Carbon-13 nuclear magnetic resonance spectroscopy of phospholipids in solution. Spectral and stereochemical assignments based on carbon-13-phosphorus-31 and carbon-13-nitrogen-14 couplings

Murari, Ramaswamy; El-Rahman, M.M.A. Abd; Wedmid, Yuri; Parthasarathy, Sampath; Baumann, Wolfgang J.

doi:10.1021/jo00132a034

Cited by 49 publications

(28 citation statements)

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“…1:2 and 2:1), the SPM and POPC resonances were assigned to the inner (Ϫ0.246 and Ϫ0.900 ppm, respectively) and outer (7.596 and 5.203 ppm, respectively) leaflets. The peak assignments agree well with earlier reports (35)(36)(37)(38). The larger Pr 3ϩ -induced downfield shift of outer leaflet SPM (compared with PC) and the distinct 31 P resonances of SPM and POPC in the absence of lanthanide ions were consistent with earlier findings (32,38,40).…”

Section: Spm Alters the Transmembrane Distribution Of Galcer-tosupporting

confidence: 92%

Sphingomyelin Modulates the Transbilayer Distribution of Galactosylceramide in Phospholipid Membranes

Mattjus¹,

Malewicz²,

Valiyaveettil³

et al. 2002

Journal of Biological Chemistry

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The interrelationships among sphingolipid structure, membrane curvature, and glycosphingolipid transmembrane distribution remain poorly defined despite the emerging importance of sphingolipids in curved regions and vesicle buds of biomembranes. Here, we describe a novel approach to investigate the transmembrane distribution of galactosylceramide in phospholipid small unilamellar vesicles by 13 C NMR spectroscopy. Quantitation of the transbilayer distribution of [6-13 C]galactosylceramide (99.8% isotopic enrichment) was achieved by exposure of vesicles to the paramagnetic ion, Mn 2؉ . The data show that [6-13 C]galactosylceramide prefers (70%) the inner leaflet of phosphatidylcholine vesicles. Increasing the sphingomyelin content of the 1-palmitoyl-2-oleoyl-phosphatidylcholine vesicles shifted galactosylceramide from the inner to the outer leaflet. The amount of galactosylceramide localized in the inner leaflet decreased from 70% in pure 1-palmitoyl-2-oleoyl-phosphatidylcholine vesicles to only 40% in 1-palmitoyl-2-oleoyl-phosphatidylcholine/ sphingomyelin (1:2) vesicles. The present study demonstrates that sphingomyelin can dramatically alter the transbilayer distribution of a monohexosylceramide, such as galactosylceramide, in 1-palmitoyl-2-oleoylphosphatidylcholine/sphingomyelin vesicles. The results suggest that sphingolipid-sphingolipid interactions that occur even in the absence of cholesterol play a role in controlling the transmembrane distributions of cerebrosides.Sphingolipids participate in a number of important cellular processes that require membrane budding, fission, or vesiculation (1, 2). Examples include infectious processes involving bacterial toxin and envelope virus entry into cells (3, 4), exosomal antigen presentation (5), and processes related to the terminal stages of apoptosis (6). Many recent investigations, by this laboratory and others, have focused on the in-plane lateral interactions among sphingolipids, cholesterol, and other membrane lipids (7-10). As a result, significant new insights into sphingolipid organization in membranes have emerged, including the identification and characterization of sphingolipid-enriched, liquid-ordered microdomains, often referred to as rafts (11-13). With so much emphasis on lipid lateral interactions, studies of sphingolipid transmembrane distribution have been relatively few (14), and the interrelationships among sphingolipid structure, membrane curvature, and glycosphingolipid transmembrane distribution remain poorly understood (15).Much of what is currently known about the mechanical forces affecting membrane curvature has been achieved by investigations of phosphoglyceride model membranes (16). The elastic constants associated with a fluid membrane are the bending elastic modulus and the spontaneous curvature (17, 18). The bending elastic modulus is the resistance of membranes to curvature or the bending rigidity, whereas the spontaneous curvature is the inherent curvature of an unconstrained membrane section and changes with lipid structure. Bec...

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Section: Spm Alters the Transmembrane Distribution Of Galcer-tosupporting

confidence: 92%

Sphingomyelin Modulates the Transbilayer Distribution of Galactosylceramide in Phospholipid Membranes

Mattjus¹,

Malewicz²,

Valiyaveettil³

et al. 2002

Journal of Biological Chemistry

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“…l-Palmitoyl-sn-glycerol-3-phosphocholine (lyso-PtdCho) was purchased from Sigma Chemical Co. The lyso-PtdCho analogues, l-palmityl-propanediol-3-phosphocholine, 1-palmityl-ethanediol-2-phosphocholine, and 1-palmitoyl-ethanediol-2-phosphocholine were a kind gift of Dr. W. J. Baumann (Hormel Institute, Austin, MN), prepared according to Murari et al (20) and analyzed for purity using nuclear magnetic resonance spectroscopy. Analysis by TLC using a solvent system of CHC13/CH3OH/H20 (65:35:6, vol/vol/vol) indicated that all samples were pure and migrated as a single species.…”

Section: Methodsmentioning

confidence: 99%

Oxidatively modified low density lipoprotein is a chemoattractant for human T lymphocytes.

