Dependence of phosphatidylcholine phosphorus-31 relaxation times and phosphorus-31 {proton} nuclear Overhauser effect distribution on aggregate structure

Burns, Ramon A.; Vidusek, David A.; Roberts, Mary F.

doi:10.1021/bi00291a006

Cited by 15 publications

(7 citation statements)

References 17 publications

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“…One-dimensional 31 P magic-angle spinning (MAS) NMR techniques have been extensively applied to the study of lipid bilayer systems (24)(25)(26)(27)(28)(29)(30)(31)(32) and have been recently utilized to study raft formation in tertiary lipid systems containing cholesterol (33). A few reports on the application of two-dimensional 1 H/ 31 P heteronuclear Overhauser effect spectroscopy (HOESY) (26,34) have appeared on PC and phosphatidylethanolamine lipids, although the bulk of 31 P nuclear Overhauser effect (NOE) studies are of the one-dimensional variety (35)(36)(37)(38)(39)(40). NMR experiments involving 1 H/ 13 C cross-polarization (CP) have also been shown to be useful in the study of lipid membrane systems and have been implemented in both one-dimensional (25,(41)(42)(43)(44) and twodimensional (45)(46)(47) experiments.…”

Section: Introductionmentioning

confidence: 99%

Unique Backbone-Water Interaction Detected in Sphingomyelin Bilayers with 1H/31P and 1H/13C HETCOR MAS NMR Spectroscopy

Holland

Alam

2008

Biophysical Journal

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Two-dimensional (1)H/(31)P dipolar heteronuclear correlation (HETCOR) magic-angle spinning nuclear magnetic resonance (NMR) is used to investigate the correlation of the lipid headgroup with various intra- and intermolecular proton environments. Cross-polarization NMR techniques involving (31)P have not been previously pursued to a great extent in lipid bilayers due to the long (1)H-(31)P distances and high degree of headgroup mobility that averages the dipolar coupling in the liquid crystalline phase. The results presented herein show that this approach is very promising and yields information not readily available with other experimental methods. Of particular interest is the detection of a unique lipid backbone-water intermolecular interaction in egg sphingomyelin (SM) that is not observed in lipids with glycerol backbones like phosphatidylcholines. This backbone-water interaction in SM is probed when a mixing period allowing magnetization exchange between different (1)H environments via the nuclear Overhauser effect (NOE) is included in the NMR pulse sequence. The molecular information provided by these (1)H/(31)P dipolar HETCOR experiments with NOE mixing differ from those previously obtained by conventional NOE spectroscopy and heteronuclear NOE spectroscopy NMR experiments. In addition, two-dimensional (1)H/(13)C INEPT HETCOR experiments with NOE mixing support the (1)H/(31)P dipolar HETCOR results and confirm the presence of a H(2)O environment that has nonvanishing dipolar interactions with the SM backbone.

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Section: Introductionmentioning

confidence: 99%

Unique Backbone-Water Interaction Detected in Sphingomyelin Bilayers with 1H/31P and 1H/13C HETCOR MAS NMR Spectroscopy

Holland

Alam

2008

Biophysical Journal

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“…Both detergent/phosphatidylcholine mixed micelles (Lichtenberg etal., 1983;Verger, 1980;Dennis, 1973a,b) and pure short-chain lecithins (Lewis et al, 1990;DeBose et al, 1985; Little, 1977; Verger & De Haas, 1976;Wells, 1974;Bonsen etal., 1972b;De Haas etal., 1971) have, therefore, been used extensively in the investigation of watersoluble phospholipases. In the latter systems, the individual lecithin molecules have many of the same dynamic features of naturally occurring lecithins in bilayers with the exception that the area per headgroup is considerably larger and intermolecular interactions with the aggregate are looser (Bian & Roberts, 1992;Lin et al, 1986Lin et al, , 1987aBurns et al, 1983;Burns & Roberts, 1980). An implicit assumption in using these micellar phospholipid systems for phospholipase kinetics is that there is a rapid reorganization of lipid components when the micelle concentration is decreased or when other f This work has been supported by NIH Grant GM 26762. amphiphilic molecules are added.…”

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confidence: 99%

Fluorescence Studies of Phosphatidylcholine Micelle Mixing: Relevance to Phospholipase Kinetics

