Direct measuring of single-heterogeneous bubble nucleation mediated by surface topology.

Heterogeneous bubble nucleation is one of the most fundamental interfacial processes ranging from nature to technology. There is excellent evidence that surface topology is important in directing heterogeneous nucleation; however, deep understanding of the energetics by which nanoscale architectures promote nucleation is still challenging. Herein, we report a direct and quantitative measurement of single-bubble nucleation on a single silica nanoparticle within a microsized droplet using scanning electrochemical cell microscopy. Local gas concentration at nucleation is determined from finite element simulation at the corresponding faradaic current of the peak-featured voltammogram. It is demonstrated that the criteria gas concentration for nucleation first drops and then rises with increasing nanoparticle radius. An optimum nanoparticle radius around 10 nm prominently expedites the nucleation by facilitating the special topological nanoconfinements that consequently catalyze the nucleation. Moreover, the experimental result is corroborated by our theoretical calculations of free energy change based on the classic nucleation theory. This study offers insights into the impact of surface topology on heterogenous nucleation that have not been previously observed.

A capillary-induced negative pressure is able to initiate heterogeneous cavitation.

A capillarity-induced negative pressure is of general importance for understanding the phase behaviors of liquids in small pores and cracks. A unique example is the embolism in the xylem of plants and the cavitation at the limiting negative pressure generated by evaporation of water from nanocapillaries in the cell walls of leaves. In this work, by combining the effect of a capillary and cavitation together, we demonstrate with molecular dynamics (MD) simulations that capillarity is able to induce spontaneous cavitation in the presence of hydrophobic heterogeneities. Our simulation results reveal separately how the capillary generates a negative pressure and how the generated negative pressure affects the onset of cavitation. We then interpret the cavitation mechanism and determine the occurrence of cavitation as a function of the hydrophobicity of the nucleating substrates where the cavitation initiates and as a function of the hydrophilicity of the capillary tube from which the negative pressure generates. Our results reveal that the capillary-induced cavitation can be described well with a heterogeneous nucleation mechanism, within the framework of classical nucleation theory.

Solutal Marangoni force controls lateral motion of electrolytic gas bubbles.

Electrochemical gas-evolving reactions have been widely used for industrial energy conversion and storage processes. Gas bubbles form frequently at the electrode surface due to a small gas solubility, thereby reducing the effective reaction area and increasing the over-potential and ohmic resistance. However, the growth and motion mechanisms for tiny gas bubbles on the electrode remains elusive. Combining molecular dynamics (MD) and fluid dynamics simulations (CFD), we show that there exists a lateral solutal Marangoni force originating from an asymmetric distribution of dissolved gas near the bubble. Both MD and CFD simulations deliver a similar magnitude of the Marangoni force of ∼0.01 nN acting on the bubble. We demonstrate that this force may lead to lateral bubble oscillations and analyze the phenomenon of dynamic self-pinning of bubbles at the electrode boundary.

N-Doping CQDs as an Efficient Fluorescence Probe Based on Dynamic Quenching for Determination of Copper Ions and Alcohol Sensing in Baijiu.

To address an accurate detection of heavy metal ions in Baijiu production, a nitrogen-doping carbon quantum dots (N-CQDs) was prepared by hydrothermal method from citric acid and urea. The as-prepared N-CQDs had an average particle size of 2.74 nm, and a large number of functional groups (amino, carbonyl group, etc.) attached on its surface, which obtained a 9.6% of quantum yield (QY) with relatively high and stable fluorescence performance. As a fluorescent sensor, the fluorescence of N-CQDs at 380 nm excitation wavelength could be quenched quantitatively by adding Cu2+, due to the dynamic quenching of electron transfer caused by the binding of amine groups and Cu2+, which showed excellent sensitivity and selectivity to Cu2+ in the range of 0.5-5 µM with a detection limit (LOD) of 0.032 µM. In addition, the N-CQDs as well as could be applied to quantitative determine alcohol content in the range of 10-80 V/V% depending on the fluorescence enhancement. Upon the experiment, the fluorescent mechanism was studied by Molecular dynamics (MD) simulations, which demonstrated that solvent effect played an influential role on sensing alcohol content in Baijiu. Overall, the work provided a theoretically guide for the design of fluorescence sensors to monitor heavy metal ion in liquid drinks and sense alcohol content.

Einstein-Stokes relation for small bubbles at the nanoscale.

