Oskar Engberg, Viola Döbel, Kathrin M Engel, Daniel Huster
{"title":"Characterization of lipid chain order and dynamics in asymmetric membranes by solid-state NMR spectroscopy.","authors":"Oskar Engberg, Viola Döbel, Kathrin M Engel, Daniel Huster","doi":"10.1039/d4fd00192c","DOIUrl":"https://doi.org/10.1039/d4fd00192c","url":null,"abstract":"<p><p>We studied the structure and dynamics of asymmetric POPC<sup>out</sup>/(POPE/POPG)<sup>in</sup> and POPS<sup>out</sup>/(POPE/POPG)<sup>in</sup> lipid membranes. To this end, the outer layer of multilamellar POPE/POPG (molar ratio 9 : 1) vesicles was exchanged (using methyl-β-cyclodextrin) by either chain deuterated POPC-<i>d</i><sub>31</sub> or POPS-<i>d</i><sub>31</sub>, for which <sup>2</sup>H NMR order parameters were measured. As controls, we prepared symmetric POPC-<i>d</i><sub>31</sub>/POPE/POPG and POPS-<i>d</i><sub>31</sub>/POPE/POPG membranes of the composition of just the outer membrane of the asymmetric multilamellar vesicles and pure POPC-<i>d</i><sub>31</sub> or POPS-<i>d</i><sub>31</sub> multilamellar vesicles. Compared to symmetric membranes of the same lipid composition, chain order parameters (<i>S</i>) of the asymmetric preparations were higher in the upper half of the chain and lower in the lower half. This reshuffling of acyl chain order is also expressed in higher <sup>2</sup>H NMR Zeeman order relaxation rates (<i>R</i><sub>1Z</sub>) of the chain segments in asymmetric membranes indicating alterations in the elastic properties of asymmetric bilayers as inferred from plots of <i>R</i><sub>1Z</sub><i>vs. S</i><sup>2</sup>. Asymmetric membranes showed increased stiffness and rigidity although the lipid acyl chain composition between the inner and outer leaflets were identical. There were no indications for chain interdigitation between the two leaflets in the NMR spectra, which led us to speculate that the interleaflet coupling could be accomplished by sensing the differences in lipid packing densities between the two leaflets. These alterations in leaflet properties should have consequences for lipid protein interaction and ultimately protein function.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143953415","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Spiers memorial lecture: Experimental discovery of asymmetric bilayers, and a recent asymmetry example.","authors":"Gerald W Feigenson","doi":"10.1039/d5fd00041f","DOIUrl":"https://doi.org/10.1039/d5fd00041f","url":null,"abstract":"<p><p>This introductory <i>Faraday Discussions</i> lecture considers the wide range of subjects that involve asymmetric bilayer membranes. The <i>Discussions</i> organizers have chosen four themes that describe the current interest in asymmetric bilayers. The main part of this introductory lecture starts with the discovery from over 50 years ago that the plasma membrane of mature, human erythrocytes has different composition and properties in each leaflet of the plasma membrane. We also comment on what is newly recognized in the asymmetric membrane field. The asymmetric bilayer is a remarkable state of matter. Newly recognized, we can describe it as a \"new state of matter\". Like other biological matter, it evolved to be in its particular form. There is new appreciation for the properties of the asymmetric bilayer, and there has been progress in understanding these emerging properties. Asymmetric lipid bilayers have a remarkable range of characteristics that involve the physically and chemically special connection of the two different monolayer leaflets. Much of this work is an explanation of how the \"van Deenen researchers\", over 50 years ago, quantitatively measured the phosphatidylcholine, sphingomyelin, and phosphatidylethanolamine content of the erythrocyte plasma membrane exoplasmic leaflet. Their use of surface chemistry principles was important in proper quantitation, and this introductory lecture explains these research findings in detail. We also present a detailed discussion of one remarkable example of a newly-discovered behavior of asymmetric bilayers, which we term \"induced order\". This discovery has an absolute requirement for microscopy image data to reveal the superposition of induced order with the thermodynamic order of liquid-ordered + disordered phase separation.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144052972","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ben John, Sarabjeet Kaur, Martin Wolf, Martin Thämer, Alexander P Fellows
