Protonation-Driven Aqueous Lyotropic Self-Assembly of Synthetic Six-Tail Lipidoids

James Jennings; Matthew C.D. Carter; Chang Yun Son; Qiang Cui; David M. Lynn; Mahesh K. Mahanthappa

doi:10.1021/acs.langmuir.0c01369

Protonation-Driven Aqueous Lyotropic Self-Assembly of Synthetic Six-Tail Lipidoids

James Jennings, Matthew C.D. Carter, Chang Yun Son, Qiang Cui, David M. Lynn, Mahesh K. Mahanthappa

Chemical Engineering and Materials Science

Research output: Contribution to journal › Article › peer-review

5 Scopus citations

Abstract

We report the aqueous lyotropic mesophase behaviors of protonated amine-based "lipidoids,"a class of synthetic lipid-like molecules that mirrors essential structural features of the multitail bacterial amphiphile lipid A. Small-angle X-ray scattering (SAXS) studies demonstrate that the protonation of the tetra(amine) headgroups of six-tail lipidoids in aqueous HCl, HNO3, H2SO4, and H3PO4 solutions variably drives their self-assembly into lamellar (Lα) and inverse micellar (III) lyotropic liquid crystals (LLCs), depending on acid identity and concentration, amphiphile tail length, and temperature. Lipidoid assemblies formed in H2SO4(aq) exhibit rare inverse body-centered cubic (BCC) and inverse face-centered cubic (FCC) micellar morphologies, the latter of which unexpectedly coexists with zero mean curvature Lα phases. Complementary atomistic molecular dynamics (MD) simulations furnish detailed insights into this unusual self-assembly behavior. The unique aqueous lyotropic mesophase behaviors of ammonium lipidoids originate in their dichotomous ability to adopt both inverse conical and chain-extended molecular conformations depending on the number of counterions and their identity, which lead to coexisting supramolecular assemblies with remarkably different mean interfacial curvatures.

Original language	English (US)
Pages (from-to)	8240-8252
Number of pages	13
Journal	Langmuir
Volume	36
Issue number	28
DOIs	https://doi.org/10.1021/acs.langmuir.0c01369
State	Published - Jul 21 2020

Bibliographical note

Funding Information:
This work was financially supported by the National Science Foundation Materials Research Science and Engineering Center (MRSEC) at the University of Wisconsin—Madison under DMR-1121288 and CHE-1807330 (M.K.M.) and made use of core user facilities at the University of Wisconsin—Madison partially supported by DMR-1121288, CHE-9974839, and CHE-1048642. Synchrotron SAXS studies were conducted at Sector 12 of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. M.C.D.C acknowledges the Natural Sciences and Engineering Research Council of Canada for a graduate research fellowship.

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© 2020 American Chemical Society.

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title = "Protonation-Driven Aqueous Lyotropic Self-Assembly of Synthetic Six-Tail Lipidoids",

abstract = "We report the aqueous lyotropic mesophase behaviors of protonated amine-based {"}lipidoids,{"}a class of synthetic lipid-like molecules that mirrors essential structural features of the multitail bacterial amphiphile lipid A. Small-angle X-ray scattering (SAXS) studies demonstrate that the protonation of the tetra(amine) headgroups of six-tail lipidoids in aqueous HCl, HNO3, H2SO4, and H3PO4 solutions variably drives their self-assembly into lamellar (Lα) and inverse micellar (III) lyotropic liquid crystals (LLCs), depending on acid identity and concentration, amphiphile tail length, and temperature. Lipidoid assemblies formed in H2SO4(aq) exhibit rare inverse body-centered cubic (BCC) and inverse face-centered cubic (FCC) micellar morphologies, the latter of which unexpectedly coexists with zero mean curvature Lα phases. Complementary atomistic molecular dynamics (MD) simulations furnish detailed insights into this unusual self-assembly behavior. The unique aqueous lyotropic mesophase behaviors of ammonium lipidoids originate in their dichotomous ability to adopt both inverse conical and chain-extended molecular conformations depending on the number of counterions and their identity, which lead to coexisting supramolecular assemblies with remarkably different mean interfacial curvatures.",

