The properties of membranes formed from cyclopentanoid analogues of phosphatidylcholine

Singer, Michael; Jain, Mahendra Kumar; Sable, Henry Z.; Pownall, Henry J.; Mantulin, William W.; Lister, Mark D.; Hancock, Anthony J.

doi:10.1016/0005-2736(83)90030-5

Cited by 20 publications

(9 citation statements)

References 9 publications

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“…DSC traces of (RP)-DPPsC of greater isomeric purity (>99%), showing the time dependence of the metastable gel phase. The sample (4.20 mg) was heated to 70 °C for 5 min and then equilibrated at 25 °C for 0 (a), 0.25 (b), 0.5 (c), and 65 h (d). Thermal equilibration of the calorimeter with the sample was conducted at 38 °C for 10-15 min just prior to scanning.…”

Section: Resultsmentioning

confidence: 99%

Phospholipids chiral at phosphorus. 12. Configurational effect on the thermotropic properties of chiral dipalmitoylthiophosphatidylcholine

Wisner¹,

Rosario-Jansen²,

Tsai³

1986

J. Am. Chem. Soc.

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Differential scanning calorimetry (DSC) studies of the diastereomers of 1,2-dipalmitoyl-sn-glycer0-3-thiophosphocholine (DPPsC) have been carried out to determine the effect of phosphate structure and configuration on the phase-transition properties of these analogues of natural 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) in the multilamellar form. Both the Sp and RP + Sp isomers showed a "pretransition" (Tpt = 43.7 and 43.8 OC, respectively) and a "main transition" ( T , = 45.0 and 44.8 OC, respectively). The corresponding values for DPPC were 35.1 and 41 $5 OC, respectively. (Rp)-DPPsC, however, showed a single, broad transition at 45.9 OC with significantly higher AH. Addition of 15% (&)-DPPsC to the RP isomer converted the broad DSC trace to a "normal" pattern, with Tpt and T, at 42.8 and 44.7 OC, respectively. These suggest that the broad, highly endothermic transition is a unique property of pure (Rp)-DPPsC, which could be a superposition of subtransition, pretransition, and main transition based on the following results. While (Sp)-and (RP + Sp)-DPPsC showed a subtransition near 20 OC following prolonged incubation at 0 OC, a property also possessed by DPPC, (Rp)-DPPsC showed no discernible subtransition following incubation at 0 OC. Furthermore, it was found that (Rp)-DPPsC can indeed exist in the gel phase but relaxes rapidly to a lower energy phase, presumably the subphase. The half-life of the metastable gel phase was found to increase with decreasing diastereomeric purity of (Rp)-DPPsC. These studies suggest that (Rp)-DPPsC is thermodynamically and kinetically more stable at the subphase and demonstrate that the structure and configuration at the phosphate group of phospholipids have a large effect on the thermotropic properties of membranes, particularly in the subtransition temperature. The results are discussed in terms of intermolecular interactions and chiral discrimination in phospholipid membranes.The effect of chirality on the molecular interactions of membranes has received increasing attention in recent years.' One important question is whether there are chiral discrimination factors in membranes, as their main constituents and many of the compounds which must traverse them are chiral. The general approach to determine "enantiomer discrimination" has been to compare the physical properties of isomerically pure phospholipids with those of the mixture of enantiomers. Arnett and co-workers have clearly demonstrated enantiomer discrimination in the monolayers of enantiomeric and racemic N-(a-methylbenzy1)-stearamide.'q3 Chiral discrimination between monolayers of enantiomeric and racemic phospholipids has also been reported in the force-area isotherms of monolayers of 1-stearoyl-2-lauroylph~sphatidylcholine~ and in the differential scanning calorimetry (DSC) studies of multilamellar DPPC5-' However, Arnett and Gold* have been unable to detect any significant difference between racemic DPPC and its enantiomers in their meticulous studies using DSC, NMR, and monolayer techniques. (1) For pa...

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Section: Resultsmentioning

confidence: 99%

Phospholipids chiral at phosphorus. 12. Configurational effect on the thermotropic properties of chiral dipalmitoylthiophosphatidylcholine

Wisner¹,

Rosario-Jansen²,

Tsai³

1986

J. Am. Chem. Soc.

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“…Figure 6 compares the temperature profiles derived from the I (2850 cm −1 )/ I (2885 cm −1 ), I (2940 cm −1 )/ I (2850 cm −1 ) and I (2940 cm −1 )/ I (2885 cm −1 ) peak height intensity ratios for 1,3/2- 1P-dipalmitoylcyclopentane-1,2,3-triol phosphatidic acid, an analog of DPPC in which the glycerol backbone is replaced by a more rigid cyclopentane triol [ 13 ]. All three profiles give the same value for the phase transition temperature within the limits of the standard deviations obtained from the least squares fit.…”

Section: Analysis Of Temperature Profiles Derived From Raman Intensity Ratiosmentioning

confidence: 99%

Description of the thermotropic behavior of membrane bilayers in terms of raman spectral parameters - a 2-state model

Kirchhoff¹,

Levin²

1987

J. RES. NATL. BUR. STAN.

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An analytical expression is developed for describing the thermotropic behavior of membrane bilayers as studied by Raman spectroscopy. The expression is derived from a two-state model of the main gel to liquid crystalline phase transition in lipid bilayers. Experimental data for a variety of diacylphosphatidylcholines and their derivatives have been fit by least squares to the two-state expression to within currently achievable measurement error. Numerical techniques have been developed for placing bounds on the parameters of the two-state model in situations of sparse data in the phase transition region. By fitting the model to the measured spectroscopic data, estimates of the extent of cooperativity in the phase transition can be obtained in a systematic manner.

