Nuclear magnetic resonance investigation of hydrocarbon chain packing in bilayers of polyunsaturated phospholipids

Holte, Laura L.; Separovic, F.; Gawrisch, Klaus

doi:10.1007/bf02637076

Cited by 53 publications

(30 citation statements)

References 36 publications

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“…In addition to the importance of the phospholipid head group, also the degree of phospholipid acyl chain unsaturation will determine [30] part of the CPZ interaction with the bilayer. The observed increased signal intensity of CfC SDPS's DHA acyl chain carbon resonances and an increase in the corresponding T 1 -values for two (out of three that could be measured) of the CfC peaks where the C 4 and C 5 resonances reside and, thus, the reduced mobility of C 4 and C 5 appear to be due to CPZ binding.…”

Section: Discussionmentioning

confidence: 99%

Importance of polyunsaturated acyl chains in chlorpromazine interaction with phosphatidylserines: A 13C and 31P solid-state NMR study

Song

Gjerde

Holmsen

et al. 2005

Biophysical Chemistry

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Section: Discussionmentioning

confidence: 99%

Importance of polyunsaturated acyl chains in chlorpromazine interaction with phosphatidylserines: A 13C and 31P solid-state NMR study

Song

Gjerde

Holmsen

et al. 2005

Biophysical Chemistry

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“…31 In addition, from 2 H NMR it has been observed that increasing unsaturation results in a lower order parameter. 32,33 Quantum mechanical calculations predict a high degree of conformational flexibility for polyunsaturated acyl chains. 34 Not only do the pure 20 : 4/20 : 4-PC and 22 : 6/22 : 6-PC have sufficient flexibility not to exhibit a resonance signal for the terminal methyl group with the pure PC, but also this resonance is not present in equimolar mixtures of cholesterol with 20 : 4/20 : 4-PC or 22 : 6/22 : 6-PC.…”

Section: Discussionmentioning

confidence: 99%

Properties of polyunsaturated phosphatidylcholine membranes in the presence and absence of cholesterol

Epand

Bain

Sayer

et al. 2004

Magnetic Reson in Chemistry

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Mixtures of cholesterol with phosphatidylcholine species containing the polyunsaturated acyl chains arachidonoyl or docosahexaenoyl were studied by (13)C magic angle spinning (MAS) NMR using both cross-polarization and direct polarization, by (31)P NMR and by differential scanning calorimetry. Several unique features of these systems were observed. The separation of cholesterol in crystalline form occurred at much lower molar fractions than with other forms of phosphatidylcholine. The crystals that were formed were sensitive to the history of the sample. At cholesterol molar fractions below 0.5, they dissolved into the membrane by sequential heating and cooling scans. With higher molar fractions of cholesterol, larger amounts of anhydrous crystals were formed after the first heating. This was accompanied by the formation of non-lamellar phases. The cholesterol crystals that were formed generally were not observed by direct polarization (13)C MAS NMR, even with delay times of 100 s. This suggests that the cholesterol crystals are in a more rigid state in mixtures with these lipids. This is in contrast with the terminal methyl group of the acyl chains that is too mobile to allow cross-polarization using 1 ms contact times.

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“…[23][24][25][26][27][28][29][30] In this way, unsaturation is an important determinant of bilayer mechanical properties. Natural bilayer lipids exist with a wide range of unsaturation levels, and the adaptive value of such a range is not obvious.…”

Section: Discussionmentioning

confidence: 99%

Effect of Cholesterol on the Chain-Ordering Transition of 1-Palmitoyl-2-arachidonoyl Phosphatidylcholine

et al. 1999

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Deuterium nuclear magnetic resonance and differential scanning calorimetery were used to study the phase behavior, chain order, and dynamics of bilayers consisting of 1-palmitoyl-2-arachidonoyl phosphatidylcholine perdeuterated on the saturated acyl chain (16:0-20:4 PC-d 31 ) alone and in mixed bilayers containing 15 and 30 mol % cholesterol. In the liquid crystalline phase, saturated chain orientational order increases with increasing cholesterol concentration. The transition to a highly ordered phase is centered on -25°C regardless of cholesterol concentration. The observation of coexisting ordered and liquid crystalline phase spectral contributions near the transition in the absence of cholesterol implies a discontinuous transition. In the presence of cholesterol, the phase change is continuous and no evidence of coexisting domains of ordered and fluid phase lipid is observed. The observation of spectral intensity near (63 kHz in the ordered phase suggests near-immobilization of the methylene deuterons and is reminiscent of the subgel or L C phase of disaturated phospholipids. Cholesterol does not alter the apparent splitting of methylene deuterons in the ordered phase but does narrow the spectral contribution from methyl deuterons on the saturated chain. Quadrupole echo decay time measurements are used to gain some insight into long-range and more localized lipid motions that modulate the orientation-dependent quadrupole interaction on the time scale of the quadrupole echo experiment. The observed temperature dependence of the echo decay times suggests that echo decay in the ordered phase of 16:0-20:4 PC-d 31 bilayers is dominated by different motions than in disaturated phospholipids. These observations are compared with results from an earlier study on bilayers containing 16:0-18:2 PC-d 31 . While the difference in unsaturated chain has little effect on the chain-ordering transition temperature, small but potentially significant differences are observed in the response of the bilayer transition and dynamics to cholesterol.

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Nuclear magnetic resonance investigation of hydrocarbon chain packing in bilayers of polyunsaturated phospholipids

Cited by 53 publications

References 36 publications

Importance of polyunsaturated acyl chains in chlorpromazine interaction with phosphatidylserines: A 13C and 31P solid-state NMR study

Importance of polyunsaturated acyl chains in chlorpromazine interaction with phosphatidylserines: A 13C and 31P solid-state NMR study

Properties of polyunsaturated phosphatidylcholine membranes in the presence and absence of cholesterol

Effect of Cholesterol on the Chain-Ordering Transition of 1-Palmitoyl-2-arachidonoyl Phosphatidylcholine

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