Abstract
In this paper, we present a synergistic, experimental, and computational study of the self-assembly of N,N′-disubstituted polysulfamides driven by hydrogen bonds (H-bonds) between the H-bonding donor and acceptor groups present in repeating sulfamides as a function of the structural design of the polysulfamide backbone. We developed a coarse-grained (CG) polysulfamide model that captures the directionality of H-bonds between the sulfamide groups and used this model in molecular dynamics (MD) simulations to study the self-assembly of these polymers in implicit solvent. The CGMD approach was validated by reproducing experimentally observed trends in the extent of crystallinity for three polysulfamides synthesized with aliphatic and/or aromatic repeating units. After validation of our CGMD approach, we computationally predicted the effect of repeat unit bulkiness, length, and uniformity of segment lengths in the polymers on the extent of orientational and positional order among the self-assembled polysulfamide chains, providing key design principles for tuning the extent of crystallinity in polysulfamides in experiments. Those computational predictions were then experimentally tested through the synthesis and characterization of polysulfamide architectures.
| Original language | English |
|---|---|
| Pages (from-to) | 5033-5049 |
| Number of pages | 17 |
| Journal | Macromolecules |
| Volume | 56 |
| Issue number | 13 |
| DOIs | |
| State | Published - Jul 11 2023 |
| Externally published | Yes |
Funding
The authors thank DOE Grant DE-SC0023264 for the financial support required for the computational work and the determination of the crystallinity of polysulfamides. The simulations in this paper are done on UD Caviness supercomputing cluster and UD DARWIN supercomputing cluster. The development of reaction conditions for the SuFEx polymerization en route to polysulfamides, including the purchase of SO2F2, was supported by the National Institute of General Medical Sciences at the National Institutes of Health under Award R35GM138079. The Welch Foundation (A-2004-20190330) is also acknowledged for early support of J.W.W., as well as the use of the NMR and X-ray facilities in the Department of Chemistry and the Soft Matter Facility (RRID: SCR_022482) at Texas A&M University. The authors thank DOE Grant DE-SC0023264 for the financial support required for the computational work and the determination of the crystallinity of polysulfamides. The simulations in this paper are done on UD Caviness supercomputing cluster and UD DARWIN supercomputing cluster. The development of reaction conditions for the SuFEx polymerization en route to polysulfamides, including the purchase of SOF, was supported by the National Institute of General Medical Sciences at the National Institutes of Health under Award R35GM138079. The Welch Foundation (A-2004-20190330) is also acknowledged for early support of J.W.W., as well as the use of the NMR and X-ray facilities in the Department of Chemistry and the Soft Matter Facility (RRID: SCR_022482) at Texas A&M University. 2 2