title: New approaches to the simulation of heat-capacity curves and phase diagrams of pseudobinary phospholipid mixtures.
abstract: A simulation program using least-squares minimization was developed to calculate and fit heat capacity (cp) curves to experimental thermograms of dilute aqueous dispersions of phospholipid mixtures determined by high-sensitivity differential scanning calorimetry. We analyzed cp curves and phase diagrams of the pseudobinary aqueous lipid systems 1,2-dimyristoyl-sn-glycero-3-phosphatidylglycerol/ 1,2-dipalmitoyl-sn-glycero-3phosphatidylcholine (DMPG/DPPC) and 1,2-dimyristoyl-sn-glycero-3-phosphatidic acid/1, 2-dipalmitoyl-sn-glycero-3-phosphatidylcholine (DMPA/DPPC) at pH 7. The simulation of the cp curves is based on regular solution theory using two nonideality parameters rho g and rho l for symmetric nonideal mixing in the gel and the liquid-crystalline phases. The broadening of the cp curves owing to limited cooperativity is incorporated into the simulation by convolution of the cp curves calculated for infinite cooperativity with a broadening function derived from a simple two-state transition model with the cooperative unit size n = delta HVH/delta Hcal as an adjustable parameter. The nonideality parameters and the cooperative unit size turn out to be functions of composition. In a second step, phase diagrams were calculated and fitted to the experimental data by use of regular solution theory with four different model assumptions. The best fits were obtained with a four-parameter model based on nonsymmetric, nonideal mixing in both phases. The simulations of the phase diagrams show that the absolute values of the nonideality parameters can be changed in a certain range without large effects on the shape of the phase diagram as long as the difference of the nonideality parameters for rho g for the gel and rho l for the liquid-crystalline phase remains constant. The miscibility in DMPG/DPPC and DMPA/DPPC mixtures differs remarkably because, for DMPG/DPPC, delta rho = rho l -rho g is negative, whereas for DMPA/DPPC this difference is positive. For DMPA/DPPC, this difference is interpreted as being caused by a negative rho g value, indicating complex formation of unlike molecules in the gel phase.
authors.affiliation: Fachbereich Chemie, Universität Kaiserslautern, Germany.
authors.forename: C
authors.initials: C
authors.lastname: Johann
authors.forename: P
authors.initials: P
authors.lastname: Garidel
authors.forename: L
authors.initials: L
authors.lastname: Mennicke
authors.forename: A
authors.initials: A
authors.lastname: Blume
mesh_terms: D015060:1,2-Dipalmitoylphosphatidylcholine; D000814:Aniline Compounds; D002152:Calorimetry, Differential Scanning; D003198:Computer Simulation; D006863:Hydrogen-Ion Concentration; D016018:Least-Squares Analysis; D008962:Models, Theoretical; D010715:Phosphatidylglycerols; D012680:Sensitivity and Specificity; D012997:Solvents; D013816:Thermodynamics; D014867:Water
chemical_list: D000814:Aniline Compounds; D010715:Phosphatidylglycerols; D012997:Solvents; D014867:Water; D015060:1,2-Dipalmitoylphosphatidylcholine; C050795:N,N-dimethyl-4-anisidine; C002773:dimyristoylphosphatidylglycerol