Ordering Transitions of Liquid Crystals Triggered by Metal Oxide-catalyzed Reactions of Sulfur Oxide Species.

Liquid crystals (LCs), when supported on reactive surfaces, undergo changes in ordering that can propagate over distances of micrometers, thus providing a general and facile mechanism to amplify atomic-scale transformations on surfaces into the optical scale. While reactions on organic and metal substrates have been coupled to LC-ordering transitions, metal oxide substrates, which offer unique catalytic activities for reactions involving atmospherically important chemical species such as oxidized sulfur species, have not been explored. Here, we investigate this opportunity by designing LCs that contain 4'-cyanobiphenyl-4-carboxylic acid (CBCA) and respond to surface reactions triggered by parts-per-billion concentrations of SO2 gas on anatase (101) substrates. We used electronic structure calculations to predict that the carboxylic acid group of CBCA binds strongly to anatase (101) in a perpendicular orientation, a prediction that we validated in experiments in which CBCA (0.005 mol %) was doped into an LC (4'-n-pentyl-4-biphenylcarbonitrile). Both experiment and computational modeling further demonstrated that SO3-like species, produced by a surface-catalyzed reaction of SO2 with H2O on anatase (101), displace CBCA from the anatase surface, resulting in an orientational transition of the LC. Experiments also reveal the LC response to be highly selective to SO2 over other atmospheric chemical species (including H2O, NH3, H2S, and NO2), in agreement with our computational predictions for anatase (101) surfaces. Overall, we establish that the catalytic activities of metal oxide surfaces offer the basis of a new class of substrates that trigger LCs to undergo ordering transitions in response to chemical species of relevance to atmospheric chemistry.

Ligand Lipophilicity Determines Molecular Mechanisms of Nanoparticle Adsorption to Lipid Bilayers.

The interactions of ligand-functionalized nanoparticles with the cell membrane affect cellular uptake, cytotoxicity, and related behaviors, but relating these interactions to ligand properties remains challenging. In this work, we perform coarse-grained molecular dynamics simulations to study how the adsorption of ligand-functionalized cationic gold nanoparticles (NPs) to a single-component lipid bilayer (as a model cell membrane) is influenced by ligand end group lipophilicity. A set of 2 nm diameter NPs, each coated with a monolayer of organic ligands that differ only in their end groups, was simulated to mimic NPs recently studied experimentally. Metadynamics calculations were performed to determine key features of the free energy landscape for adsorption as a function of the distance of the NP from the bilayer and the number of NP-lipid contacts. These simulations revealed that NP adsorption is thermodynamically favorable for all NPs due to the extraction of lipids from the bilayer and into the NP monolayer. To resolve ligand-dependent differences in adsorption behavior, string method calculations were performed to compute minimum free energy pathways for adsorption. These calculations revealed a surprising nonmonotonic dependence of the free energy barrier for adsorption on ligand end group lipophilicity. Large free energy barriers are predicted for the least lipophilic end groups because favorable NP-lipid contacts are initiated only through the unfavorable protrusion of lipid tail groups out of the bilayer. The smallest free energy barriers are predicted for end groups of intermediate lipophilicity which promote NP-lipid contacts by intercalating within the bilayer. Unexpectedly, large free energy barriers are also predicted for the most lipophilic end groups which remain sequestered within the ligand monolayer rather than intercalating within the bilayer. These trends are broadly in agreement with past experimental measurements and reveal how subtle variations in ligand lipophilicity dictate adsorption mechanisms and associated kinetics by influencing the interplay of lipid-ligand interactions.

Elucidating Molecular-Scale Principles Governing the Anchoring of Liquid Crystal Mixtures on Solid Surfaces.

Computational chemistry calculations are broadly useful for guiding the atom-scale design of hard-soft material interfaces including how molecular interactions of single-component liquid crystals (LCs) at inorganic surfaces lead to preferred orientations of the LC far from the surface. The majority of LCs, however, are not single-component phases but comprise of mixtures, such as a mixture of mesogens, added to provide additional functions such as responsiveness to the presence of targeted organic compounds (for chemical sensing). In such LC mixtures, little is understood about the near-surface composition and organization of molecules and how that organization propagates into the far-field LC orientation. Here, we address this broad question by using a multiscale computational approach that combines density functional theory (DFT)-based calculations and classical molecular dynamics (MD) simulations to predict the interfacial composition and organization of a binary LC mixture of 4'-cyano-4-biphenylcarbolxylic acid (CBCA) and 4'-n-pentyl-4-biphenylcarbonitrile (5CB) supported on anatase (101) titania surfaces. DFT calculations determine the surface composition and atomic-scale organization of CBCA and 5CB at the titania surface, and classical MD simulations build upon the DFT description to describe the evolution of the near-surface order into the bulk LC. A surprising finding is that the 5CB and CBCA molecules adopt orthogonal orientations at the anatase surface and that, above a threshold concentration of CBCA, this mixture of orientations evolves away from the surface to define a uniform far-field homeotropic orientation. These results demonstrate that molecular-level knowledge achieved through a combination of computational techniques permits the design and understanding of functional LC mixtures at interfaces.

Curvature-driven adsorption of cationic nanoparticles to phase boundaries in multicomponent lipid bilayers.

Understanding the interactions between surface-functionalized gold nanoparticles (NPs) and lipid bilayers is necessary to guide the design of NPs for biomedical applications. Recent experiments found that cationic NPs adsorb more strongly to phase-separated multicomponent lipid bilayers than single-component liquid-disordered bilayers, suggesting that phase separation affects NP-bilayer interactions. In this work, we use coarse-grained molecular dynamics simulations to investigate the effect of lipid phase behavior on the adsorption of small cationic NPs. We first determined the free energy change for adsorbing a NP to one-phase liquid-disordered and one-phase liquid-ordered bilayers. The simulations indicate that NP adsorption depends on a competition between favorable NP-lipid interactions and the unfavorable curvature deformation of the bilayer, resulting in stronger interactions with the liquid-disordered bilayer due to its lower bending modulus. We then measured the free energy change associated with moving a NP across the surface of a phase-separated bilayer and identified a free energy minimum at the phase boundary. The free energy minimum is attributed to the thickness gradient between the two phases that enables favorable NP-lipid interactions without necessitating large curvature deformations. The simulation results thus indicate that the intrinsic curvature present at phase boundaries drives preferential interactions with surface-adsorbed NPs, providing new insight into the forces that drive NP behavior at multicomponent, phase-separated lipid bilayers.