{"title":"Using phase-resolved vibrational sum-frequency imaging to probe the impact of head-group functionality on hierarchical domain structure in lipid membranes.","authors":"Ben John, Sarabjeet Kaur, Martin Wolf, Martin Thämer, Alexander P Fellows","doi":"10.1039/d4fd00187g","DOIUrl":"https://doi.org/10.1039/d4fd00187g","url":null,"abstract":"<p><p>The substantial diversity in phospholipids within a plasma membrane, varying in tail length, degree of saturation, and head-group functionality, generates widespread structural heterogeneity. This exists both laterally across the membrane through the spontaneous formation of condensed domains that differ from their surrounding expanded phase in density, composition, and molecular packing order, as well as between its two leaflets, which normally maintain significant compositional asymmetry. Of particular importance is the exposure of phosphatidylserine (PS) lipids which is a marker for important physiological processes <i>e.g.</i> apoptosis. Despite this, the molecular-level alterations to the phase-structure of the membrane that result from PS exposure remain generally unknown. In this work, we utilise recently developed phase-resolved azimuthal-scanned sum-frequency generation (SFG) microscopy to investigate structural changes that occur heterogeneously across model membranes as a result of PS-lipid exposure. Specifically, by probing mixed monolayers of 1,2-dipalmitoylphosphatidylcholine (DPPC) and deuterated 1-palmitoyl-2-oleoylphosphatidylcholine (dPOPC) in both the C-H and C-D stretching regions as well as equivalent films with DPPC exchanged with DPPS, we analyse the variations in the apparent phase distributions and domain morphologies, and quantitatively extract the density, composition, and relative out-of-plane packing order for both mixtures. We find that, in these mixtures, DPPS shows vast differences in the domain growth and coalescence behaviour compared to DPPC, as well as in the relative compositions and molecular ordering within each phase. This demonstrates the critical role the head-group plays in the heterogeneous phase structure of the membrane and may give insights into their impact on important physiological processes.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143951439","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
K. Kahle, Petra M. Klinge, Jenna E. Koschnitzky, Abhaya V. Kulkarni, Nanna MacAulay, Shenandoah Robinson, Steven J. Schiff, J. Strahle
{"title":"Paediatric hydrocephalus","authors":"K. Kahle, Petra M. Klinge, Jenna E. Koschnitzky, Abhaya V. Kulkarni, Nanna MacAulay, Shenandoah Robinson, Steven J. Schiff, J. Strahle","doi":"10.1038/s41572-024-00519-9","DOIUrl":"https://doi.org/10.1038/s41572-024-00519-9","url":null,"abstract":"","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":"23 9","pages":"1-16"},"PeriodicalIF":81.5,"publicationDate":"2024-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140967670","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mark Aarts, Martin Z. Bazant, Lydéric Bocquet, Fabio Cicoira, Robert A. W. Dryfe, Sanli Faez, Y. K. Catherine Fung, Ehud Haimov, Bee Hockin, Christian Holm, Tim M. Kamsma, Frédéric Kanoufi, Alexei A. Kornyshev, Serge G. Lemay, Yan Levin, Sophie Marbach, Elalyaa Mohamed, Joan Montes de Oca, Frieder Mugele, Monica Olvera de la Cruz, Susan Perkin, Jenny Pringle, Paul Robin, Benjamin Rotenberg, Alexander Schlaich, Igor Siretanu, Zuzanna S. Siwy, Derek Stein, René van Roij, Tanja Vidaković-Koch, Kislon Voïtchovsky, Gilad Yossifon and Yujia Zhang
{"title":"Iontronic dynamics: general discussion","authors":"Mark Aarts, Martin Z. Bazant, Lydéric Bocquet, Fabio Cicoira, Robert A. W. Dryfe, Sanli Faez, Y. K. Catherine Fung, Ehud Haimov, Bee Hockin, Christian Holm, Tim M. Kamsma, Frédéric Kanoufi, Alexei A. Kornyshev, Serge G. Lemay, Yan Levin, Sophie Marbach, Elalyaa Mohamed, Joan Montes de Oca, Frieder Mugele, Monica Olvera de la Cruz, Susan Perkin, Jenny Pringle, Paul Robin, Benjamin Rotenberg, Alexander Schlaich, Igor Siretanu, Zuzanna S. Siwy, Derek Stein, René van Roij, Tanja Vidaković-Koch, Kislon Voïtchovsky, Gilad Yossifon and Yujia Zhang","doi":"10.1039/D3FD90032K","DOIUrl":"10.1039/D3FD90032K","url":null,"abstract":"","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":"246 ","pages":" 322-355"},"PeriodicalIF":3.4,"publicationDate":"2023-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41090532","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sidahmed Abayzeed, Tarique Anwar, Alexander Barnaveli, Martin Z. Bazant, Lyderic Bocquet, Aleksandar Donev, Robert A. W. Dryfe, Sanli Faez, Amritha Janardanan, Felipe Jiménez-Ángeles, Tim M. Kamsma, Frédéric Kanoufi, Alexei A. Kornyshev, Serge G. Lemay, Yan Levin, Sophie Marbach, Joan Montes de Oca, Paul Robin, Zuzanna S. Siwy, Derek Stein, Rene van Roij, Tanja Vidaković-Koch, Gilad Yossifon and Yujia Zhang
{"title":"Iontronic coupling: general discussion","authors":"Sidahmed Abayzeed, Tarique Anwar, Alexander Barnaveli, Martin Z. Bazant, Lyderic Bocquet, Aleksandar Donev, Robert A. W. Dryfe, Sanli Faez, Amritha Janardanan, Felipe Jiménez-Ángeles, Tim M. Kamsma, Frédéric Kanoufi, Alexei A. Kornyshev, Serge G. Lemay, Yan Levin, Sophie Marbach, Joan Montes de Oca, Paul Robin, Zuzanna S. Siwy, Derek Stein, Rene van Roij, Tanja Vidaković-Koch, Gilad Yossifon and Yujia Zhang","doi":"10.1039/D3FD90031B","DOIUrl":"10.1039/D3FD90031B","url":null,"abstract":"","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":"246 ","pages":" 157-178"},"PeriodicalIF":3.4,"publicationDate":"2023-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41090783","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}