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Efforts to create block-polymer-based templates with ultrasmall domain sizes has stimulated integrated experimental and theoretical work in an effort to design and prepare self-assembled systems that can achieve unprecedented domain sizes. We recently reported the utilization of molecular dynamics simulations with transferable force fields to identify amphiphilic oligomers capable of self-assembling into ordered layered and cylindrical morphologies with sub-3 nm domain sizes. Motivated by these predictions, we prepared a sugar-based amphiphile with a hydrocarbon tail that shows thermotropic self-assembly to give a lamellar mesophase with a 3.5 nm pitch and sub-2 nm nanodomains above the melting temperature and below the liquid-crystalline clearing temperature. Complementary atomistic simulations of the molecular assemblies gave morphologies and spacings that were in near-perfect agreement with the experimental results. The effective combination of molecular design, simulation, synthesis, and structural characterization demonstrates the power of this integrated approach for next-generation templating technologies.
Bibliographical noteFunding Information:
This work was supported primarily by the MRSEC program, under award DMR-1420013. We thank Nicholas Hampu for help performing X-ray scattering experiments. Use of the Advanced Photon Source (APS) at Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, under contract DE-AC02-06CH11357. SAXS measurements were performed at the DuPont-Northwestern- Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the APS, supported by E. I. DuPont de Nemours and Co., The Dow Chemical Company, and Northwestern University. NMR data reported in this publication made use of the LeClaire-Dow instrumentation facility, which is supported by the Office of the Director, National Institutes of Health, under Award Number S10OD011952. The content is solely the responsibility of the authors and does not necessarily represent the official views of the National Institutes of Health. Advanced 2-D NMR was carried out at the Minnesota NMR Center, whose funding is provided by the Office of the Vice President for Research, the Medical School, the College of Biological Science, NIH, NSF, and the Minnesota Medical Foundation. Adeline Espinasse is gratefully acknowledged for her help with HRMS samples. In addition to computers made available through DMR-1420013, this work also used computer resources provided by the Minnesota Supercomputing Institute.
© 2019 American Chemical Society.
- lamellar morphology
- liquid crystal
How much support was provided by MRSEC?
PubMed: MeSH publication types
- Journal Article
- Research Support, Non-U.S. Gov't
- Research Support, U.S. Gov't, Non-P.H.S.
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