Soltys

Roberts²

1994

Biochemistry

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Two fluorescent micellar phospholipid probes (1-hexanoyl-2-(1-pyrenebutyroyl)phosphatidylcholine and 1-octanoyl-2-(1-pyrenebutyroyl)phosphatidylcholine) have been synthesized, characterized, and used to monitor the dynamics of lipid/amphiphile exchange in a variety of detergents and phospholipid micelles using both steady-state and stopped-flow fluorescence techniques. The ratio of the pyrene monomer to excimer band is a good indicator of the extent of lipid mixing at equilibrium. Following the time dependence of increase in the monomer band with stopped-flow methodology provides a rate constant for this exchange process (most systems were well fit with a single exponential). Short-chain pyrene-labeled phosphatidylcholine mixing with Triton X-100 micelles is extremely fast and follows a concentration dependence indicative of the importance of micelle collisions for the exchange process. Submicellar amounts of Triton have no effect on the fluorescent dynamics of the probe molecule. Other detergents such as beta-octyl glucoside and deoxycholate are also effective at higher concentrations, although significant differences exist in the extent of probe mixing. Short-chain diacylphosphatidylcholine and lysophosphatidylcholine mixing rates are moderately fast with mixing times that decrease as the hydrophobicity/chain length of the diluent matrix increases. The rate constants for lipid exchange can be compared to turnover rates of several phospholipases in these assay systems. Anomalous mixing behavior of unusual micelle forming lipids [bolaforms and omega-carboxylate phosphatidylcholines [Lewis, K. A., Bian, J., Sweeny, A., & Roberts, M. F. (1994) Biochemistry 29, 9962-9970] and polymerizable phosphatidylcholines [Soltys, C. E., Bian, J., & Roberts, M. F. (1993) Biochemistry 32, 9545-9551] is particularly helpful in understanding kinetics of water-soluble phospholipases on these systems.

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“…Diheptanoyl-PC (di-C7-PC) forms rod-shaped micelles, with a minimum aggregation number of 27 and a cmc of 2 mM (Hershberg et al, 1976); these micelles increase in length with increasing lipid concentration (Tausk et al, 1974). The largest lecithin in the series, dioctanoyl-PC (di-Cg-PC), has a cmc of 0.3 mM and forms very large, concentration-dependent micelles above this concentration (Burns et al, 1983).…”

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confidence: 99%

Gramicidin A/Short-Chain Phospholipid Dispersions: Chain Length Dependence of Gramicidin Conformation and Lipid Organization

Greathouse¹,

Hinton²,

Kim³

et al. 1994

Biochemistry

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Gramicidin-lipid interactions were investigated using diacylphosphatidylcholines that contained two identical acyl chains of varying length, between 6 and 14 carbons. The gramicidin A (gA) conformation was monitored by circular dichroism (CD) spectroscopy and high-performance size-exclusion chromatography, and the lipid organization was investigated using 31P and 1H NMR spectroscopy and negative-stain electron microscopy. Diacylphosphatidylcholine (PC) lipids with chain lengths between 4 and 8 carbons have been previously shown to have a micellar organization in aqueous solution [Lin, T.-L., et al. (1986) J. Am. Chem. Soc. 108, 3499-3507]. CD spectra of aqueous gA/lipid dispersions, at a ratio of 1:28, demonstrated that the channel conformation of gA can be readily obtained when the acyl chain length is > or = 10, but not when the chain length is < or = 7. Size-exclusion chromatography revealed that the fraction of gA that could easily be dissociated into monomers in the dispersions increased with increasing acyl chain length, in agreement with the CD results. For a chain length of 8, the results were intermediate. The formation of the channel structure was found to depend on the "solvent-history", the temperature, the gA and lipid concentrations, the gA:lipid ratio, and consequently on the method of sample preparation. 1H and 31P NMR results suggest that codispersed gA increases the size of dioctanoyl-PC aggregates, but not of dihexanoyl-PC micelles. Negative-stain electron microscopy directly supports these findings. Dihexanoyl-PC (28 mM) was able to solubilize 1 mM gA in H2O, but the gA was not in the "channel" conformation.(ABSTRACT TRUNCATED AT 250 WORDS)

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Dependence of phosphatidylcholine phosphorus-31 relaxation times and phosphorus-31 {proton} nuclear Overhauser effect distribution on aggregate structure

Cited by 15 publications

References 17 publications

Unique Backbone-Water Interaction Detected in Sphingomyelin Bilayers with 1H/31P and 1H/13C HETCOR MAS NMR Spectroscopy

Unique Backbone-Water Interaction Detected in Sphingomyelin Bilayers with 1H/31P and 1H/13C HETCOR MAS NMR Spectroscopy

Fluorescence Studies of Phosphatidylcholine Micelle Mixing: Relevance to Phospholipase Kinetics

Gramicidin A/Short-Chain Phospholipid Dispersions: Chain Length Dependence of Gramicidin Conformation and Lipid Organization

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