Investigating the Hydrogen Bond-Induced Self-Assembly of Polysulfamides Using Molecular Simulations and Experiments

ZJ Wu and JW Wu and Q Michaudel and A Jayaraman, MACROMOLECULES, 56, 5033-5049 (2023).

DOI: 10.1021/acs.macromol.3c01093

In this paper, we present a synergistic, experimental,and computationalstudy of the self-assembly of N,N & PRIME;-disubstituted polysulfamides driven by hydrogen bonds (H-bonds)between the H-bonding donor and acceptor groups present in repeatingsulfamides as a function of the structural design of the polysulfamidebackbone. We developed a coarse-grained (CG) polysulfamide model thatcaptures the directionality of H-bonds between the sulfamide groupsand used this model in molecular dynamics (MD) simulations to studythe self-assembly of these polymers in implicit solvent. The CGMDapproach was validated by reproducing experimentally observed trendsin the extent of crystallinity for three polysulfamides synthesizedwith aliphatic and/or aromatic repeating units. After validation ofour CGMD approach, we computationally predicted the effect of repeatunit bulkiness, length, and uniformity of segment lengths in the polymerson the extent of orientational and positional order among the self-assembledpolysulfamide chains, providing key design principles for tuning theextent of crystallinity in polysulfamides in experiments. Those computationalpredictions were then experimentally tested through the synthesisand characterization of polysulfamide architectures.

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