Size-Pore-Dependent Methanol Sequestration from Water-Methanol Mixtures by an Embedded Graphene Slit.

The separation of liquid mixture components is relevant to many applications-ranging from water purification to biofuel production-and is a growing concern related to the UN Sustainable Development Goals (SDGs), such as "Clean water and Sanitation" and "Affordable and clean energy". One promising technique is using graphene slit-pores as filters, or sponges, because the confinement potentially affects the properties of the mixture components in different ways, favoring their separation. However, no systematic study has shown how the size of a pore changes the thermodynamics of the surrounding mixture. Here, we focus on water-methanol mixtures and explore, using Molecular Dynamics simulations, the effects of a graphene pore, with size ranging from 6.5 to 13 Å, for three compositions: pure water, 90%-10%, and 75%-25% water-methanol. We show that tuning the pore size can change the mixture pressure, density and composition in bulk due to the size-dependent methanol sequestration within the pore. Our results can help in optimizing the graphene pore size for filtering applications.

High energy vibrational excitations of nitromethane in liquid water.

The pathways and timescales of vibrational energy flow in nitromethane are investigated in both gas and condensed phases using classical molecular mechanics, with a particular focus on relaxation in liquid water. We monitor the flow of excess energy deposited in vibrational modes of nitromethane into the surrounding solvent. A marked energy flux anisotropy is found when nitromethane is immersed in liquid water, with a preferential flow to those water molecules in contact to the nitro group. The factors that permit such anisotropic energy relaxation are discussed, along with the potential implications on the molecule's non-equilibrium dynamics. In addition, the energy flux analysis allows us to identify the solvent motions responsible for the uptake of solute energy, confirming the crucial role of water librations. Finally, we also show that no anisotropic vibrational energy relaxation occurs when nitromethane is surrounded by argon gas.

Unveiling the Rolling to Kayak Transition in Propelling Nanorods with Cargo Trapping and Pumping.

Magnetic nanorods driven by rotating fields in water can be rapidly steered along any direction while generating strong and localized hydrodynamic flow fields. Here we show that, when raising the frequency of the rotating field, these nanopropellers undergo a dynamic transition from a rolling to a kayak-like motion due to the increase in viscous drag and acquire a finite inclination angle with respect to the plane perpendicular to the bottom surface. We explain these experimental observations with a theoretical model which considers the nanorod as a pair of ferromagnetic particles hydrodynamically interacting with a close stationary surface. Further, we quantify how efficiently microscopic cargoes can be trapped or expelled from the moving nanorod and use numerical simulations to unveil the generated hydrodynamic flow field. These propulsion regimes can be implemented in microfluidic devices to perform precise operations based on the selective sorting of microscopic cargoes.

Friction Induces Anisotropic Propulsion in Sliding Magnetic Microtriangles.

In viscous fluids, motile microentities such as bacteria or artificial swimmers often display different transport modes than macroscopic ones. A current challenge in the field aims at using friction asymmetry to steer the motion of microscopic particles. Here we show that lithographically shaped magnetic microtriangles undergo a series of complex transport modes when driven by a precessing magnetic field, including a surfing-like drift close to the bottom plane. In this regime, we exploit the triangle asymmetric shape to obtain a transversal drift which is later used to transport the microtriangle in any direction along the plane. We explain this friction-induced anisotropic sliding with a minimal numerical model capable to reproduce the experimental results. Due to the flexibility offered by soft-lithographic sculpturing, our method to guide anisotropic-shaped magnetic microcomposites can be potentially extended to many other field responsive structures operating in fluid media.

Modeling and Simulation of Lipid Membranes.

Cell membranes separate the interior of cells and the exterior environment, providing protection, controlling the passage of substances, and governing the interaction with other biomolecules and signalling processes [...].

A broad perspective to particle-laden fluid interfaces systems: from chemically homogeneous particles to active colloids.