author = "James Jennings and Carter, {Matthew C.D.} and Son, {Chang Yun} and Qiang Cui and Lynn, {David M.} and Mahanthappa, {Mahesh K.}",

note = "Funding Information: This work was financially supported by the National Science Foundation Materials Research Science and Engineering Center (MRSEC) at the University of Wisconsin—Madison under DMR-1121288 and CHE-1807330 (M.K.M.) and made use of core user facilities at the University of Wisconsin—Madison partially supported by DMR-1121288, CHE-9974839, and CHE-1048642. Synchrotron SAXS studies were conducted at Sector 12 of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. M.C.D.C acknowledges the Natural Sciences and Engineering Research Council of Canada for a graduate research fellowship. Publisher Copyright: {\textcopyright} 2020 American Chemical Society.",

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AU - Cui, Qiang

AU - Lynn, David M.

AU - Mahanthappa, Mahesh K.

N1 - Funding Information: This work was financially supported by the National Science Foundation Materials Research Science and Engineering Center (MRSEC) at the University of Wisconsin—Madison under DMR-1121288 and CHE-1807330 (M.K.M.) and made use of core user facilities at the University of Wisconsin—Madison partially supported by DMR-1121288, CHE-9974839, and CHE-1048642. Synchrotron SAXS studies were conducted at Sector 12 of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. M.C.D.C acknowledges the Natural Sciences and Engineering Research Council of Canada for a graduate research fellowship. Publisher Copyright: © 2020 American Chemical Society.

PY - 2020/7/21

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N2 - We report the aqueous lyotropic mesophase behaviors of protonated amine-based "lipidoids,"a class of synthetic lipid-like molecules that mirrors essential structural features of the multitail bacterial amphiphile lipid A. Small-angle X-ray scattering (SAXS) studies demonstrate that the protonation of the tetra(amine) headgroups of six-tail lipidoids in aqueous HCl, HNO3, H2SO4, and H3PO4 solutions variably drives their self-assembly into lamellar (Lα) and inverse micellar (III) lyotropic liquid crystals (LLCs), depending on acid identity and concentration, amphiphile tail length, and temperature. Lipidoid assemblies formed in H2SO4(aq) exhibit rare inverse body-centered cubic (BCC) and inverse face-centered cubic (FCC) micellar morphologies, the latter of which unexpectedly coexists with zero mean curvature Lα phases. Complementary atomistic molecular dynamics (MD) simulations furnish detailed insights into this unusual self-assembly behavior. The unique aqueous lyotropic mesophase behaviors of ammonium lipidoids originate in their dichotomous ability to adopt both inverse conical and chain-extended molecular conformations depending on the number of counterions and their identity, which lead to coexisting supramolecular assemblies with remarkably different mean interfacial curvatures.

AB - We report the aqueous lyotropic mesophase behaviors of protonated amine-based "lipidoids,"a class of synthetic lipid-like molecules that mirrors essential structural features of the multitail bacterial amphiphile lipid A. Small-angle X-ray scattering (SAXS) studies demonstrate that the protonation of the tetra(amine) headgroups of six-tail lipidoids in aqueous HCl, HNO3, H2SO4, and H3PO4 solutions variably drives their self-assembly into lamellar (Lα) and inverse micellar (III) lyotropic liquid crystals (LLCs), depending on acid identity and concentration, amphiphile tail length, and temperature. Lipidoid assemblies formed in H2SO4(aq) exhibit rare inverse body-centered cubic (BCC) and inverse face-centered cubic (FCC) micellar morphologies, the latter of which unexpectedly coexists with zero mean curvature Lα phases. Complementary atomistic molecular dynamics (MD) simulations furnish detailed insights into this unusual self-assembly behavior. The unique aqueous lyotropic mesophase behaviors of ammonium lipidoids originate in their dichotomous ability to adopt both inverse conical and chain-extended molecular conformations depending on the number of counterions and their identity, which lead to coexisting supramolecular assemblies with remarkably different mean interfacial curvatures.

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EP - 8252

JO - Langmuir

JF - Langmuir

IS - 28

ER -

Protonation-Driven Aqueous Lyotropic Self-Assembly of Synthetic Six-Tail Lipidoids

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