Vishnu Sresht

Dominance of Dispersion Interactions and Entropy over Electrostatics in Determining the Wettability and Friction of Two-Dimensional MoS2 Surfaces

The existence of partially ionic bonds in molybdenum disulfide (MoS2), as opposed to covalent bonds in graphene, suggests that polar (electrostatic) interactions should influence the interfacial behavior of two-dimensional MoS2 surfaces. In this work, using molecular dynamics simulations, we show that electrostatic interactions play a negligible role in determining not only the equilibrium contact angle on the MoS2 basal plane, which depends solely on the total interaction energy between the surface and the liquid, but also the friction coefficient and the slip length, which depend on the spatial variations in the interaction energy. While the former is found to result from the exponential decay of the electric potential above the MoS2 surface, the latter results from the trilayered sandwich structure of the MoS2 monolayer, which causes the spatial variations in dispersion interactions in the lateral direction to dominate over those in electrostatic interactions in the lateral direction. Further, we show that the nonpolarity of MoS2 is specific to the two-dimensional basal plane of MoS2 and that other planes (e.g., the zigzag plane) in MoS2 are polar with respect to interactions with water, thereby illustrating the role of edge effects, which could be important in systems involving vacancies or nanopores in MoS2. Finally, we simulate the temperature dependence of the water contact angle on MoS2 to show that the inclusion of entropy, which has been neglected in recent mean-field theories, is essential in determining the wettability of MoS2. Our findings reveal that the basal planes in graphene and MoS2 are unexpectedly similar in terms of their interfacial behavior.

2D equation-of-state model for corona phase molecular recognition on single-walled carbon nanotube and graphene surfaces.

Corona phase molecular recognition (CoPhMoRe) has been recently introduced as a means of generating synthetic molecular recognition sites on nanoparticle surfaces. A synthetic heteropolymer is adsorbed and confined to the surface of a nanoparticle, forming a corona phase capable of highly selective molecular recognition due to the conformational imposition of the particle surface on the polymer. In this work, we develop a computationally predictive model for analytes adsorbing onto one type of polymer corona phase composed of hydrophobic anchors on hydrophilic loops around a single-walled carbon nanotube (SWCNT) surface using a 2D equation of state that takes into consideration the analyte-polymer, analyte-nanoparticle, and polymer-nanoparticle interactions using parameters determined independently from molecular simulation. The SWCNT curvature is found to contribute weakly to the overall interaction energy, exhibiting no correlation for three of the corona phases considered, and differences of less than 5% and 20% over a larger curvature range for two other corona phases, respectively. Overall, the resulting model for this anchor-loop CoPhMoRe is able to correctly predict 83% of an experimental 374 analyte-polymer library, generating experimental fluorescence responses within 20% error of the experimental values. The modeling framework presented here represents an important step forward in the design of suitable polymers to target specific analytes.

Understanding Miltefosine-Membrane Interactions Using Molecular Dynamics Simulations.

Coarse-grained molecular dynamics simulations are used to calculate the free energies of transfer of miltefosine, an alkylphosphocholine anticancer agent, from water to lipid bilayers to study its mechanism of interaction with biological membranes. We consider bilayers containing lipids with different degrees of unsaturation: dipalmitoylphosphatidylcholine (DPPC, saturated, containing 0%, 10%, and 30% cholesterol), dioleoylphosphatidylcholine (DOPC, diunsaturated), palmitoyloleoylphosphatidylcholine (POPC, monounsaturated), diarachidonoylphosphatidylcholine (DAPC, polyunsaturated), and dilinoleylphosphatidylcholine (DUPC, polyunsaturated). These free energies, calculated using umbrella sampling, were used to compute the partition coefficients (K) of miltefosine between water and the lipid bilayers. The K values for the bilayers relative to that of pure DPPC were found to be 5.3 (DOPC), 7.0 (POPC), 1.0 (DAPC), 2.2 (DUPC), 14.9 (10% cholesterol), and 76.2 (30% cholesterol). Additionally, we calculated the free energy of formation of miltefosine-cholesterol complexes by pulling the surfactant laterally in the DPPC + 30% cholesterol system. The free energy profile that we obtained provides further evidence that miltefosine tends to associate with cholesterol and has a propensity to partition into lipid rafts. We also quantified the kinetics of the transport of miltefosine through the various bilayers by computing permeance values. The highest permeance was observed in DUPC bilayers (2.28 × 10(-2) m/s) and the lowest permeance in the DPPC bilayer with 30% cholesterol (1.10 × 10(-7) m/s). Our simulation results show that miltefosine does indeed interact with lipid rafts, has a higher permeability in polyunsaturated, loosely organized bilayers, and has higher flip-flop rates in specific regions of cellular membranes.

Understanding the colloidal dispersion stability of 1D and 2D materials: Perspectives from molecular simulations and theoretical modeling

The colloidal dispersion stability of 1D and 2D materials in the liquid phase is critical for scalable nano-manufacturing, chemical modification, composites production, and deployment as conductive inks or nanofluids. Here, we review recent computational and theoretical studies carried out by our group to model the dispersion stability of 1D and 2D materials, including single-walled carbon nanotubes, graphene, and graphene oxide in aqueous surfactant solutions or organic solvents. All-atomistic (AA) molecular dynamics (MD) simulations can probe the molecular level details of the adsorption morphology of surfactants and solvents around these materials, as well as quantify the interaction energy between the nanomaterials mediated by surfactants or solvents. Utilizing concepts from reaction kinetics and diffusion, one can directly predict the rate constants for the aggregation kinetics and dispersion life times using MD outputs. Furthermore, the use of coarse-grained (CG) MD simulations allows quantitative prediction of surfactant adsorption isotherms. Combined with the Poisson-Boltzmann equation, the Langmuir isotherm, and the DLVO theory, one can directly use CGMD outputs to: (i) predict electrostatic potentials around the nanomaterial, (ii) correlate surfactant surface coverages with surfactant concentrations in the bulk dispersion medium, and (iii) determine energy barriers against coagulation. Finally, we discuss challenges associated with studying emerging 2D materials, such as, hexagonal boron nitride (h-BN), phosphorene, and transition metal dichalcogenides (TMDCs), including molybdenum disulfide (MoS2). An outlook is provided to address these challenges with plans to develop force-field parameters for MD simulations to enable predictive modeling of emerging 2D materials in the liquid phase.