Particles adsorbed to fluid interfaces are ubiquitous in industry, nature or life. The wide range of properties arising from the assembly of particles at fluid interface has stimulated an intense research activity on shed light to the most fundamental physico-chemical aspects of these systems. These include the mechanisms driving the equilibration of the interfacial layers, trapping energy, specific inter-particle interactions and the response of the particle-laden interface to mechanical perturbations and flows. The understanding of the physico-chemistry of particle-laden interfaces becomes essential for taking advantage of the particle capacity to stabilize interfaces for the preparation of different dispersed systems (emulsions, foams or colloidosomes) and the fabrication of new reconfigurable interface-dominated devices. This review presents a detailed overview of the physico-chemical aspects that determine the behavior of particles trapped at fluid interfaces. This has been combined with some examples of real and potential applications of these systems in technological and industrial fields. It is expected that this information can provide a general perspective of the topic that can be exploited for researchers and technologist non-specialized in the study of particle-laden interfaces, or for experienced researcher seeking new questions to solve.

Nanoconfined Fluids: Uniqueness of Water Compared to Other Liquids.

Nanoconfinement can drastically change the behavior of liquids, puzzling us with counterintuitive properties. It is relevant in applications, including decontamination and crystallization control. However, it still lacks a systematic analysis for fluids with different bulk properties. Here we address this gap. We compare, by molecular dynamics simulations, three different liquids in a graphene slit pore: (1) A simple fluid, such as argon, described by a Lennard-Jones potential; (2) an anomalous fluid, such as a liquid metal, modeled with an isotropic core-softened potential; and (3) water, the prototypical anomalous liquid, with directional HBs. We study how the slit-pore width affects the structure, thermodynamics, and dynamics of the fluids. All the fluids show similar oscillating properties by changing the pore size. However, their free-energy minima are quite different in nature: (i) are energy-driven for the simple liquid; (ii) are entropy-driven for the isotropic core-softened potential; and (iii) have a changing nature for water. Indeed, for water, the monolayer minimum is entropy driven, at variance with the simple liquid, while the bilayer minimum is energy driven, at variance with the other anomalous liquid. Also, water has a large increase in diffusion for subnm slit pores, becoming faster than bulk. Instead, the other two fluids have diffusion oscillations much smaller than water, slowing down for decreasing slit-pore width. Our results, clarifying that water confined at the subnm scale behaves differently from other (simple or anomalous) fluids under similar confinement, are possibly relevant in nanopores applications, for example, in water purification from contaminants.

Structure and dynamics of nanoconfined water and aqueous solutions.

This review is devoted to discussing recent progress on the structure, thermodynamic, reactivity, and dynamics of water and aqueous systems confined within different types of nanopores, synthetic and biological. Currently, this is a branch of water science that has attracted enormous attention of researchers from different fields interested to extend the understanding of the anomalous properties of bulk water to the nanoscopic domain. From a fundamental perspective, the interactions of water and solutes with a confining surface dramatically modify the liquid's structure and, consequently, both its thermodynamical and dynamical behaviors, breaking the validity of the classical thermodynamic and phenomenological description of the transport properties of aqueous systems. Additionally, man-made nanopores and porous materials have emerged as promising solutions to challenging problems such as water purification, biosensing, nanofluidic logic and gating, and energy storage and conversion, while aquaporin, ion channels, and nuclear pore complex nanopores regulate many biological functions such as the conduction of water, the generation of action potentials, and the storage of genetic material. In this work, the more recent experimental and molecular simulations advances in this exciting and rapidly evolving field will be reported and critically discussed.

Static and Dynamic Self-Assembly of Pearl-Like-Chains of Magnetic Colloids Confined at Fluid Interfaces.

