Interactions between phospholipid head groups at membrane interfaces: a deuterium and phosphorus NMR and spin-label ESR study

Sixl, F.; Watts, Anthony

doi:10.1021/bi00268a020

Cited by 52 publications

(42 citation statements)

References 40 publications

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“…Spin lattice relaxation times for all three headgroup segments of Myr2-PtdCho are very similar in pure and in mixed Myr2-PtdCho/Myr2-PtdGro bilayers. (9), supporting the assumption of a mainly conformational change to account for the quadrupole splitting changes reported here. Second, the smaller steric.…”

Section: Methodssupporting

confidence: 87%

“…Mixed bilayers containing deuterated Myr2-PtdCho and Myr2-PtdGro gave similar but even more substantial changes in the quadrupole splittings compared to those from Myr2-PtdCho/ Myr2-PtdSer dispersions ( (9). Spin lattice relaxation times for all three headgroup segments of Myr2-PtdCho are very similar in pure and in mixed Myr2-PtdCho/Myr2-PtdGro bilayers.…”

Section: Methodsmentioning

confidence: 89%

“…The following specifically deuterated dimyristoyl derivatives of sn-phosphatidylcholine (Myr2-PtdCho), phosphatidyl-3-glycerol (Myr2-PtdGro), and phosphatidylethanolamine (Myr2-PtdEtn) were synthesized as described (9)…”

Section: Methodsmentioning

confidence: 99%

“…In particular, 2H NMR has been used to investigate conformational changes induced by ions, cholesterol, and anesthetics (6)(7)(8). However, limited information is available on lipid structure at membrane surfaces if more than one naturally occurring phospholipid type is present (9)(10)(11)(12).…”

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Headgroup interactions in mixed phospholipid bilayers

Sixl¹,

Watts²

1983

Proc. Natl. Acad. Sci. U.S.A.

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2H NMR methods have been used to study how bilayer-forming phospholipids interact with each other at the membrane surface. Aqueous dispersions of dimyristoyl-sn-phosphatidylcholine (Myr2-PtdCho), dimyristoyl-sn-phosphatidylethanolamine (Myr2-PtdEtn), and dimyristoyl-sn-phosphatidyl-3-glycerol, specifically deuterated at different positions in their headgroups, give well-resolved 2H NMR powder spectra. These spectra are characteristic of a lipid bilayer with quadrupole splittings that are sensitive to the amplitude of headgroup motion. In binary mixed bilayers of deuterated lipids with an unlabeled component, all parts of the deuterated headgroup monitor the presence of the second lipid from changes in the measured quadrupole splittings. The headgroups of the charged lipids, dimyristoyl-sn-phosphatidylserine and dimyristoyl-mn-phosphatidyl-3-glycerol, interact to the largest extent with the choline moiety of Myr2-PtdCho and the ethanolamine moiety of Myr2-PtdEtn, whereas a somewhat smaller but still marked alteration in headgroup motion was observed in Myr2-PtdCho/Myr2-PtdEtn mixtures. The large changes in the deuterium quadrupole splittings for the zwitterionic lipids after addition of a charged lipid suggest that either a strong perturbation in the hydrogen bonding occurs or changes take place in the water structure at the membrane surface, or possibly both.The lipid component of biological membranes is usually composed of a limited number of phospholipid types, which are identified by the chemical nature of their polar headgroup. Both the conformational and motional properties of lipid headgroups are well characterized for model membranes containing single phospholipid species, mainly on the basis of proton, deuterium, and phosphorus NMR and neutron diffraction studies (1)(2)(3)(4)(5). In particular, 2H NMR has been used to investigate conformational changes induced by ions, cholesterol, and anesthetics (6-8). However, limited information is available on lipid structure at membrane surfaces if more than one naturally occurring phospholipid type is present (9-12).Here we present results from 2H;NMR studies of fully hydrated bilayers of phospholipids deuterated in their headgroups, which suggest that strong interactions occur at the membrane surface between different lipids in binary mixed bilayers. In particular, phospholipids that carry a residual negative charge significantly change the measured quadrupole splittings for zwitterionic lipids. These observations imply that headgroup reorientations and motional amplitude changes can be induced in mixed lipid bilayers by alterations in the structured water layer at the membrane surface. MATERIALS AND METHODSMaterials. The following specifically deuterated dimyristoyl derivatives of sn-phosphatidylcholine (Myr2-PtdCho), phosphatidyl-3-glycerol (Myr2-PtdGro), and phosphatidylethanolamine (Myr2-PtdEtn) were synthesized as described (9): R-O-C2H2-C2Hr-N+(CH3)3 = Myr2-PtdCho-d4; R-O-CH2-CH2-N+(C2H3)3 = Myr2-PtdCho-d9; R-O-C2H2-C2Hg-N+H3 = Myr2-PtdEtn-d4; and ...