McMurray¹,

Parthasarathy²,

Steinberg³

1993

J. Clin. Invest.

245

112

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Oxidatively modified low density lipoprotein (Ox-LDL) is a known chemoattractant for monocytes. Here we demonstrate, using a modified Boyden chamber assay, that human peripheral blood T lymphocytes, but not B lymphocytes, also respond chemotactically to Ox-LDL, showing a threefold increase over control and an optimum response at 10 ;tg/ml. Copper and endothelial cell-oxidized LDL and #l-VLDL were used and gave similar results. The activity was not chemokinetic and native LDL possessed no chemoattractant activity. The chemoattractant activity was found to reside in the lipid fraction of Ox-LDL. Lysophosphatidylcholine is a major phospholipid component of Ox-LDL and is known to be chemotactic for monocytes. We show that lysophosphatidylcholine is also chemotactic for T lymphocytes with a maximal fourfold increase at 10 MM. Nonmetabolizable analogues of lysophosphatidylcholine had no such chemotactic effect. Thus, Ox-LDL, by virtue of its lysophosphatidylcholine content, may contribute to the recruitment of both T lymphocytes and monocytes into developing atherosclerotic lesions. (J. Clin. Invest. 1993. 92:1004-1008

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“…The signals from carbons situated close to the phosphate in the molecule appear as doublets due to the 13 C-31 P spinspin coupling. For glycerophospholipids 3 J CP is generally larger than 2 J CP , owing to the preferred trans conformation of the sn-3 C-O bond which gives a torsion angle of approximately 180° (41,42). In N-acyl-PE this is demonstrated by comparing the coupling constants for the sn-2 carbon in the glycerol (8 Hz) and C-2 in the ethanolamine moiety (7 Hz) with the coupling constants for the sn-3 carbon (5 Hz) and C-1 in the ethanolamine moiety (5 Hz).…”

Section: Resultsmentioning

confidence: 99%

Characterization of N‐acylphosphatidylethanolamine and acylphosphatidylglycerol in oats

Holmbäck

Karlsson

Arnoldsson³

2001

Lipids

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Two polar lipid classes, both with three acyl groups, were isolated from an extract of oats and characterized by nuclear magnetic resonance spectroscopy, electrospray mass spectrometry (MS), and electron ionization MS (EIMS). Distortionless enhancement by polarization transfer (DEPT) and the two-dimensional correlation experiments 1H-detected heteronuclear multiple quantum coherence spectroscopy, heteronuclear multiple bond correlation spectroscopy, double quantum filtered correlation spectroscopy, and total correlation spectroscopy provided sufficient information for determination of the structure of the two lipid classes. The polar lipid classes were found to be N-acylphosphatidylethanolamine [1,2-diacyl-sn-glycero-3-phospho-(N-acyl)-1'-ethanolamine; N-acyl-PE] and acylphosphatidylglycerol [1,2-diacyl-sn-glycero-3-phospho-(3'-acyl)-1'-sn-glycerol]. High-performance liquid chromatography with electrospray ionization MS (HPLC-ESMS) and with electrospray ionization tandem MS (HPLC-MS/MS) were utilized for the separation and subsequent determination of molecular species. With HPLC-ESMS, ions of deprotonated molecules were obtained and with HPLC-MS/MS carboxylate ions (representing acyl groups) were obtained as well as other structurally significant ions. Fifty molecular species of N-acylphosphatidylethanolamine and 24 molecular species of acylphosphatidylglycerol were found, with a molecular mass range of 924-1032 Da and 959-1035 Da, respectively. Identification of the fatty acid isomers, as picolinyl ester derivatives, was done with gas chromatography with EIMS. Three isomers of 16:1 fatty acids were found in N-acyl-PE, and their double bond positions were determined to 6, 9, and 11 with a relative abundance of 4:10:1.

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Carbon-13 nuclear magnetic resonance spectroscopy of phospholipids in solution. Spectral and stereochemical assignments based on carbon-13-phosphorus-31 and carbon-13-nitrogen-14 couplings

Cited by 49 publications

References 1 publication

Sphingomyelin Modulates the Transbilayer Distribution of Galactosylceramide in Phospholipid Membranes

Sphingomyelin Modulates the Transbilayer Distribution of Galactosylceramide in Phospholipid Membranes

Oxidatively modified low density lipoprotein is a chemoattractant for human T lymphocytes.

Characterization of N‐acylphosphatidylethanolamine and acylphosphatidylglycerol in oats

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