PubMed · 8092464
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D Dollimore. 1994-06-15. Thermal analysis.. https://doi.org/10.1021/ac00084a002
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Effects of cholesterol on the lamellar and the inverted hexagonal (HII ) phases of dielaidoylphosphatidylethanolamine (DEPE) were studied by means of not only differential scanning calorimetry (DSC) but also simultaneous X-ray diffraction and DSC (XDDSC). XDDSC shows that structural changes are related to thermotropic events of the mixtures. Addition of cholesterol to DEPE induces to broaden the transition from the lamellar gel (L beta) to lamellar liquid-crystalline (L alpha) phase. In fact, in the broad transition region, a coexistence of two lamellar X-ray diffraction peaks of the L beta and L alpha phases take place. In samples containing above 30 mol% cholesterol, no peak at the L beta-L alpha phase transition was observed in the DSC thermogram. On the other hand, cholesterol causes biphasic effects on the L alpha-HII phase transition: At low cholesterol concentrations below 20 mol%, the incorporation of cholesterol reduces the transition temperature and at high cholesterol concentrations about 30 mol%, the transition temperature increases by addition of cholesterol. Based upon the results of X-ray diffraction, the thermal expansion coefficients of lattice spacings, i.e., the temperature dependence of lattice spacings, were calculated in each phase. Addition of cholesterol reduces the thermal expansion coefficients of the lamellar phases and, in contrast, increases that of the HII phase. From the above results it is suggested that cholesterol in cell membranes works in keeping the bilayer membrane nature notwithstanding the change of external conditions.
In this study we have examined the effects of analogues of cholesterol differing with respect to alkyl side-chain length and structure on the thermotropic phase behavior of bilayers formed from 1-stearoyl-2-oleoyl-sn-glycero-3-phosphocholine (SOPC), an important subclass of naturally occurring phosphatidylcholines (PCs). The synthetic sterols we studied contained either a terminally unbranched (n-series) or a single methyl-branched (iso-series) side chain of 3 to 10 carbon atoms. The phase transition behavior was examined by high-sensitivity differential scanning calorimetry (DSC). The main phase transition endotherm of SOPC/sterol bilayers consists of superimposed sharp and broad components, which represent the hydrocarbon chain melting of sterol-poor and sterol-rich phospholipid domains, respectively. The transition temperature and the cooperativity of the sharp component are moderately reduced upon sterol incorporation and the enthalpy decreases to zero when sterol levels of 20-30 mol% are reached. The enthalpy of the broad component transition initially increases to a maximum around 25 or 25-30 mol% sterol and thereafter decreases with further increases in sterol concentration. However, the broad transition of SOPC bilayers containing both short (C-22, i-C5 and n-C3) and long (i-C9 and i-C10) side-chain sterols still persists at levels of 50 mol% sterol. Thus the effective stoichiometry of SOPC-sterol interactions varies with changes in sterol alkyl side-chain length. The incorporation of short linear or branched side-chain sterols (C-22, n-C3, n-C4, i-C5) causes the broad component transition temperature and cooperativity to decrease dramatically, whereas the incorporation of medium- and long-chain sterols in both the n- and iso-series has less effect on the transition temperature and cooperativity of the broad component. Overall, no significant differences were found between the n- and iso-series sterols for a given side-chain length. A comparison of the phase behavior of dipalmitoylphosphatidylcholine (DPPC)/sterol (McMullen et al. (1995) Biophys. J. 69, 169-176) and SOPC/sterol mixtures indicates that the primary factor responsible for changes in the thermotropic phase behavior of these systems is the extent of the hydrophobic mismatch between the sterol and the host lipid bilayer. However, sterol miscibility in PC bilayers, and thus the stoichiometry of lipid-sterol interactions, also appears to depend on the degree of unsaturation of the host lipid bilayer.
The partitioning of cholesterol between gel and fluid phases of model membrane bilayers has been studied by differential scanning calorimetry. The partition coefficients and thermodynamics of transfer between phases of dimyristoyl-, dipalmitoyl-, distearoyl- and diarachidoylphosphatidylcholines were determined using a regular solution model for the partitioning process. The partition coefficient, which is the ratio of cholesterol in fluid to gel phase lipid, varies from 2.3 to 8.4 as the acyl chain length increases from the C14 to the C20 bilayer and determined at the phase transition temperature. The enthalpies of transfer increase from -46 to +32 kcal/mol as the chain length increases, and there is a compensating increase in the entropy of transfer. The results are interpreted in terms of a disruption of gel phase lipid by the cholesterol, which for the thinner bilayers is increased because the cholesterol molecule spans across the two leafs of the bilayer. At bilayer thicknesses between 18 and 19 carbons, the cholesterol can fit into one-half of the gel phase bilayer, and the enthalpy becomes positive, suggesting less disruption in the gel phase relative to the thinner bilayers. The data support the interpretation that cholesterol does mediate fluidity by acting to disrupt gel domains of lipid.