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Section: Methodssupporting

confidence: 87%

Section: Methodsmentioning

confidence: 89%

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

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Headgroup interactions in mixed phospholipid bilayers

Sixl¹,

Watts²

1983

Proc. Natl. Acad. Sci. U.S.A.

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“…The DMPC head group splittings are sen-FEBS LET 'TERS sitive to the presence of DMPS [26] and any loss of DMPS from the mixed lipid phase by binding to spectrin would be expected to be reflected in a decreased PS-induced perturbation of the DMPC head group quadrupole splittings [ 19,221. Moreover, it has been shown that fluorescent labeled phosphatidylserine has a faster lateral diffusion on the inner face of the erythrocyte membrane where spectrin is present, than on the outer face [35], with no detectable immobilized component .…”

Section: Discussionmentioning

confidence: 99%

Weak interaction of spectrin with phosphatidylcholine‐phosphatidylserine multilayers: A ²H and ³¹P NMR study

et al. 1989

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Spectrin from human erythrocytes binds to bilayer dispersions of both DMPC and DMPSDMPC (I: 1, w/w). However, no effect of bound spectrin on the conformation of the lipid head groups, as measured from the deuterium quadrupolar splittings of DMPC or DMPS specifically deuterated in the polar head groups, was detected in I:1 mixtures of the two lipids containing either deuterated DMPC or DMPS. Neither the phase transition of the DMPS:DMPC mixtures, nor the spin-lattice relaxation time (T,) of the deuterated DMPS head group, was affected by spectrin. These results argue against any strong interaction of spectrin with phosphatidylserine and rule out the possibility that spectrin is responsible for the maintainance of PS in the inner monolayer of the erythrocyte membrane during the whole life-span of this cell.

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Structure and dynamics of the phosphatidylcholine and the phosphatidylethanolamine head group in L-M fibroblasts as studied by deuterium nuclear magnetic resonance.

Scherer

Seelig

1987

The EMBO Journal

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Mouse fibroblast L‐M cells were grown in tissue culture medium containing selectively deuterated choline or ethanolamine. Both compounds were incorporated into the corresponding phospholipids at levels greater than 50% thus leading to a selective deuteration of these phospholipid head groups. Choline and ethanolamine were labeled at either the alpha‐ or the beta‐carbon atom and well‐resolved deuterium and phosphorus n.m.r. spectra were obtained from intact cells, crude plasma membranes and lipid extracts, leading to the following conclusions. (i) A large fraction, if not all, of the phospholipids in the intact L‐M cell membranes were organized in a liquid crystalline bilayer. (ii) The phosphoethanolamine and the phosphocholine head group conformation were found to be remarkably similar in pure lipid bilayers and in intact L‐M cell membranes with the head group dipoles being oriented parallel to the membrane surface. (iii) The deuterium T1 spin lattice relaxation times fell in the range of 7‐25 ms and were similar in intact L‐M cells and in pure lipid model membranes, suggesting that the two head groups are not involved in strong interactions with membrane proteins. The rotational diffusion rate of the two head groups was reduced by at least a factor of 10 compared to molecules of the same size in aqueous solution. (iv) The phosphocholine head group was sensitive to the size and sign of membrane surface charges as verified in mixing experiments with charged lipids. In L‐M cell membranes the phosphocholine appeared to sense an electrically neutral environment in spite of the fact that L‐M cell membranes contain 10‐20% negatively charged lipids.

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Interactions between phospholipid head groups at membrane interfaces: a deuterium and phosphorus NMR and spin-label ESR study

Cited by 52 publications

References 40 publications

Headgroup interactions in mixed phospholipid bilayers

Headgroup interactions in mixed phospholipid bilayers

Weak interaction of spectrin with phosphatidylcholine‐phosphatidylserine multilayers: A ²H and ³¹P NMR study

Structure and dynamics of the phosphatidylcholine and the phosphatidylethanolamine head group in L-M fibroblasts as studied by deuterium nuclear magnetic resonance.

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Interactions between phospholipid head groups at membrane interfaces: a deuterium and phosphorus NMR and spin-label ESR study

Cited by 52 publications

References 40 publications

Headgroup interactions in mixed phospholipid bilayers

Headgroup interactions in mixed phospholipid bilayers

Weak interaction of spectrin with phosphatidylcholine‐phosphatidylserine multilayers: A 2H and 31P NMR study

Structure and dynamics of the phosphatidylcholine and the phosphatidylethanolamine head group in L-M fibroblasts as studied by deuterium nuclear magnetic resonance.

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Weak interaction of spectrin with phosphatidylcholine‐phosphatidylserine multilayers: A ²H and ³¹P NMR study