Long-term memory and synapse-like dynamics in two-dimensional nanofluidic channels.

Fine-tuned ion transport across nanoscale pores is key to many biological processes, including neurotransmission. Recent advances have enabled the confinement of water and ions to two dimensions, unveiling transport properties inaccessible at larger scales and triggering hopes of reproducing the ionic machinery of biological systems. Here we report experiments demonstrating the emergence of memory in the transport of aqueous electrolytes across (sub)nanoscale channels. We unveil two types of nanofluidic memristors depending on channel material and confinement, with memory ranging from minutes to hours. We explain how large time scales could emerge from interfacial processes such as ionic self-assembly or surface adsorption. Such behavior allowed us to implement Hebbian learning with nanofluidic systems. This result lays the foundation for biomimetic computations on aqueous electrolytic chips.

Studying polymer diffusiophoresis with non-equilibrium molecular dynamics.

We report a numerical study of the diffusiophoresis of short polymers using non-equilibrium molecular dynamics simulations. More precisely, we consider polymer chains in a fluid containing a solute that has a concentration gradient and examine the variation of the induced diffusiophoretic velocity of the polymer chains as the interaction between the monomer and the solute is varied. We find that there is a non-monotonic relation between the diffusiophoretic mobility and the strength of the monomer-solute interaction. In addition, we find a weak dependence of the mobility on the length of the polymer chain, which shows clear difference from the diffusiophoresis of a solid particle. Interestingly, the hydrodynamic flow through the polymer is much less screened than for pressure driven flows.

Local and global force balance for diffusiophoretic transport.

Electro- and diffusio- phoresis of particles correspond respectively to the transport of particles under electric field and solute concentration gradients. Such interfacial transport phenomena take their origin in a diffuse layer close to the particle surface, and the motion of the particle is force-free. In the case of electrophoresis, it is further expected that the stress acting on the moving particle vanishes locally as a consequence of local electroneutrality. But the argument does not apply to diffusiophoresis, which takes its origin in solute concentration gradients. In this paper we investigate further the local and global force balance on a particle undergoing diffusiophoresis. We calculate the local tension applied on the particle surface and show that, counter-intuitively, the local force on the particle does not vanish for diffusiophoresis, in spite of the global force being zero as expected. Incidentally, our description allows to clarify the osmotic balance in diffusiophoresis, which has been a source of debates in the recent years. We explore various cases, including hard and soft interactions, as well as porous particles, and provide analytic predictions for the local force balance in these various systems. The existence of local stresses may induce deformation of soft particles undergoing diffusiophoresis, hence suggesting applications in terms of particle separation based on capillary diffusiophoresis.

Molecular streaming and its voltage control in ångström-scale channels.

Over the past decade, the ability to reduce the dimensions of fluidic devices to the nanometre scale (by using nanotubes1-5 or nanopores6-11, for example) has led to the discovery of unexpected water- and ion-transport phenomena12-14. More recently, van der Waals assembly of two-dimensional materials15 has allowed the creation of artificial channels with ångström-scale precision16. Such channels push fluid confinement to the molecular scale, wherein the limits of continuum transport equations17 are challenged. Water films on this scale can rearrange into one or two layers with strongly suppressed dielectric permittivity18,19 or form a room-temperature ice phase20. Ionic motion in such confined channels21 is affected by direct interactions between the channel walls and the hydration shells of the ions, and water transport becomes strongly dependent on the channel wall material22. We explore how water and ionic transport are coupled in such confinement. Here we report measurements of ionic fluid transport through molecular-sized slit-like channels. The transport, driven by pressure and by an applied electric field, reveals a transistor-like electrohydrodynamic effect. An applied bias of a fraction of a volt increases the measured pressure-driven ionic transport (characterized by streaming mobilities) by up to 20 times. This gating effect is observed in both graphite and hexagonal boron nitride channels but exhibits marked material-dependent differences. We use a modified continuum framework accounting for the material-dependent frictional interaction of water molecules, ions and the confining surfaces to explain the differences observed between channels made of graphene and hexagonal boron nitride. This highly nonlinear gating of fluid transport under molecular-scale confinement may offer new routes to control molecular and ion transport, and to explore electromechanical couplings that may have a role in recently discovered mechanosensitive ionic channels23.

