Dry martini

Abstract: In this work we study the behaviour at interfaces and the micelle self-assembly of a cationic surfactant (CTAB) by Molecular Dynamics (MD) simulations of coarse-grained models. We consider both the standard (with explicit water) Martini force field and the implicit solvent version of the Martini force field (Dry Martini). First, we study the behaviour of CTAB at a water/vacuum interface, at a water/organic solvent interface and in a pre-assembled CTAB micelle using both standard and Dry Martini and all-atomic simulations. Our results indicate that there are significant quantitative differences between the predictions of the two models. Interestingly, implicit solvent simulations with Dry Martini show good quantitative agreement with all-atomic MD simulations, better than explicit solvent Martini MD simulations. The computational efficiency of the Martini and Dry Martini models allowed us to study the self-assembly of CTAB in a large system with many micelles. We observe the self-assembly of CTAB into micelles and also the exchange of CTAB molecules between micelles by events such as micelle fusion and fission which are difficult to observe in all-atomic MD simulations due to the time and length scales involved. Under the studied conditions, both Martini models predict a rather different self-assembly behaviour. The standard Martini model predicts a final equilibrium state with spherical micelles with an average size of ≈70 CTAB molecules. In contrast, the Dry Martini model predicts the formation of large tubular micelles with ≈330 CTAB molecules. Compared with experiments, standard Martini and Dry Martini underestimate and overestimate, respectively, the micelle size.

Abstract: Surfactants are amphiphilic molecules with multiple uses and industrial applications as detergents, wetting agents, emulsifiers, and so forth. They can be divided into three main categories: nonionic, ionic, and zwitterionic. The development of a universal computational framework able to predict key properties such as their critical micelle concentration (cmc) and the size of the micelles they form and to ultimately extract phase diagrams for their aqueous solutions, possibly in the presence of salts and oils, using their chemical constitution as input, would provide valuable information for the design and the production of these materials. In this work, we focus on ionic surfactants and investigate a possible route toward the development of such a framework based on coarse-grained simulations using the MARTINI forcefield in two versions: its implicit solvent version, called Dry MARTINI, and its explicit solvent version, called Wet MARTINI. The surfactants considered in our efforts are the anionic sodium dodecyl sulfate (SDS) and the three cationic cetyl, dodecyl, and octyl trimethyl ammonium bromide (CTAB, DTAB, and OTAB, respectively). First, we choose their mapping onto coarse-grained MARTINI beads. Next, we estimate their cmc’s, their peak aggregation numbers, Nₐgg, and in the case of SDS, its small angle neutron scattering pattern at low concentrations, applying the Dry MARTINI forcefield. With a single modification to the Lennard-Jones energy parameter between hydrophobic beads and invoking Ewald summation with a physically meaningful dielectric constant for electrostatic interactions, our estimates are in very good agreement with experimental results. Furthermore, we predict the phase behavior of SDS/water and CTAB/water binary solutions using Wet MARTINI and find semiquantitative agreement with experimental phase diagrams. We conclude that the MARTINI forcefield, with careful treatment of electrostatic interactions and appropriate modification of parameters for some key functional groups, can be a powerful ally in the quest for a universal computational framework for the design of new surfactants with improved properties.

Abstract: The popular MARTINI coarse-grained model is used as a test case to analyze the adherence of top-down coarse-grained molecular dynamics models (ie, models primarily parameterized to match experimental results) to the known features of statistical mechanics for the underlying all-atom representations Specifically, the temperature dependence of various pair distribution functions, and hence their underlying potentials of mean force via the reversible work theorem, are compared between MARTINI 20, Dry MARTINI, and all-atom simulations mapped onto equivalent coarse-grained sites for certain lipid bilayers It is found that the MARTINI models do not completely capture the lipid structure seen in atomistic simulations as projected onto the coarse-grained mappings and that issues of accuracy and temperature transferability arise due to an incorrect enthalpy & entropy decomposition of these potentials of mean force The potential of mean force for the association of two amphipathic helices in a lipid bilayer is also calculated and, especially at shorter ranges, the MARTINI and all-atom projection results differ substantially The former is much less repulsive and hence will lead to a higher probability of MARTINI helix association in the MARTINI bilayer than occurs in the actual all-atom case Additionally, the bilayer height fluctuation spectra are calculated for the MARTINI model and-compared to the all-atom results-it is found that the magnitude of thermally averaged amplitudes at intermediate length scales is quite different, pointing to a number of possible consequences for realistic modeling of membrane processes Taken as a whole, the results presented here can point the way for future coarse-grained model parameterization efforts that might bring top-down coarse-grained models into better agreement with the statistical mechanics of the actual all-atom systems they aspire to represent