Morphology-induced defects enhance lipid transfer rates

Yan Xia; Kamil Charubin; Drew Marquardt; Frederick A. Heberle; John Katsaras; Jianhui Tian; Xiaolin Cheng; Ying Liu; Mu Ping Nieh

doi:10.1021/acs.langmuir.6b02099

Morphology-induced defects enhance lipid transfer rates

Yan Xia, Kamil Charubin, Drew Marquardt, Frederick A. Heberle, John Katsaras, Jianhui Tian, Xiaolin Cheng, Ying Liu, Mu Ping Nieh

Labs & Soft Matter

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

12 Scopus citations

Abstract

Molecular transfer between nanoparticles has been considered to have important implications regarding nanoparticle stability. Recently, the interparticle spontaneous lipid transfer rate constant for discoidal bicelles was found to be very different from spherical, unilamellar vesicles (ULVs). Here, we investigate the mechanism responsible for this discrepancy. Analysis of the data indicates that lipid transfer is entropically favorable, but enthalpically unfavorable with an activation energy that is independent of bicelle size and long- to short-chain lipid molar ratio. Moreover, molecular dynamics simulations reveal a lower lipid dissociation energy cost in the vicinity of interfaces ("defects") induced by the segregation of the long- and short-chain lipids in bicelles; these defects are not present in ULVs. Taken together, these results suggest that the enhanced lipid transfer observed in bicelles arises from interfacial defects as a result of the hydrophobic mismatch between the long- and short-chain lipid species. Finally, the observed lipid transfer rate is found to be independent of nanoparticle stability.

Original language	English
Pages (from-to)	9757-9764
Number of pages	8
Journal	Langmuir
Volume	32
Issue number	38
DOIs	https://doi.org/10.1021/acs.langmuir.6b02099
State	Published - Sep 27 2016

Funding

Mu-Ping Nieh, Yan Xia, Kamil Charubin, and Ying Liu acknowledge the financial support from the National Science Foundation (NSF) (CMMI 1131587 and CBET 1433903) and NSF-DMR 1228817 for the acquisition of a high-sensitivity DSC. SANS experiments were conducted at SNS (ORNL) and NCNR (NIST). The authors thank Dr. Boualem Hammouda (NIST) for his help. John Katsaras is supported through the Scientific User Facilities Division of the United States Department of Energy (DOE) Office of Basic Energy Sciences (BES) under Contract DE-AC05-00OR22725, which also supported the MD simulation work. Xiaolin Cheng is partially supported by Laboratory Directed Research and Development (LDRD) Fund P7394 (ORNL).

Funders	Funder number
NSF-DMR	1228817
United States Department of Energy
National Science Foundation	CMMI 1131587, CBET 1433903
U.S. Department of Energy
National Institute of Standards and Technology
Basic Energy Sciences	DE-AC05-00OR22725
Oak Ridge National Laboratory
Laboratory Directed Research and Development	P7394
NIST Center for Neutron Research

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title = "Morphology-induced defects enhance lipid transfer rates",

abstract = "Molecular transfer between nanoparticles has been considered to have important implications regarding nanoparticle stability. Recently, the interparticle spontaneous lipid transfer rate constant for discoidal bicelles was found to be very different from spherical, unilamellar vesicles (ULVs). Here, we investigate the mechanism responsible for this discrepancy. Analysis of the data indicates that lipid transfer is entropically favorable, but enthalpically unfavorable with an activation energy that is independent of bicelle size and long- to short-chain lipid molar ratio. Moreover, molecular dynamics simulations reveal a lower lipid dissociation energy cost in the vicinity of interfaces ({"}defects{"}) induced by the segregation of the long- and short-chain lipids in bicelles; these defects are not present in ULVs. Taken together, these results suggest that the enhanced lipid transfer observed in bicelles arises from interfacial defects as a result of the hydrophobic mismatch between the long- and short-chain lipid species. Finally, the observed lipid transfer rate is found to be independent of nanoparticle stability.",

author = "Yan Xia and Kamil Charubin and Drew Marquardt and Heberle, {Frederick A.} and John Katsaras and Jianhui Tian and Xiaolin Cheng and Ying Liu and Nieh, {Mu Ping}",

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T1 - Morphology-induced defects enhance lipid transfer rates

AU - Xia, Yan

AU - Charubin, Kamil

AU - Marquardt, Drew

AU - Heberle, Frederick A.

AU - Katsaras, John

AU - Tian, Jianhui

AU - Cheng, Xiaolin

AU - Liu, Ying

AU - Nieh, Mu Ping

PY - 2016/9/27

Y1 - 2016/9/27

N2 - Molecular transfer between nanoparticles has been considered to have important implications regarding nanoparticle stability. Recently, the interparticle spontaneous lipid transfer rate constant for discoidal bicelles was found to be very different from spherical, unilamellar vesicles (ULVs). Here, we investigate the mechanism responsible for this discrepancy. Analysis of the data indicates that lipid transfer is entropically favorable, but enthalpically unfavorable with an activation energy that is independent of bicelle size and long- to short-chain lipid molar ratio. Moreover, molecular dynamics simulations reveal a lower lipid dissociation energy cost in the vicinity of interfaces ("defects") induced by the segregation of the long- and short-chain lipids in bicelles; these defects are not present in ULVs. Taken together, these results suggest that the enhanced lipid transfer observed in bicelles arises from interfacial defects as a result of the hydrophobic mismatch between the long- and short-chain lipid species. Finally, the observed lipid transfer rate is found to be independent of nanoparticle stability.

AB - Molecular transfer between nanoparticles has been considered to have important implications regarding nanoparticle stability. Recently, the interparticle spontaneous lipid transfer rate constant for discoidal bicelles was found to be very different from spherical, unilamellar vesicles (ULVs). Here, we investigate the mechanism responsible for this discrepancy. Analysis of the data indicates that lipid transfer is entropically favorable, but enthalpically unfavorable with an activation energy that is independent of bicelle size and long- to short-chain lipid molar ratio. Moreover, molecular dynamics simulations reveal a lower lipid dissociation energy cost in the vicinity of interfaces ("defects") induced by the segregation of the long- and short-chain lipids in bicelles; these defects are not present in ULVs. Taken together, these results suggest that the enhanced lipid transfer observed in bicelles arises from interfacial defects as a result of the hydrophobic mismatch between the long- and short-chain lipid species. Finally, the observed lipid transfer rate is found to be independent of nanoparticle stability.

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Morphology-induced defects enhance lipid transfer rates

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