As the physicochemical properties of ultrafine bubble systems are governed by their size, it is crucial to determine the size and distribution of such bubble systems. At present, the size or size distribution of nanometer-sized bubbles in suspension is often measured by either dynamic light scattering or the nanoparticle tracking analysis. Both techniques determine the bubble size via the Einstein-Stokes equation based on the theory of the Brownian motion. However, it is not yet clear to which extent the Einstein-Stokes equation is applicable for such ultrafine bubbles. In this work, using atomic molecular dynamics simulation, we evaluate the applicability of the Einstein-Stokes equation for gas nanobubbles with a diameter less than 10 nm, and for a comparative analysis, both vacuum nanobubbles and copper nanoparticles are also considered. The simulation results demonstrate that the diffusion coefficient for rigid nanoparticles in water is found to be highly consistent with the Einstein-Stokes equation, with slight deviation only found for nanoparticle with a radius less than 1 nm. For nanobubbles, including both methane and vacuum nanobubbles, however, large deviation from the Einstein-Stokes equation is found for the bubble radius larger than 3 nm. The deviation is attributed to the deformability of large nanobubbles that leads to a cushioning effect for collision-induced bubble diffusion.

Synergism of Surfactant Mixture in Lowering Vapor-Liquid Interfacial Tension.

Through employing molecular dynamics, in this work, we study how a two-component surfactant mixture cooperatively reduces the interfacial tension of a flat vapor-liquid interface. Our simulation results show that in the presence of a given insoluble surfactant, adding a secondary surfactant would either further reduce interfacial tension, indicating a positive synergistic effect, or increase the interfacial tension instead, indicating a negative synergistic effect. The synergism of the surfactant mixture in lowering surface tension is found to depend strongly on the structure complementary effect between different surfactant components. The synergistic mechanisms are then interpreted with minimization of the bending free energy of the composite surfactant monolayer via cooperatively changing the monolayer spontaneous curvature. By roughly describing the monolayer spontaneous curvature with the balanced distribution of surfactant heads and tails, we confirm that the positive synergistic effect in lowering surface tension is featured with the increasingly symmetric head-tail distributions, while the negative synergistic effect is featured with the increasingly asymmetric head-tail distributions. Furthermore, our simulation results indicate that minimal interfacial tension can only be observed when the spontaneous curvature is nearly zero.

The role of surface topography in the self-assembly of polymeric surfactants.

We propose a classical density functional theory model to study the self-assembly of polymeric surfactants on curved surfaces. We use this model to investigate the thermodynamics of phase separation of a binary mixture of size asymmetric miscible surfactants on cylindrical and spherical surfaces, and observe that phase separation driven by size alone is thermodynamically unfavorable on both cylindrical and spherical surfaces. We use the theory, supplemented by dissipative particle dynamics (DPD) simulations, to predict pattern formation on a non-uniform surface with regions of positive and negative curvature. Our results suggest potential ways to couple surface topography and polymeric surfactants to design surfaces coated with non-uniform patterns.

Maximizing friction by liquid flow clogging in confinement.

In the nanoscale regime, flow behaviors for liquids show qualitative deviations from bulk expectations. In this work, we reveal by molecular dynamics simulations that plug flow down to nanoscale induces molecular friction that leads to a new flow structure due to the molecular clogging of the encaged liquid. This plug-like nanoscale liquid flow shows several features differ from the macroscopic plug flow and Poiseuille flow: It leads to enhanced liquid/solid friction, producing a friction of several order of magnitude larger than that of Couette flow; the friction enhancement is sensitively dependent of the liquid column length and the wettability of the solid substrates; it leads to the local compaction of liquid molecules that may induce solidification phenomenon for a long liquid column.

The fate of bulk nanobubbles under gas dissolution.

Artificially added or undesired organic and inorganic contaminants in solution that are interfacially active always tend to be adsorbed at the gas-liquid interface of micro- and nano-bubbles, affecting the stability of the tiny bubbles. In this work, by using molecular dynamics simulations we study how the adsorbed surfactant-like molecules, with their amphiphilic character, affect the dissolution of the existing bulk nanobubbles under low gas supersaturation environments. We find that, depending on the concentration of the dissolved gas and the molecular structure of surfactants, two fates of bulk nanobubbles whose interfaces are saturated by surfactants are found: either remaining stable or being completely dissolved. With gas dissolution, the bubble shrinks and the insoluble surfactants form a monolayer with an increasing areal density until an extremely low (close to 0) surface tension is reached. In the limit of vanishing surface tension, the chemical structure of surfactants crucially affects the bubble stability by changing the monolayer elastic energy. Two basic conditions for stable nanobubbles at low gas saturation are identified: vanishing surface tension due to bubble dissolution and positive spontaneous curvature of the surfactant monolayer. Based on this observation, we discuss the similarity in the stability mechanism of bulk nanobubbles and that of microemulsions.

