期刊
LANGMUIR
卷 35, 期 37, 页码 12215-12223出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.langmuir.9b02128
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资金
- Science and Engineering Research Board [YSS/2014/000098]
- German Academic Exchange Service (DAAD) [57314018]
- Council of Scientific and Industrial Research (CSIR), India [09/254(0267)/2017-EMR-I]
- University Grant Commission (UGC), India [105743]
We compare the biophysical and structural aspects of the interaction of amphiphilic ionic liquids containing 1-alkyl-3-methylimidazolium cation ([CnMIM](+), n = 8, 12, or 16) with membranes composed of zwitterionic 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) or anionic 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-rac-glycerol (POPG). Liposome affinity and permeabilization were determined using zeta-potential and fluorescence studies, correlated with the cytoxicity of [C-n,MIM]Br-+(-) toward HeLa cell lines. Membrane affinity is strongest in the case of [C16MIM]Br-+(-) followed by [C12MIM]Br-+(-) and [C8MIM]Br-+(-) for both membranes, and trends remained the same in the case of membrane permeability and cytotoxicity. Solid-state NMR spectroscopy was used to localize [CnMIM](+) inside the lipid bilayers and to study their impact on the head group and acyl chain structures and dynamics of the lipid molecules. The charged ring moiety of the [CnMIM](+) is localized in the lipid-water interface of the membranes irrespective of the chain length and membrane surface charge. While [C8MIM](+) binds the membrane most weakly, it induces the largest disorder in the lipid chain region. A lack of fast flip-flop motions of the amphiphiles in the case of long chain [C16MIM](+) is suggested to render the membrane unstable, which increases its permeability. Between the lipid molecules, the POPC membrane incurs larger disorder in lipid chain packing upon insertion of [CnMIM](+) molecules. The study provides structural details of the impact of increasing chain lengths in [CnMIM](+) on the structural properties of lipid bilayers.
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