MicroMegascope.

Atomic force microscopy (AFM) allows us to reconstruct the topography of surfaces with resolution in the nanometer range. The exceptional resolution attainable with the AFM makes this instrument a key tool in nanoscience and technology. The core of a standard AFM set-up relies on the detection of the change of the mechanical motion of a micro-oscillator when approaching the sample to image. This is despite the fact that AFM is nowadays a very common instrument for both fundamental and applied research. The fabrication of the micrometric scale mechanical oscillator is still a very complicated and expensive task requiring dedicated platforms. Being able to perform AFM with a macroscopic oscillator would make the instrument more versatile and accessible for an even larger spectrum of applications and audience. Here, we present atomic force imaging with a centimetric oscillator, an aluminum tuning fork of centimeter size as a sensor on which an accelerometer is glued on one prong to measure the oscillations. We show that it is possible to perform topographic images of nanometric resolution with a gram tuning fork. In addition to the stunning sensitivity, we show the high versatility of such an oscillator by imaging both in air and liquid. The set-up proposed here can be extended to numerous experiments where the probe has to be heavy and/or very complex, and so too the environment.

Electrostatic interactions between ions near Thomas-Fermi substrates and the surface energy of ionic crystals at imperfect metals.

The electrostatic interaction between two charged particles is strongly modified in the vicinity of a metal. This situation is usually accounted for by the celebrated image charges approach, which was further extended to account for the electronic screening properties of the metal at the level of the Thomas-Fermi description. In this paper we build upon a previous approach [M. A. Vorotyntsev and A. A. Kornyshev, Zh. Eksp. Teor. Fiz., 1980, 78(3), 1008-1019] and successive works to calculate the 1-body and 2-body electrostatic energy of ions near a metal in terms of the Thomas-Fermi screening length. We propose workable approximations suitable for molecular simulations of ionic systems close to metallic walls. Furthermore, we use this framework to calculate analytically the electrostatic contribution to the surface energy of a one dimensional crystal at a metallic wall and its dependence on the Thomas-Fermi screening length. These calculations provide a simple interpretation for the surface energy in terms of image charges, which allows for an estimation of the interfacial properties in more complex situations of a disordered ionic liquid close to a metal surface. The counter-intuitive outcome is that electronic screening, as characterized by a molecular Thomas-Fermi length lTF, profoundly affects the wetting of ionic systems close to a metal, in line with the recent experimental observation of capillary freezing of ionic liquids in metallic confinement.

Osmotic flow through fully permeable nanochannels.

Osmosis across membranes is intrinsically associated with the concept of semipermeability. Here, however, we demonstrate that osmotic flow can be generated by solute gradients across nonselective, fully permeable nanochannels. Using a fluorescence imaging technique, we are able to measure the water flow rate inside single nanochannels to an unprecedented sensitivity of femtoliters per minute flow rates. Our results indicate the onset of a convective liquid motion under salinity gradients, from the higher to lower electrolyte concentration, which is attributed to diffusio-osmotic transport. To our knowledge, this is the first experimental evidence and quantitative investigation of this subtle interfacially driven transport, which need to be accounted for in nanoscale dynamics. Finally, diffusio-osmotic transport under a neutral polymer gradient is also demonstrated. The experiments highlight the entropic depletion of polymers that occurs at the nanochannel surface, resulting in convective flow in the opposite direction to that seen for electrolytes.

Ultrahigh interlayer friction in multiwalled boron nitride nanotubes.

Friction at the nanoscale has revealed a wealth of behaviours that depart strongly from the long-standing macroscopic laws of Amontons-Coulomb. Here, by using a 'Christmas cracker'-type of system in which a multiwalled nanotube is torn apart between a quartz-tuning-fork-based atomic force microscope (TF-AFM) and a nanomanipulator, we compare the mechanical response of multiwalled carbon nanotubes (CNTs) and multiwalled boron nitride nanotubes (BNNTs) during the fracture and telescopic sliding of the layers. We found that the interlayer friction for insulating BNNTs results in ultrahigh viscous-like dissipation that is proportional to the contact area, whereas for the semimetallic CNTs the sliding friction vanishes within experimental uncertainty. We ascribe this difference to the ionic character of the BN, which allows charge localization. The interlayer viscous friction of BNNTs suggests that BNNT membranes could serve as extremely efficient shock-absorbing surfaces.

