA) with shorter CSLs displayed a longer residence time, slower self-diffusion, and lower coordination number of interfacial water molecules than N-(3-hydroxypropyl)acrylamide (HPAA) and N-(5-hydroxypentyl)-acrylamide (HPenAA) with longer CSLs. The shorter CSLs allow water molecules to form bridging hydrogen bonds with different hydrophilic groups in the same AM chain, thus enhancing the hydration capacity of AMs. Consequently, different from HPenAA, which had a weak but detectable interaction with the protein, HMAA, HEAA, and HPAA had almost zero interactions with the protein. This computational work provides a better fundamental understanding of the surface hydration and protein interaction of different AMs with subtle structural changes from structural, dynamic, and energy aspects at the atomic level, which hopefully will guide the design of new and effective nonfouling materials.