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“…Other approaches to the study of the effects of lipid interfacial structure on lipid phase behavior have involved comparisons of glycerolipids with ester-linked hydrocarbon chains with appropriate amido-linked counterparts (Curatolo et al, 1982(Curatolo et al, , 1985Chowdhry et al, 1984b), comparisons of normal glycerolipids with analogs containing "conformationally restricted backbones" (Blume and Eibl, 1981;Singer et al, 1983), and comparisons of glycerolipids with 1,3-linked hydrocarbon chains with comparable 1,2-linked analogs (Eibl and Blume, 1979;Serralach et al, 1983;Stumpel et al, 1981;Chowdhry et al, 1984a;Dluhy et al, 1985). It has also been demonstrated that the propensity of some glycerolipids to form inverted nonlamellar phases can be altered by the chirality of the glycerol backbone (Mannock et al, 1992(Mannock et al, , 1994) and by the location of modestly sized hydrophobic groups near the glycerol backbone of the lipid (Lewis et al, 1994a).…”

Section: Introductionmentioning

confidence: 99%

The interfacial structure of phospholipid bilayers: differential scanning calorimetry and Fourier transform infrared spectroscopic studies of 1,2-dipalmitoyl-sn-glycero-3-phosphorylcholine and its dialkyl and acyl-alkyl analogs

Lewis

Pohle

McElhaney

1996

Biophysical Journal

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The thermotropic phase behavior of aqueous dispersions of dipalmitoylphosphatidylcholine (DPPC) and its 1,2-dialkyl, 1-acyl 2-alkyl and 1-alkyl 2-acyl analogs was examined by differential scanning calorimetry, and the organization of these molecules in those hydrated bilayers was studied by Fourier transform infrared spectroscopy. The calorimetric data indicate that substitution of either or both of the acyl chains of DPPC with the corresponding ether-linked hydrocarbon chain results in relatively small increases in the temperature (< 4 degrees C) and enthalpy (< 1 kcal/mol) of the lipid chain-melting phase transition. The spectroscopic data reveal that replacement of one or both of the ester-linked hydrocarbon chains of DPPC with its ether-linked analog causes structural changes in the bilayer assembly, which result in an increase in the polarity of the local environments of the phosphate headgroups and of the ester carbonyl groups at the bilayer polar/apolar interface. The latter observation is unexpected, given that ester linkages are considered to be intrinsically more polar that ether linkages. This finding cannot be satisfactorily rationalized unless the conformation of the glycerol backbones of the analogs containing ether-linked hydrocarbon chains differs significantly from that of diacyl glycerolipids such as DPPC. A comparison of the alpha-methylene scissoring bands and the methylene wagging band progressions of these lipids with the corresponding absorption bands of specifically chain-perdeuterated analogs of DPPC also supports the conclusion that replacement of the ester-linked hydrocarbon chains of DPPC with the corresponding ether-linked analog induces conformational changes in the lipid glycerol backbone. The suggestion that the conformation of glycerol backbones in the alkyl-acyl and dialkyl derivatives of DPPC differs from that of the naturally occurring 1,2-diacyl glycerolipid suggests that mono- and di-alkyl glycerolipids may not be good models of their diacyl analogs. These results, and previously published evidence that DPPC analogs with ether-linked hydrocarbon chains spontaneously form chain-interdigitated gel phases at low temperatures, clearly indicate that the properties of lipid bilayers can be substantially altered by small changes in the chemical structures of their polar/polar interfaces, and highlight the critical role of the interfacial region as a determinant of the structure and organization of lipid assemblies.

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The properties of membranes formed from cyclopentanoid analogues of phosphatidylcholine

Cited by 20 publications

References 9 publications

Phospholipids chiral at phosphorus. 12. Configurational effect on the thermotropic properties of chiral dipalmitoylthiophosphatidylcholine

Phospholipids chiral at phosphorus. 12. Configurational effect on the thermotropic properties of chiral dipalmitoylthiophosphatidylcholine

Description of the thermotropic behavior of membrane bilayers in terms of raman spectral parameters - a 2-state model

The interfacial structure of phospholipid bilayers: differential scanning calorimetry and Fourier transform infrared spectroscopic studies of 1,2-dipalmitoyl-sn-glycero-3-phosphorylcholine and its dialkyl and acyl-alkyl analogs

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