ABSTRACT
We present a dissipative particle dynamics (DPD) model capable of capturing the liquid state phase behavior of nonionic surfactants from the alkyl ethoxylate (CnEm) family. The model is based upon our recent work [Anderson et al. J. Chem. Phys. 2017, 147, 094503] but adopts tighter control of the molecular structure by setting the bond angles with guidance from molecular dynamics simulations. Changes to the geometry of the surfactants were shown to have little effect on the predicted micelle properties of sampled surfactants, or the water-octanol partition coefficients of small molecules, when compared to the original work. With these modifications the model is capable of reproducing the binary water-surfactant phase behavior of nine surfactants (C8E4, C8E5, C8E6, C10E4, C10E6, C10E8, C12E6, C12E8, and C12E12) with a good degree of accuracy.
ABSTRACT
Dissipative particle dynamics (DPD) simulations of nonionic surfactants with an added salt show that the Setschenow relationship is reproduced; that is, the critical micelle concentration is log-linearly dependent on the added salt concentration. The simulated Setschenow coefficients depend on the DPD bead-bead repulsion amplitudes, and matching to the experimentally determined values provides a systematic method to parameterize the interactions between salt ion beads and surfactant beads. The optimized ion-specific interaction parameters appear to be transferrable and follow the same trends as the empirical Hofmeister series.
Subject(s)
Pulmonary Surfactants , Surface-Active Agents , Excipients , MicellesABSTRACT
Dissipative particle dynamics (DPD) can be used to simulate the self-assembly properties of surfactants in aqueous solutions, but in order to simulate a new compound, a large number of new parameters are required. New methods for the calculation of reliable DPD parameters directly from chemical structure are described, allowing the DPD approach to be applied to a much wider range of organic compounds. The parameters required to describe the bonded interactions between DPD beads were calculated from molecular mechanics structures. The parameters required to describe the nonbonded interactions were calculated from surface site interaction point (SSIP) descriptions of molecular fragments that represent individual beads. The SSIPs were obtained from molecular electrostatic potential surfaces calculated using density functional theory and used in the SSIMPLE algorithm to calculate transfer free energies between different bead liquids. This approach was used to calculate DPD parameters for a range of different types of surfactants, which include ester, amide, and sugar moieties. The parameters were used to simulate the self-assembly properties in aqueous solutions, and comparison of the results for 27 surfactants with the available experimental data shows that these DPD simulations accurately predict critical micelle concentrations, aggregation numbers, and the shapes of the supramolecular assemblies formed. The methods described here provide a general approach to determining DPD parameters for neutral organic compounds of arbitrary structure.
ABSTRACT
Dissipative particle dynamics (DPD) is a coarse-grained approach to the simulation of large supramolecular systems, but one limitation has been that the parameters required to describe the noncovalent interactions between beads are not readily accessible. A first-principles computational method has been developed so that bead interaction parameters can be calculated directly from ab initio gas-phase molecular electrostatic potential surfaces of the molecular fragments that represent the beads. A footprinting algorithm converts the molecular electrostatic potential surfaces into a discrete set of surface site interaction points (SSIPs), and these SSIPs are used in the SSIMPLE (surface site interaction model for the properties of liquids at equilibrium) algorithm to calculate the free energies of transfer of one bead into a solution of any other bead. The bead transfer free energies are then converted into the required DPD interaction parameters for all pairwise combinations of different beads. The reliability of the parameters was demonstrated using DPD simulations of a range of alkyl ethoxylate surfactants. The simulations reproduce the experimentally determined values of the critical micelle concentration and mean aggregation number well for all 22 surfactants studied.
Subject(s)
Micelles , Surface-Active Agents , Entropy , Reproducibility of Results , Static ElectricityABSTRACT
UV/Vis absorption and NMR spectroscopy titrations have been used to investigate the formation of complexes between cations and neutral H-bond acceptors in organic solvents. Complexes formed by two different H-bond acceptors with fifteen different cations were studied in acetone and in acetonitrile. The effects of water and ion pairing with the counter-anion were found to be negligible in the two polar solvents employed for this study. The data were used to determine self-consistent H-bond donor parameters (α) for a series of organic and inorganic cations; guanidinium, primary, tertiary and quaternary ammonium, imidazolium, methylpyridinium, lithium, sodium, potassium, rubidium and caesium. The results demonstrate the transferability of α parameters for cations between different solvents and different H-bond acceptor partners, allowing reliable prediction of cation recognition properties in different environments. Lithium and protonated nitrogen cations form the most stable complexes, but the α parameter is only 5.0, which is similar to the neutral H-bond donor 3-trifluoromethyl,4-nitrophenol (α = 5.1). Quaternary ammonium is the weakest H-bond donor investigated with an α value of 2.7, which is comparable to an alcohol. The α parameters for alkali metal cations decrease down the group from 5.0 (Li+) to 3.5 (Cs+).