Gas-liquid transition of van der Waals fluid confined in fluctuating nano-space.

Gas-liquid transition is generally a complex process, which involves nucleation of droplets and their growth by evaporation-condensation or collision-coalescence processes. Here, we focus on a microscopic system in which there is only one liquid droplet at most. In this case, we can develop an equilibrium theory for the formation of the droplet in the gas phase using the classical nucleation theory. We use the van der Waals fluid model with surface tension and calculate the size fluctuation of the droplet for various confinement conditions, NVT (in which the volume V of the system is fixed), NPT (in which the pressure P of the system is fixed), and NBT (in which the system is confined in a nano-bubble immersed in a host liquid, where both V and P can fluctuate). We show that in the NBT system, the size flexibility along with space confinement induces a wealth of properties that are not found in NVT and NPT. It exhibits richer phase behaviors: a stable droplet appears and coexists with the pure gas phase and/or pure liquid phase. When compared to the NVT system, the NBT system shows not only the oscillatory fluctuation between the two stable states but also a large fluctuation in the total volume and the pressure.

Dynamic Equilibrium Model for Surface Nanobubbles in Electrochemistry.

Gas bubbles are ubiquitous in electrochemical processes, particularly in water electrolysis. Due to the development of gas-evolving electrocatalysis and energy conversion technology, a deep understanding of gas bubble behaviors at the electrode surface is highly desirable. In this work, by combining theoretical analysis and molecular simulations, we study the behaviors of a single nanobubble electrogenerated at a nanoelectrode. With the dynamic equilibrium model, the stability criteria for stationary surface nanobubbles are established. We show theoretically that a slight change in either the gas solubility or solute concentration results in various nanobubble dynamic states at a nanoelectrode: contact line pinning in aqueous and ethylene glycol solutions, oscillation of pinning states in dimethyl sulfoxide, and mobile nanobubbles in methanol. The above complex nanobubble behavior at the electrode/electrolyte interface is explained by the competition between gas influx into the nanobubble and outflux from the nanobubble.

Molecular Sizes and Antibacterial Performance Relationships of Flexible Ionic Liquid Derivatives.

Cationic agents, such as ionic liquids (ILs)-based species, have broad-spectrum antibacterial activities. However, the antibacterial mechanisms lack systematic and molecular-level research, especially for Gram-negative bacteria, which have highly organized membrane structures. Here, we designed a series of flexible fluorescent diketopyrrolopyrrole-based ionic liquid derivatives (ILDs) with various molecular sizes (1.95-4.2 nm). The structure-antibacterial activity relationships of the ILDs against Escherichia coli (E. coli) were systematically studied thorough antibacterial tests, fluorescent tracing, morphology analysis, molecular biology, and molecular dynamics (MD) simulations. ILD-6, with a relatively small molecular size, could penetrate through the bacterial membrane, leading to membrane thinning and intracellular activities. ILD-6 showed fast and efficient antimicrobial activity. With the increase of molecular sizes, the corresponding ILDs were proven to intercalate into the bacterial membrane, leading to the destabilization of the lipid bilayer and further contributing to the antimicrobial activities. Moreover, the antibacterial activity of ILD-8 was limited, where the size was not large enough to introduce significant membrane disorder. Relative antibacterial experiments using another common Gram-negative bacteria, Pseudomonas aeruginosa (PAO1), further confirmed the proposed structure-antibacterial activity relationships of ILDs. More impressively, both ILD-6 and ILD-12 displayed significant in vivo therapeutic effects on the PAO1-infected rat model, while ILD-8 performed poorly, which confirmed the antibacterial mechanism of ILDs and proved their potentials for future application. This work clarifies the interactions between molecular sizes of ionic liquid-based species and Gram-negative bacteria and will provide useful guidance for the rational design of high-performance antibacterial agents.

Inhibiting Ostwald Ripening by Scaffolding Droplets.

