Stereoselective Recognition in Phospholipid Monolayers

Arnett, Edward M.; Gold, Jeffrey M.; Harvey, Noel G.; Johnson, Eric A.; Whitesell, L. G.

doi:10.1007/978-1-4684-7908-9_3

Cited by 11 publications

(3 citation statements)

References 13 publications

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“…Because the phospholipids and sterols found in cellular membranes contain one or more chiral carbon atoms and occur in an enantimerically pure form, enantiospecific inter-actions can in principle occur in the lipid bilayers of such membranes. However, previous studies of phospholipidphospholipid (van Deenen et al, 1962;Rainier et al, 1979;Arnett et al, 1988;Rose et al, 1993) and sterol-phospholipid (Ghosh et al, 1971;Arnett and Gold, 1982;Hermetter and Paltauf, 1982;Guyer and Block, 1983;Agarwal et al, 1986a,b) interactions utilizing dipalmitoylphosphatidylcholine (DPPC) or close structural analogs have not provided evidence for significant enantioselectivity for either type of interaction. Recently, however, a report has appeared in which enantioselective interactions between natural cholesterol or enantiomeric cholesterol and egg SpM in monolayer films have apparently been detected (Lalitha et al, 2001).…”

Section: Introductionmentioning

confidence: 98%

Effects of Natural and Enantiomeric Cholesterol on the Thermotropic Phase Behavior and Structure of Egg Sphingomyelin Bilayer Membranes

Mannock

McIntosh

Jiang

et al. 2003

Biophysical Journal

108

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Phospholipids, sphingolipids, and sterols are the major lipid components of the plasma membranes of eukaryotic cells. Because these three lipid classes occur naturally as enantiomerically pure compounds, enantiospecific lipid-lipid and lipid-sterol interactions could in principle occur in the lipid bilayers of eukaryotic plasma membranes. Although previous biophysical studies of phospholipid and phospholipid-sterol model membrane systems have consistently failed to observe such enantiomerically selective interactions, a recent monolayer study of the interactions of natural and enantiomeric cholesterol with egg sphingomyelin has apparently revealed the existence of enantiospecific sterol-sphingolipid interactions. To determine whether enantiospecific sterol-sphingolipid interactions also occur in more biologically relevant lipid-bilayer systems, differential scanning calorimetric, x-ray diffraction, and neutral buoyant-density measurements were utilized to study the effects of natural and enantiomeric cholesterol on the thermotropic phase behavior and structure of egg sphingomyelin bilayers. The calorimetry experiments show that the natural and enantiomeric cholesterol have essentially identical effects on the temperature, enthalpy, and cooperativity of the gel/liquid-crystalline phase transition of egg sphingomyelin bilayers within the limits of experimental error. As well, the x-ray diffraction and neutral buoyancy experiments indicate that bilayers formed from mixtures of natural or enantiomeric cholesterol and egg sphingomyelin have, within experimental uncertainty, the same structure and mass density. We thus conclude that significant enantioselective cholesterol-sphingolipid interactions do not occur in this lipid-bilayer model membrane system.

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Section: Introductionmentioning

confidence: 98%

Effects of Natural and Enantiomeric Cholesterol on the Thermotropic Phase Behavior and Structure of Egg Sphingomyelin Bilayer Membranes

Mannock

McIntosh

Jiang

et al. 2003

Biophysical Journal

108

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“…Therefore, chiral recognition cannot be induced in 100% polymerized systems and in almost homogeneous PDA liposome membranes prepared by only DiynePC. In addition to the exposure of chiral centers, S-IBU would preferentially interact with the chiral centers, 40,41 especially with the exposed chiral center at the boundary, for the reduction of interfacial free energy. 42 Thus, we can conclude that a large number of complex nanodomains and boundary edges are important for the chiral recognition of IBU and that these factors can be easily controlled by the lipid composition and polymerization degree.…”

Section: ■ Discussionmentioning

confidence: 99%

Induction of Chiral Recognition with Lipid Nanodomains Produced by Polymerization

et al. 2017

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We report the induction and control of chiral recognition in liposomal membranes by the photopolymerization of diacetylenic lipids (DiynePC). The specific properties of polymerized DiynePC liposomes were characterized, and then the chiral separation performance was estimated. As the polymerization proceeds, chiral recognition to ibuprofen was induced, and its efficiency increased due to the formation of rigid nanodomains and boundary edges. Furthermore, the chiral recognition and adsorbed amount could be controlled by the ratio of rigid nanodomains, varying the composition ratio of DiynePC. Finally, the optimum condition and dominant interactions for enantioselective adsorption were clarified. Thus, our findings and results will be helpful to understand the induction of chiral recognition by polymerizable liposomes, and also become a guideline for the construction of liposomal chiral stationary phases.

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“…There is significant disagreement among previous studies of the effects of lipid stereochemistry on bilayer properties and affinities. Some studies have shown that phospholipids showed no preferential interaction with either R or S chiral molecules and that the changing the stereocenters of the lipids did not affect bilayer physical properties 21–23 . While more recent work has shown that after 24–48 hour incubation periods enantiomerically pure liposomes could preferentially absorb L-amino acids and preferentially absorb higher concentrations of one ibuprofen enantiomer over the other 24,25 .…”

Section: Introductionmentioning

confidence: 99%

Sphingomyelin ability to act as chiral selector using nanodisc electrokinetic chromatography

Penny

Palmer

2018

Chemistry and Physics of Lipids

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Understanding how stereochemistry affects interactions with cell membranes is important for effective drug development. Chirality has been shown to greatly effect pharmaceutical distribution and metabolism within the cell. However it has been thought that interactions with, and passive diffusion through, the membrane are not stereochemically selective. Various studies have produced conflicting results regarding whether interactions with lipid bilayers are or can be stereoselective. In the current work, stereoselective interactions between a pair of atropisomers, R-(+)/(S)-(-) 1,1'-Bi-2-naphthol, and sphingomyelin nanodisc bilayers, are demonstrated. This is accomplished using nanodisc electrokinetic chromatography, demonstrating that this approach is sensitive to subtle differences in affinity between small molecule probes and lipid bilayers. Using the same approach, no evidence of stereoselectivity was observed using enantiomer or diastereomer probes of varied chemistry and structure.

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Stereoselective Recognition in Phospholipid Monolayers

Cited by 11 publications

References 13 publications

Effects of Natural and Enantiomeric Cholesterol on the Thermotropic Phase Behavior and Structure of Egg Sphingomyelin Bilayer Membranes

Effects of Natural and Enantiomeric Cholesterol on the Thermotropic Phase Behavior and Structure of Egg Sphingomyelin Bilayer Membranes

Induction of Chiral Recognition with Lipid Nanodomains Produced by Polymerization

Sphingomyelin ability to act as chiral selector using nanodisc electrokinetic chromatography

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