Combined Molecular Dynamics Simulation-Molecular Thermodynamic Theory Framework for Predicting Surface Tensions

A molecular modeling approach is presented with a focus on quantitative predictions of the surface tension of aqueous surfactant solutions. The approach combines classical Molecular Dynamics (MD) simulations with a molecular-thermodynamic theory (MTT) [ Y. J. Nikas, S. Puvvada, D. Blankschtein, Langmuir 1992 , 8 , 2680 ]. The MD component is used to calculate thermodynamic and molecular parameters that are needed in the MTT model to determine the surface tension isotherm. The MD/MTT approach provides the important link between the surfactant bulk concentration, the experimental control parameter, and the surfactant surface concentration, the MD control parameter. We demonstrate the capability of the MD/MTT modeling approach on nonionic alkyl polyethylene glycol surfactants at the air-water interface and observe reasonable agreement of the predicted surface tensions and the experimental surface tension data over a wide range of surfactant concentrations below the critical micelle concentration. Our modeling approach can be extended to ionic surfactants and their mixtures with both ionic and nonionic surfactants at liquid-liquid interfaces.

Predicting Surface Tensions of Surfactant Solutions from Statistical Mechanics

The importance of surfactants to various industries necessitates a predictive understanding of their surface tension and adsorption behavior in terms of molecular characteristics. Previous models are highly empirical, require fitting parameters, and have limited applicability at various temperatures. Here, we provide a surface tension model based on statistical mechanics that (1) is thermodynamically consistent, (2) provides a higher predictive power, wherein surface tension can be calculated for any tail length, concentration, and temperature from molecular parameters, and (3) provides a physical understanding of the important molecular interactions at play. This model is applicable to both nonionic and ionic surfactants, where the effects of the electric double layer have been taken into account in the latter case. For nonionic surfactants, we were able to extend our model to predict dynamic surface tension as well. We have validated our model with tensiometry experiments for various surfactants, concentrations, and temperatures. In addition, we have validated our model with a diverse set of literature data, wherein agreement within a few mN M-1 and a correct prediction of phase change behavior is shown. The model could enable a more informed design of surfactant systems and serve as the theoretical basis for theory on more complex surfactant systems such as mixtures.

CO2 -Reactive Ionic Liquid Surfactants for the Control of Colloidal Morphology

This article reports on a new class of stimuli-responsive surfactant generated from commercially available amphiphiles such as dodecyltrimethylammmonium bromide (DTAB) by substitution of the halide counterion with counterions such as 2-cyanopyrrolide, 1,2,3-triazolide, and L-proline that complex reversibly with CO2. Through a combination of small-angle neutron scattering (SANS), electrical conductivity measurements, thermal gravimetric analysis, and molecular dynamics simulations, we show how small changes in charge reorganization and counterion shape and size induced by complexation with CO2 allow for fine-tunability of surfactant properties. We then use these findings to demonstrate a range of potential practical uses, from manipulating microemulsion droplet morphology to controlling micellar and vesicular aggregation. In particular, we focus on the binding of these surfactants to DNA and the reversible compaction of surfactant-DNA complexes upon alternate bubbling of the solution with CO2 and N2.

Understanding Miltefosine-Membrane Interactions using Molecular Dynamics Simulations

Miltefosine is an anticancer alkylphospholipid whose primary target is the plasma membrane (PM); however, the precise mechanism of interaction has not been elucidated. Some data suggest that Miltefosine disrupts rafts and alters nonvesicular transport of cholesterol from the PM to the endoplasmatic reticulum, leading to cell apoptosis. Other experiments show that in the pharmacologically relevant concentration range, Miltefosine does not affect the biophysical properties of lipid rafts or PM. In this work, we have used coarse-grained molecular dynamics simulations to calculate the free energy change (ΔG) of transferral of Miltefosine from water to the interior of different bilayers: DPPC (containing 0%, 10% and 30% cholesterol), DOPC, POPC, DAPC and DUPC. ΔG values calculated through umbrella sampling simulations were used to compute the partition coefficient (K) of Miltefosine between the bilayer interiors and water. Compared to the pure DPPC bilayer, the relative K values were: 5.4 (DOPC), 2.30 (POPC), 1.06 (DAPC), 2.27 (DUPC), 14.30 (10% cholesterol), and 75.9 (30% cholesterol). The systems were also simulated with 5mol% and 10mol% of Miltefosine. The formation of micelles and the exchange of monomers between the micelles and bilayers was observed. The simulation results show that Miltefosine has high affinity for cholesterol enriched systems, suggesting a propensity for interactions with rafts. Despite the change in the area/lipid, of all the bilayers considered, only the DAPC bilayer developed major defects. Our results indicate that in most biological contexts, the mechanism of action probably has less to do with PM disruption than with alterations in lipid transport and in the function of membrane proteins. PM disruption may play a larger role in membranes rich in poly-unsaturated lipids, like those found in some hematological cancers.