Nanoemulsions as colloidal dispersions of deformable nanodroplets promise wide range of applications in pharmaceuticals, cosmetics, and agriculture. The main limitation that reduces their industrial applications is stability, with Ostwald ripening acting as the main destabilization mechanism. Different from the conventional methods by functionalizing nanoemulsions with adequate ripening inhibitors, here we propose an alternative strategy to stabilize nanoemulsions by inhibiting Ostwald ripening. We report via Lattice Boltzmann method (LBM) and theoretical analysis that the evolution of droplets can be manipulated with the help of solid substrates, either along or against the direction of Ostwald ripening. It turns out that through pinning contact line of sessile droplets, heterogeneous substrates or solid nanoparticles can behave as a scaffold to suppress Ostwald ripening, to regulate droplet morphology and to enhance droplet stability. The identical curvature and unexpected stability of scaffolding droplets are then interpreted with free energy analysis. In addition, by simulating substrates with various heterogeneities and solid particles of different shapes, we demonstrate that it is a common phenomenon that scaffolding droplets can evolve beyond Ostwald ripening.

Surface enrichment of ions leads to the stability of bulk nanobubbles.

Numerous experiments have shown that bulk nanobubble suspensions are often characterized by a high magnitude of zeta potential. However, the underlying physical mechanism of how the bulk nanobubbles can stably exist has remained unclear so far. In this paper, based on theoretical analysis, we report a stability mechanism for charged bulk nanobubbles. The strong affinity of negative charges for the nanobubble interface causes charge enrichment, and the resulting electric field energy gives rise to a local minimum for the free energy cost of bubble formation, leading to thermodynamic metastability of the charged nanobubbles. The excess surface charges mechanically generate a size-dependent force, which balances the Laplace pressure and acts as a restoring force when a nanobubble is thermodynamically perturbed away from its equilibrium state. With this negative feedback mechanism, we discuss the nanobubble stability as a function of surface charge and gas supersaturation. We also compare our theoretical prediction with recent experimental observations, and a good agreement is found. This mechanism provides new fundamental insights into the origin of the unexplained stability of bulk nanobubbles.

Mechanics of the Formation, Interaction, and Evolution of Membrane Tubular Structures.

Membrane nanotubes, also known as membrane tethers, play important functional roles in many cellular processes, such as trafficking and signaling. Although considerable progresses have been made in understanding the physics regulating the mechanical behaviors of individual membrane nanotubes, relatively little is known about the formation of multiple membrane nanotubes due to the rapid occurring process involving strong cooperative effects and complex configurational transitions. By exerting a pair of external extraction upon two separate membrane regions, here, we combine molecular dynamics simulations and theoretical analysis to investigate how the membrane nanotube formation and pulling behaviors are regulated by the separation between the pulling forces and how the membrane protrusions interact with each other. As the force separation increases, different membrane configurations are observed, including an individual tubular protrusion, a relatively less deformed protrusion with two nanotubes on its top forming a V shape, a Y-shaped configuration through nanotube coalescence via a zipper-like mechanism, and two weakly interacting tubular protrusions. The energy profile as a function of the separation is determined. Moreover, the directional flow of lipid molecules accompanying the membrane shape transition is analyzed. Our results provide new, to our knowledge, insights at a molecular level into the interaction between membrane protrusions and help in understanding the formation and evolution of intra- and intercellular membrane tubular networks involved in numerous cell activities.

Stability of Surface Nanobubbles without Contact Line Pinning.

Although the stability of most surface nanobubbles observed can be well interpreted by contact line pinning and supersaturation theory, there is increasing evidence that at least for certain situations, contact line pinning is not required for nanobubble stability. This raises a significant question of what is the stability mechanism for those sessile nanobubbles. Through theoretical analysis and molecular dynamics simulations, in this work, we report two mechanisms for stabilizing surface nanobubbles on flat and homogeneous substrates. One is attributed to constant adsorption of trace impurities on the nanobubble gas?liquid interface, through which nanobubble growing or shrinking causes the increase and decrease of interfacial tension, acting as a restoring force to bring the nanobubble to its equilibrium size. The other is attributed to the deformation of a soft substrate induced by the formed nanobubble, which in turn stabilizes the nanobubble via impeding the contact line motion, similar to self-pinning of microdroplets on soft substrates. Both mechanisms can interpret, depending on the specified conditions, how surface nanobubbles can remain stable in the absence of contact line pinning.

Directional and Rotational Motions of Nanoparticles on Plasma Membranes as Local Probes of Surface Tension Propagation.