Magnetic colloids adsorbed at a fluid interface are unique model systems to understand self-assembly in confined environments, both in equilibrium and out of equilibrium, with important potential applications. In this work the pearl-chain-like self-assembled structures of superparamagnetic colloids confined to a fluid-fluid interface under static and time-dependent actuations are investigated. On the one hand, it is found that the structures generated by static fields transform as the tilt angle of the field with the interface is increased, from 2D crystals to separated pearl-chains in a process that occurs through a controllable and reversible zip-like thermally activated mechanism. On the other hand, the actuation with precessing fields about the axis perpendicular to the interface induces dynamic self-assembled structures with no counterpart in non-confined systems, generated by the interplay of averaged magnetic interactions, interfacial forces, and hydrodynamics. Finally, how these dynamic structures can be used as remotely activated roller conveyors, able to transport passive colloidal cargos at fluid interfaces and generate parallel viscous flows is shown. The latter can be used in the mixture of adsorbed molecules and the acceleration of surface-chemical reactions, overcoming diffusion limitations.

Redefining the concept of hydration water near soft interfaces.

Water determines the properties of biological systems. Therefore, understanding the nature of the mutual interaction between water and biosystems is of primary importance for a proper assessment of any biological activity, e.g., the efficacy of new drugs or vaccines. A convenient way to characterize the interactions between biosystems and water is to analyze their impact on water density and dynamics in the proximity of the interfaces. It is commonly accepted that water bulk density and dynamical properties are recovered at distances of the order of 1 nm away from the surface of biological systems. This notion leads to the definition of hydration or biological water as the nanoscopic layer of water covering the surface of biosystems and to the expectation that all the effects of the water-interface interaction are limited to this thin region. Here, we review some of our latest contributions, showing that phospholipid membranes affect the water dynamics, structural properties, and hydrogen bond network at a distance that is more than twice as large as the commonly evoked ∼1nm thick layer and of the order of 2.4 nm. Furthermore, we unveil that at a shorter distance ∼0.5nm from the membrane, instead, there is an additional interface between lipid-bound and unbound water. Bound water has a structural role in the stability of the membrane. Our results imply that the concept of hydration water should be revised or extended and pave the way to a deeper understanding of the mutual interactions between water and biological systems.

Self-Assembly of Microscopic Rods Due to Depletion Interaction.

In this article, using numerical simulations we investigate the self-assembly of rod-like particles in suspension due to depletion forces which naturally emerge due to the presence of smaller spherical depletant particles. We characterize the type of clusters that are formed and the evolution of aggregation departing from a random initial configuration. We show that eventually the system reaches a thermodynamic equilibrium state in which the aggregates break and reform dynamically. We investigate the equilibrium state of aggregation, which exhibits a strong dependence on depletant concentration. In addition, we provide a simple thermodynamic model inspired on the theory of self-assembly of amphiphilic molecules which allows us to understand qualitatively the equilibrium aggregate size distributions that we obtain in simulation.

Propulsion and energetics of a minimal magnetic microswimmer.

In this manuscript we describe the realization of a minimal hybrid microswimmer, composed of a ferromagnetic nanorod and a paramagnetic microsphere. The unbounded pair is propelled in water upon application of a swinging magnetic field that induces a periodic relative movement of the two composing elements, where the nanorod rotates and slides on the surface of the paramagnetic sphere. When taken together, the processes of rotation and sliding describe a finite area in the parameter space, which increases with the frequency of the applied field. We develop a theoretical approach and combine it with numerical simulations, which allow us to understand the dynamics of the propeller and explain the experimental observations. Furthermore, we demonstrate a reversal of the microswimmer velocity by varying the length of the nanorod, as predicted by the model. Finally, we determine theoretically and in experiments the Lighthill's energetic efficiency of this minimal magnetic microswimmer.

Self-thermophoresis at the nanoscale using light induced solvation dynamics.

Downsizing microswimmers to the nanoscale, and using light as an externally controlled fuel, are two important goals within the field of active matter. Here we demonstrate using all-atom molecular dynamics simulations that solvation relaxation, the solvent dynamics induced after visible light electronic excitation of a fluorophore, can be used to propel nanoparticles immersed in polar solvents. We show that fullerenes functionalized with fluorophore molecules in liquid water exhibit substantial enhanced mobility under external excitation, with a propulsion speed proportional to the power dissipated into the system. We show that the propulsion mechanism is quantitatively consistent with a molecular scale instance of self-thermophoresis. Strategies to direct the motion of functionalized fullerenes in a given direction using confined environments are also discussed.

