title: Implicit solvent simulations of DPC micelle formation.
abstract: The formation of micelles by dodecylphosphocholine (DPC) is modeled by treating the surfactants in atomic detail and the solvent implicitly, in the spirit of the EEF1 solvation model for proteins. The solvation parameters of the DPC atoms are carried over from those of similar atoms in proteins. A slight adjustment of the parameters for the headgroup was found necessary for obtaining an aggregation number consistent with experiment. Molecular dynamics simulations of 960 DPC molecules at different concentrations are used to obtain the aggregation number, the micelle size distribution, and the CMC. At 20 mM concentration we obtain an aggregation number of 53-56 and a CMC of 1.25 mM, values close to the experimental ones. At 100 mM the aggregation number increases to 90. Simulations of individual micelles of varying size show that the effective energy per surfactant molecule is initially a decreasing function of aggregation number but stabilizes at about 60 molecules. The van der Waals term and the desolvation of nonpolar groups contribute to micellization, whereas the desolvation of polar groups opposes it. From the difference between the effective energy and the free energy (calculated from the CMC), the translational and rotational entropy contributions to the free energy are estimated at about 7 kcal/mol per monomer. The micelles obtained here are more irregular than those obtained in explicit water simulations. This modeling approach allows the study of larger surfactant aggregates for longer times and the extraction of thermodynamic in addition to structural information.
authors.affiliation: Department of Chemistry, City College of New York/CUNY, 138th Street and Convent Avenue, New York, New York 10031, USA. tlazaridis@ccny.cuny.edu
authors.forename: Themis
authors.initials: T
authors.lastname: Lazaridis
authors.forename: Buddhadeb
authors.initials: B
authors.lastname: Mallik
authors.forename: Yong
authors.initials: Y
authors.lastname: Chen
mesh_terms: D003198:Computer Simulation; D003902:Detergents; D008823:Micelles; D008958:Models, Molecular; D008968:Molecular Conformation; D010767:Phosphorylcholine / Q000031:analogs & derivatives* / Q000737:chemistry; D012997:Solvents / Q000737:chemistry*; D055672:Static Electricity; D013816:Thermodynamics
chemical_list: D003902:Detergents; D008823:Micelles; D012997:Solvents; D010767:Phosphorylcholine; C028810:dodecylphosphocholine