Nonequilibrium self-organization of lipids into hierarchically ordered and compositionally graded cylindrical smectics
When a dry mass of certain amphiphiles encounters water, a spectacular interfacial instability ensues: It gives rise to the formation of ensembles of fingerlike tubular protrusions called myelin figures─tens of micrometers wide and tens to hundreds of micrometers long─representing a novel class of n...
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sg-ntu-dr.10356-1618842022-09-23T01:56:49Z Nonequilibrium self-organization of lipids into hierarchically ordered and compositionally graded cylindrical smectics Ho, James Chin Shing Su, Wan-Chih Wang, Xuan Chun Parikh, Atul N. Liedberg, Bo School of Materials Science and Engineering Centre for Biomimetic Sensor Science (CBSS) Engineering::Materials Cholesterol Lipid Bilayers When a dry mass of certain amphiphiles encounters water, a spectacular interfacial instability ensues: It gives rise to the formation of ensembles of fingerlike tubular protrusions called myelin figures─tens of micrometers wide and tens to hundreds of micrometers long─representing a novel class of nonequilibrium higher-order self-organization. Here, we report that when phase-separating mixtures of unsaturated lipid, cholesterol, and sphingomyelin are hydrated, the resulting myelins break symmetry and couple their compositional degrees of freedom with the extended myelinic morphology: They produce complementary, interlamellar radial gradients of concentrations of cholesterol (and sphingomyelin) and unsaturated lipid, which stands in stark contrast to interlamellar, lateral phase separation in equilibrated morphologies. Furthermore, the corresponding gradients of molecule-specific chemistries (i.e., cholesterol extraction by methyl-β-cyclodextrin and GM1 binding by cholera toxin) produce unusual morphologies comprising compositionally graded vesicles and buckled tubes. We propose that kinetic differences in the information processing of hydration characteristics of individual molecules while expending energy dictate this novel behavior of lipid mixtures undergoing hydration. Ministry of Education (MOE) The authors also acknowledge the support from the Ministry of Education Singapore (grant no. MOE2018-T2-1-025). J.C.S.H. also acknowledges the support from Singapore Centre for Environmental Life Sciences Engineering (SCELSE). W-C.S. and A.N.P. acknowledge support from the National Science Foundation (United States) through a grant from the Division of Materials Research (#1810540). A.N.P.’s contributions are also supported by a grant from the U.S. National Science Foundation (DMR2104123). 2022-09-23T01:56:49Z 2022-09-23T01:56:49Z 2022 Journal Article Ho, J. C. S., Su, W., Wang, X. C., Parikh, A. N. & Liedberg, B. (2022). Nonequilibrium self-organization of lipids into hierarchically ordered and compositionally graded cylindrical smectics. Langmuir, 38(3), 1045-1056. https://dx.doi.org/10.1021/acs.langmuir.1c02576 0743-7463 https://hdl.handle.net/10356/161884 10.1021/acs.langmuir.1c02576 35020400 2-s2.0-85123879114 3 38 1045 1056 en MOE2018-T2-1-025 Langmuir © 2022 American Chemical Society. All rights reserved. |
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Engineering::Materials Cholesterol Lipid Bilayers Ho, James Chin Shing Su, Wan-Chih Wang, Xuan Chun Parikh, Atul N. Liedberg, Bo Nonequilibrium self-organization of lipids into hierarchically ordered and compositionally graded cylindrical smectics |
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When a dry mass of certain amphiphiles encounters water, a spectacular interfacial instability ensues: It gives rise to the formation of ensembles of fingerlike tubular protrusions called myelin figures─tens of micrometers wide and tens to hundreds of micrometers long─representing a novel class of nonequilibrium higher-order self-organization. Here, we report that when phase-separating mixtures of unsaturated lipid, cholesterol, and sphingomyelin are hydrated, the resulting myelins break symmetry and couple their compositional degrees of freedom with the extended myelinic morphology: They produce complementary, interlamellar radial gradients of concentrations of cholesterol (and sphingomyelin) and unsaturated lipid, which stands in stark contrast to interlamellar, lateral phase separation in equilibrated morphologies. Furthermore, the corresponding gradients of molecule-specific chemistries (i.e., cholesterol extraction by methyl-β-cyclodextrin and GM1 binding by cholera toxin) produce unusual morphologies comprising compositionally graded vesicles and buckled tubes. We propose that kinetic differences in the information processing of hydration characteristics of individual molecules while expending energy dictate this novel behavior of lipid mixtures undergoing hydration. |
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School of Materials Science and Engineering |
author_facet |
School of Materials Science and Engineering Ho, James Chin Shing Su, Wan-Chih Wang, Xuan Chun Parikh, Atul N. Liedberg, Bo |
format |
Article |
author |
Ho, James Chin Shing Su, Wan-Chih Wang, Xuan Chun Parikh, Atul N. Liedberg, Bo |
author_sort |
Ho, James Chin Shing |
title |
Nonequilibrium self-organization of lipids into hierarchically ordered and compositionally graded cylindrical smectics |
title_short |
Nonequilibrium self-organization of lipids into hierarchically ordered and compositionally graded cylindrical smectics |
title_full |
Nonequilibrium self-organization of lipids into hierarchically ordered and compositionally graded cylindrical smectics |
title_fullStr |
Nonequilibrium self-organization of lipids into hierarchically ordered and compositionally graded cylindrical smectics |
title_full_unstemmed |
Nonequilibrium self-organization of lipids into hierarchically ordered and compositionally graded cylindrical smectics |
title_sort |
nonequilibrium self-organization of lipids into hierarchically ordered and compositionally graded cylindrical smectics |
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2022 |
url |
https://hdl.handle.net/10356/161884 |
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1745574653023223808 |