Controlled disassembly of colloidal aggregates confined at fluid interfaces using magnetic dipolar interactions.

HYPOTHESIS: Field induced assembling/disassembling of paramagnetic colloids is strongly influenced by the configuration of the applied field, the surface chemistry of the particles, the nearby presence of an external boundary or the particle density. The trapping of the particles at fluid-fluid interface is expected to promote different assembling/disassembling routes together with new approaches for controlled manipulation of self-assembled structures and the fabrication of new functional patterned surfaces. EXPERIMENTS: We study the reversible disassembly itineraries that emerge in linear aggregates of micrometer-sized magnetic particles adsorbed onto a fluid interface when the applied field is abruptly tilted out of the confining surface: the unzipping of chains laterally aggregated, the partial fragmentation of the chains, the gradual separation of the monomers and the abrupt colloidal explosion. FINDINGS: By combining experiments, simulations and theoretical arguments, we elucidate different dissociation mechanisms strongly influenced by subtle changes in the orientation of the applied field, the particle's position relative to the confining interface and the mutual induction of the particles. Moreover, we show that the understanding of the mechanisms can be applied to pinpoint exactly particle detachments in two-dimensional binary mixtures.

Direct measurement of Lighthill's energetic efficiency of a minimal magnetic microswimmer.

The realization of artificial microscopic swimmers able to propel in viscous fluids is an emergent research field of fundamental interest and vast technological applications. For certain functionalities, the efficiency of the microswimmer in converting the input power provided through an external actuation into propulsive power output can be critical. Here we use a microswimmer composed by a self-assembled ferromagnetic rod and a paramagnetic sphere and directly determine its swimming efficiency when it is actuated by a swinging magnetic field. Using fast video recording and numerical simulations we fully characterize the dynamics of the propeller and identify the two independent degrees of freedom which allow its propulsion. We then obtain experimentally the Lighthill's energetic efficiency of the swimmer by measuring the power consumed during propulsion and the energy required to translate the propeller at the same speed. Finally, we discuss how the efficiency of our microswimmer could be increased upon suitable tuning of the different experimental parameters.

Magnetically tunable bidirectional locomotion of a self-assembled nanorod-sphere propeller.

Field-driven direct assembly of nanoscale matter has impact in disparate fields of science. In microscale systems, such concept has been recently exploited to optimize propulsion in viscous fluids. Despite the great potential offered by miniaturization, using self-assembly to achieve transport at the nanoscale remains an elusive task. Here we show that a hybrid propeller, composed by a ferromagnetic nanorod and a paramagnetic microsphere, can be steered in a fluid in a variety of modes, from pusher to puller, when the pair is dynamically actuated by a simple oscillating magnetic field. We exploit this unique design to build more complex structures capable of carrying several colloidal cargos as microscopic trains that quickly disassemble at will under magnetic command. In addition, our prototype can be extended to smaller nanorods below the diffraction limit, but still dynamically reconfigurable by the applied magnetic field.

Pair interactions among ternary DPPC/POPC/cholesterol mixtures in liquid-ordered and liquid-disordered phases.

Saturated phospholipids, unsaturated phospholipids, and cholesterol are essential components of cell membranes, making the understanding of their mutual interactions of great significance. We have performed microsecond molecular dynamics simulations on the ternary mixtures of DPPC/POPC/cholesterol to systematically examine lipid-lipid and cholesterol-lipid interactions in the liquid-ordered and the liquid-disordered phases. The results show that there exists a competition between the tighter packing of cholesterol-lipid and the looser packing of lipid-lipid as the membrane changes from the liquid-disordered phase to the liquid-ordered phase. Depending on the lipid saturation, the favor of lipid-lipid interactions is in the order of saturated-saturated > monounsaturated-monounsaturated > saturated-monounsaturated. Cholesterol-saturated lipid interactions are more favorable than cholesterol-monounsaturated lipid ones. The results are consistent with the push-pull forces derived from experiments and give general insights into the interactions among membrane components.