Mechanical heterogeneity is ubiquitous in plasma membranes and of essential importance to cellular functioning. As a feedback of mechanical stimuli, local surface tension can be readily changed and immediately propagated through the membrane, influencing structures and dynamics of both inclusions and membrane-associated proteins. Using the nonequilibrium coarse-grained membrane simulation, here we investigate the inter-related processes of tension propagation, lipid diffusion, and transport of nanoparticles (NPs) adhering on the membrane of constant tension gradient, mimicking that of migrating cells or cells under prolonged stimulation. Our results demonstrate that the lipid bilayer membrane can by itself propagate surface tension in defined rates and pathways to reach a dynamic equilibrium state where surface tension is linearly distributed along the gradient maintained by the directional flow-like motion of lipids. Such lipid flow exerts shearing forces to transport adhesive NPs toward the region of a larger surface tension. Under certain conditions, the shearing force can generate nonzero torques driving the rotational motion of NPs, with the direction of the NP rotation determined by the NP-membrane interaction state as functions of both NP property and local membrane surface tension. Such features endow NPs with promising applications ranging from biosensing to targeted drug delivery.

Active microrheology in two-dimensional magnetic networks.

We study active microrheology in two-dimensional (2D) magnetic networks. To this end, we use Langevin dynamics computer simulations where single non-magnetic or magnetic tracer particles are pulled through the network structures via a constant force f. Structural changes in the network around the pulled tracer particle are characterized in terms of pair correlation functions. These functions indicate that the non-magnetic tracer particles tend to strongly affect the network structure leading to the formation of channels at sufficiently high forces, while the magnetic tracer particles modify the network structure only slightly. At zero pulling force, f = 0, both non-magnetic and magnetic tracer particles are localized, i.e. they do not show diffusive behavior in the long-time limit. Nevertheless, the friction coefficient, as obtained from the steady-state velocity of the tracer particles, seems to indicate a linear-response regime at small values of f. Beyond the latter linear response regime, the diffusion dynamics of the tracer particles are anisotropic with superdiffusive behavior in force direction. This transport anomaly is investigated via van Hove correlation functions and residence time distributions.

Surface Nanobubbles Nucleate Liquid Boiling.

Surface nanobubbles have been presumed to lead to the experimental observation that liquid boiling often occurs at a much lower supersaturation than expected, yet no qualitative theory exists to explain how they participate in the process. Here, we report through a simple theoretical analysis on how the metastable nanobubbles nucleate the liquid-to-vapor transition by serving as an intermediate phase. The appearance of metastable nanobubbles inhibits the shrink of the bubble nucleus and changes bubble nucleation into a multistep process. We show three possible mechanisms for heterogeneous nucleation starting from metastable surface nanobubbles: nucleation from pinned nanobubbles, nucleation via nanobubble depinning, and nucleation through nanobubble coalescence, each predicting a significant reduction in a nucleation barrier. The occurrence of a specific nucleation pathway of bubble nucleation depends on the detailed geometry of local substrate roughness. These results give insight into how the appearance of surface nanobubbles changes the nucleation mechanisms of liquid boiling.

Role of Lipid Coating in the Transport of Nanodroplets across the Pulmonary Surfactant Layer Revealed by Molecular Dynamics Simulations.

Hydrophilic drugs can be delivered into lungs via nebulization for both local and systemic therapies. Once inhaled, ultrafine nanodroplets preferentially deposit in the alveolar region, where they first interact with the pulmonary surfactant (PS) layer, with nature of the interaction determining both efficiency of the pulmonary drug delivery and extent of the PS perturbation. Here, we demonstrate by molecular dynamics simulations the transport of nanodroplets across the PS layer being improved by lipid coating. In the absence of lipids, bare nanodroplets deposit at the PS layer to release drugs that can be directly translocated across the PS layer. The translocation is quicker under higher surface tensions but at the cost of opening pores that disrupt the ultrastructure of the PS layer. When the PS layer is compressed to lower surface tensions, the nanodroplet prompts collapse of the PS layer to induce severe PS perturbation. By coating the nanodroplet with lipids, the disturbance of the nanodroplet on the PS layer can be reduced. Moreover, the lipid-coated nanodroplet can be readily wrapped by the PS layer to form vesicular structures, which are expected to fuse with the cell membrane to release drugs into secondary organs. Properties of drug bioavailability, controlled drug release, and enzymatic tolerance in real systems could be improved by lipid coating on nanodroplets. Our results provide useful guidelines for the molecular design of nanodroplets as carriers for the pulmonary drug delivery.