Probability distributions for the run-and-tumble bacterial dynamics: an analogy to the Lorentz model.

In this paper, we exploit an analogy of the run-and-tumble process for bacterial motility with the Lorentz model of electron conduction in order to obtain analytical results for the intermediate scattering function. This allows to obtain an analytical result for the van Hove function in real space for two-dimensional systems. We furthermore consider the 2D circling motion of bacteria close to solid boundaries with tumbling, and show that the analogy to electron conduction in a magnetic field allows to predict the effective diffusion coefficient of the bacteria. The latter is shown to be reduced by the circling motion of the bacteria.

Dynamic clustering in active colloidal suspensions with chemical signaling.

In this Letter, we explore experimentally the phase behavior of a dense active suspension of self-propelled colloids. In addition to a solidlike and gaslike phase observed for high and low densities, a novel cluster phase is reported at intermediate densities. This takes the form of a stationary assembly of dense aggregates-resulting from a permanent dynamical merging and separation of active colloids-whose average size grows with activity as a linear function of the self-propelling velocity. While different possible scenarios can be considered to account for these observations-such as a generic velocity weakening instability recently put forward-we show that the experimental results are reproduced mathematically by a chemotactic aggregation mechanism, originally introduced to account for bacterial aggregation and accounting here for diffusiophoretic chemical interaction between colloidal swimmers.

Nanofluidics in the Debye layer at hydrophilic and hydrophobic surfaces.

By using evanescent waves, we study equilibrium and dynamical properties of liquid-solid interfaces in the Debye layer for hydrophilic and hydrophobic surfaces. We measure velocity profiles and nanotracer concentration and diffusion profiles between 20 and 300 nm from the walls in pressure-driven and electro-osmotic flows. We extract electrostatic and zeta potentials and determine hydrodynamic slip lengths with 10 nm accuracy. The spectacular amplification of the zeta potential resulting from hydrodynamic slippage allows us to clarify for the first time the dynamic origin of the zeta potential.

Boosting migration of large particles by solute contrasts.

Brownian diffusion is a keystone concept in a large variety of domains, from physics, chemistry to biology. Diffusive transport controls situations as diverse as reaction-diffusion processes in biology and chemistry, Brownian ratchet processes, dispersion in microfluidic devices or even double-diffusive instability and salt-fingering phenomena in the context of ocean mixing. Although these examples span a broad range of length scales, diffusive transport becomes increasingly inefficient for larger particles. Applications, for example, in microfluidics, usually have recourse to alternative driving methods involving external sources to induce and control migration. Here, we demonstrate experimentally a strongly enhanced migration of large particles, achieved by slaving their dynamics to that of a fast carrier species, a dilute salt. The underlying fast salt diffusion leads to an apparent diffusive-like dynamics of the large particles, which is up to two orders of magnitude faster than their natural 'bare' diffusion. Moreover both spreading and focusing of the particle assembly can be achieved on demand. A model description shows a remarkable quantitative agreement with all measured data. Applications of this process are illustrated in microfluidics for filtering and concentrating operations, as well as in conjunction with standard hydrodynamic focusing. In a wider perspective, this mechanism can affect a broad range of scales and phenomena, from biological transport to the dispersion of sediments and pollutants in oceanographic situations.

Spatial cooperativity in soft glassy flows.

Amorphous glassy materials of diverse nature-concentrated emulsions, granular materials, pastes, molecular glasses-display complex flow properties, intermediate between solid and liquid, which are at the root of their use in many applications. A general feature of such systems, well documented yet not really understood, is the strongly nonlinear nature of the flow rule relating stresses and strain rates. Here we use a microfluidic velocimetry technique to characterize the flow of thin layers of concentrated emulsions, confined in gaps of different thicknesses by surfaces of different roughnesses. We find evidence for finite-size effects in the flow behaviour and the absence of an intrinsic local flow rule. In contrast to the classical nonlinearities of the rheological behaviour of amorphous materials, we show that a rather simple non-local flow rule can account for all the velocity profiles. This non-locality of the dynamics is quantified by a length, characteristic of cooperativity within the flow at these scales, that is unobservable in the liquid state (lower emulsion concentrations) and that increases with concentration in the jammed state. Beyond its practical importance for applications involving thin layers (for example, coatings), these non-locality and cooperativity effects have parallels in the behaviour of other glassy, jammed and granular systems, suggesting a possible fundamental universality.

