Subgel Phase Structure in Monolayers of Glycosylphosphatidylinositol Glycolipids

Stefaniu, Cristina; Vilotijević, Ivan; Santer, Mark; Silva, Daniel Varón; Brezesinski, Gerald; Seeberger, Peter H.

doi:10.1002/anie.201205825

Cited by 37 publications

(45 citation statements)

References 50 publications

(20 reference statements)

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“…Despite the H-bond network, no order of the headgroups could be observed for these compounds, as recently reported for monolayers of a GPI fragment. 23 Concerning the headgroup region, the IRRA spectra additionally revealed the symmetric and asymmetric PO 2 − double-bond stretching bands occurring at 1086 (1088) cm −1 and 1221 cm −1 , respectively ( Figure 10). The frequency of 1221 cm −1 is considered to characterize a fully hydrated phosphate group.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Monolayer Properties of 1,3-Diamidophospholipids

2013

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While nature provides an endless variety of phospholipids presenting hydrolyzable ester linkages for the 1,2-positioned hydrocarbon tails, we designed and synthesized 1,3-diamidophospholipids which contain stable fatty acid amides. These new phospholipids form faceted unilamellar vesicles with mechanosensitive properties. Aiming to understand the mechanism responsible for this behavior at a molecular level, we investigated the 1,3-diamidophospholipid family in monolayers, a simplified model membrane system. Langmuir isotherms combined with in situ grazing incidence X-ray diffraction (GIXD), specular X-ray reflectivity (XR), and infrared reflection−absorption spectroscopy (IRRAS) allowed the characterization of the monolayers from a structural and thermodynamical point of view. The existence of strong headgroup interactions due to the formation of a hydrogen-bonding network was clearly revealed by IRRAS and by the high rigidity of the monolayers. GIXD showed that only the longer chain compounds of the series (Pad-PC-Pad (1,3-dipalmitamidopropan-2-phosphocholine) and Sad-PC-Sad (1,3-distearamidopropan-2-phosphocholine) were able to form ordered monolayers. The chains are strongly tilted in a rigid lattice formed due to these hydrogenbonding interactions between the headgroups. The thermodynamical analysis leads to a critical temperature of the monolayer which is clearly different from the main phase transition temperature in bulk, indicating that there must be a different structural arrangement of the 1,3-diamidophospholipids in monolayers and in bilayers.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Monolayer Properties of 1,3-Diamidophospholipids

2013

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“…GPI-anchored proteins with normally remodeled GPIs had elevated oligomerization tendency and immunoreactivity as compared to that with unremodeled GPIs [56]. Studies on a truncated GPI analog in monolayers revealed that phase-separation occurred above a threshold concentration owing to strong head-group interactions, whereas the GPI analog could mix with disordered lipid and induce order in a highly cooperative manner below this concentration [57]. The anchored proteins may also affect microdomain formation [58].…”

Section: Application Of Synthetic Gpis To Biological Studiesmentioning

confidence: 99%

Recent progress in synthetic and biological studies of GPI anchors and GPI-anchored proteins

Guo

Johnson

et al. 2013

Current Opinion in Chemical Biology

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Summary Covalent attachment of glycosylphosphatidylinositols (GPIs) to the protein C-terminus is one of the most common posttranslational modifications in eukaryotic cells. In addition to anchoring surface proteins to the cell membrane, GPIs also have many other important biological functions, determined by their unique structure and property. This account has reviewed the recent progress made in disclosing GPI and GPI-anchored protein biosynthesis, in the chemical and chemoenzymatic synthesis of GPIs and GPI-anchored proteins, and in understanding the conformation, organization, and distribution of GPIs in the lipid membrane.

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“…[14] Structural details of phospholipid monolayers incorporating gangliosides, glycolipids with branched pentasaccharide head groups, at various lateral densities were determined by XR. [45] In contrast to common studies on the lipid chain organization, [44] in this study the focus was on the saccharide head groups which form the actual interface with the aqueous phase. [49,58,76] All these studies evidenced the key role of electrostatic interactions for the LPS surface characteristics.…”

Section: Lessons From the Structure Of Single Interfacesmentioning

confidence: 99%

“…Diffraction has substantially contributed to our understanding of the structure of interfaces. Grazing-incidence diffraction and off-specular reflectometry yield information on the in-plane structure of an interface [44,45] and, respectively, on its topography in terms of static roughness and fluctuations. [28,42,46,47] Specular reflectometry, on the other hand, reveals scattering length density (SLD) profiles perpendicular to an interface.…”

Section: Structural Investigationsmentioning

confidence: 99%

“…The lateral organization of a glycolipid surface was investigated by Stefaniu et al using grazing-incidence x-ray diffraction (GIXD). [45] In contrast to common studies on the lipid chain organization, [44] in this study the focus was on the saccharide head groups which form the actual interface with the aqueous phase. The diffraction pattern allowed reconstruction of the 2D-crystalline arrangement of hydrocarbon chains and saccharide head groups.…”

Section: Lessons From the Structure Of Single Interfacesmentioning

confidence: 99%

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The Interaction between Soft Interfaces: Forces and Structural Aspects

Schneck

2016

Adv Materials Inter

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Soft interfaces constituted by two-dimensional molecular layers play important roles in numerous technological applications and are major components of all biological matter, for example in the form of biomembranes. The mutual interaction between such interfaces often crucially influences their function as well as the structural organization of the entities they form. The forces acting between two soft interfaces in liquids not only depend on their chemical properties, like charge density or hydrophilicity. They are often also closely connected to the structural response of the interfaces to their interaction, for instance in terms of molecular conformations or ion distributions. This interplay renders the description of the interaction between soft or chemically complex interfaces challenging. In the present article, various experimental and theoretical approaches to the study of interacting soft interfaces are reviewed with a focus on structural aspects

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Subgel Phase Structure in Monolayers of Glycosylphosphatidylinositol Glycolipids

Cited by 37 publications

References 50 publications

Monolayer Properties of 1,3-Diamidophospholipids

Monolayer Properties of 1,3-Diamidophospholipids

Recent progress in synthetic and biological studies of GPI anchors and GPI-anchored proteins

The Interaction between Soft Interfaces: Forces and Structural Aspects

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