Free energy landscapes of sodium ions bound to DMPC-cholesterol membrane surfaces at infinite dilution.

Exploring the free energy landscapes of metal cations on phospholipid membrane surfaces is important for the understanding of chemical and biological processes in cellular environments. Using metadynamics simulations we have performed systematic free energy calculations of sodium cations bound to DMPC phospholipid membranes with cholesterol concentration varying between 0% (cholesterol-free) and 50% (cholesterol-rich) at infinite dilution. The resulting free energy landscapes reveal the competition between binding of sodium to water and to lipid head groups. Moreover, the binding competitiveness of lipid head groups is diminished by cholesterol contents. As cholesterol concentration increases, the ionic affinity to membranes decreases. When cholesterol concentration is greater than 30%, the ionic binding is significantly reduced, which coincides with the phase transition point of DMPC-cholesterol membranes from a liquid-disordered phase to a liquid-ordered phase. We have also evaluated the contributions of different lipid head groups to the binding free energy separately. The DMPC's carbonyl group is the most favorable binding site for sodium, followed by DMPC's phosphate group and then the hydroxyl group of cholesterol.

Structural Interpretation of the Large Slowdown of Water Dynamics at Stacked Phospholipid Membranes for Decreasing Hydration Level: All-Atom Molecular Dynamics.

Hydration water determines the stability and function of phospholipid membranes as well as the interaction of membranes with other molecules. Experiments and simulations have shown that water dynamics slows down dramatically as the hydration decreases, suggesting that the interfacial water that dominates the average dynamics at low hydration is slower than water away from the membrane. Here, based on all-atom molecular dynamics simulations, we provide an interpretation of the slowdown of interfacial water in terms of the structure and dynamics of water-water and water-lipid hydrogen bonds (HBs). We calculate the rotational and translational slowdown of the dynamics of water confined in stacked phospholipid membranes at different levels of hydration, from completely hydrated to poorly hydrated membranes. For all hydrations, we analyze the distribution of HBs and find that water-lipids HBs last longer than water-water HBs and that at low hydration most of the water is in the interior of the membrane. We also show that water-water HBs become more persistent as the hydration is lowered. We attribute this effect (i) to HBs between water molecules that form, in turn, persistent HBs with lipids; (ii) to the hindering of the H-bonding switching between water molecules due to the lower water density at the interface; and (iii) to the higher probability of water-lipid HBs as the hydration decreases. Our interpretation of the large dynamic slowdown in water under dehydration is potentially relevant in understanding membrane biophysics at different hydration levels.

Specific Ion Binding at Phospholipid Membrane Surfaces.

Metal cations are ubiquitous components in biological environments and play an important role in regulating cellular functions and membrane properties. By applying metadynamics simulations, we have performed systematic free energy calculations of Na(+), K(+), Ca(2+), and Mg(2+) bound to phospholipid membrane surfaces for the first time. The free energy landscapes unveil specific binding behaviors of metal cations on phospholipid membranes. Na(+) and K(+) are more likely to stay in the aqueous solution and can bind easily to a few lipid oxygens by overcoming low free energy barriers. Ca(2+) is most stable when it is bound to four lipid oxygens of the membrane rather than being hydrated in the aqueous solution. Mg(2+) is tightly hydrated, and it shows hardly any loss of a hydration water or binding directly to the membrane. When bound to the membrane, the cations' most favorable total coordination numbers with water and lipid oxygens are the same as their corresponding hydration numbers in aqueous solution, indicating a competition between ion binding to water and lipids. The binding specificity of metal cations on membranes is highly correlated with the hydration free energy and the size of the hydration shell.