Using surface force apparatus, diffusion and velocimetry to measure slip lengths.

Determining the slip lengths for liquids flowing close to smooth walls is challenging. The reason lies in the fact that the scales that must be addressed range between a few and hundreds of nanometres. Several techniques have been used over the last few years. Here, we consider three of them based on surface force apparatus, diffusion and velocimetry, respectively. The descriptions offered here incorporate recent instrumental progress made in the field.

Slippage of water past superhydrophobic carbon nanotube forests in microchannels.

We present in this Letter an experimental characterization of liquid flow slippage over superhydrophobic surfaces made of carbon nanotube forests, incorporated in microchannels. We make use of a particle image velocimetry technique to achieve the submicrometric resolution on the flow profile necessary for accurate measurement of the surface hydrodynamic properties. We demonstrate boundary slippage on the Cassie superhydrophobic state, associated with slip lengths of a few microns, while a vanishing slip length is found in the Wenzel state when the liquid impregnates the surface. Varying the lateral roughness scale L of our carbon nanotube forest-based superhydrophobic surfaces, we demonstrate that the slip length varies linearly with L in line with theoretical predictions for slippage on patterned surfaces.

Probing the nanohydrodynamics at liquid-solid interfaces using thermal motion.

We report on a new method to characterize nanohydrodynamic properties at the liquid-solid interface relying solely on the measurement of the thermal motion of confined colloids. This equilibrium measurement of surface properties--equivalent in spirit to the passive microrheology technique used for bulk properties--is able to achieve nanometric resolution on the slip length measurement. Exploring the "zero shear rate" limit, it rules out shear rate threshold to slip effects and extends the range over which slip lengths are shown to be flow independent. Avoiding the nucleation of gas pockets (nanobubbles) through external forcing, it validates the theoretical picture for intrinsic liquid-solid interfaces, reporting nanometric slip lengths (b=18+/-5 nm) only in nonwetting situations, opening the route to quantitative study on more complex surfaces with combined effects of nonwettability and roughness.

Nucleation in hydrophobic cylindrical pores: a lattice model.

We consider the nucleation process associated with capillary condensation of a vapor in a hydrophobic cylindrical pore (capillary evaporation). The liquid-vapor transition is described within the framework of a simple lattice model. The phase properties are characterized both at the mean-field level and with Monte Carlo simulations. The nucleation process for the liquid to vapor transition is then specifically considered. Using umbrella sampling techniques, we show that nucleation occurs through the condensation of an asymmetric vapor bubble at the pore surface. Even for highly confined systems, good agreement is found with macroscopic considerations based on classical nucleation theory. The results are discussed in the context of recent experimental work on the extrusion of water in hydrophobic pores.

Dynamics of simple liquids at heterogeneous surfaces: molecular-dynamics simulations and hydrodynamic description.

In this paper we consider the effect of surface heterogeneity on the slippage of fluid, using two complementary approaches. First, MD simulations of a corrugated hydrophobic surface have been performed. A dewetting transition, leading to a super-hydrophobic state, is observed for pressure below a "capillary" pressure. Conversely, a very large slippage of the fluid on this composite interface is found in this super-hydrophobic state. Second, we propose a macroscopic estimate of the effective slip length on the basis of continuum hydrodynamics, in order to rationalize the previous MD results. This calculation allows to estimate the effect of a heterogeneous slip length pattern at the composite interface. Comparison between the two approaches shows that they are in good agreement at low pressure, but highlights the role of the exact shape of the liquid-vapor interface at higher pressure. These results confirm that small variations in the roughness of a surface can lead to huge differences in the slip effect. On the basis of these results, we propose some guidelines to design highly slippery surfaces, motivated by potential applications in microfluidics.