Mechanism of nitromethane liquid membrane oscillator containing sodium oleate

The oscillatory behavior of a liquid membrane oscillator with anionic surfactant was investigated in order to understand the oscillation mechanism at the molecular level. As a theoretical framework, an approach based on chemical kinetics laws has been used. The chosen system involved nitromethane with 2,2(')-bipyridine as liquid membrane. The aqueous donor phase contained sodium oleate and butanol, while sodium chloride was added to the aqueous acceptor phase. It was established that the oscillations take place exclusively at the aqueous acceptor phase/membrane interface. Therefore, liquid membrane oscillators with anionic surfactants behave the same way as oscillators with cationic surfactants as to the location of oscillations. An oscillation mechanism involving three stages is proposed and confirmed by numerical simulations. The oscillations of electrical potential differences between the two aqueous phases are produced by sudden adsorption and desorption of anionic surfactant in solvated form and butanol at the acceptor/membrane interface. The whole process is controlled by the slow diffusion of these species across the liquid membrane. The chaotic character of the oscillations was demonstrated by Lyapunov exponents obtained from the strange attractor of the system.     

Mechanism of a four-phase liquid membrane oscillator containing hexadecyltrimethylammonium bromide

The oscillatory behavior of a nitromethane based liquid membrane oscillator was investigated to contribute to the oscillation mechanism at the molecular level. At the beginning the system contains three phases: the aqueous donor phase in which the cationic surfactant, hexadecyltrimethylammonium bromide and ethanol are present and the aqueous acceptor phase made up by sucrose solution separated by the liquid membrane containing a constant amount of picric acid. During experiment a new phase x is created between the liquid membrane and acceptor phase. It was established that the oscillations take place at the membrane/phase x and the phase x/acceptor phase interfaces. Five basic regions can be distinguished in the oscillation pattern. The molecular events provoking the oscillations of electric potential difference between the two aqueous phases involve essentially the diffusion of hexadecyltrimethylammonium bromide and ion pairs formed by the cation of the surfactant and the picrate anion to the vicinity of the membrane/phase x interface, sudden adsorption of these ion pairs at this interface in noncatalytic and autocatalytic steps, desorption of ion pairs from the membrane/phase x interface into phase x, diffusion of ion pairs to the vicinity of phase x/acceptor phase interface, and sudden adsorption at this interface followed by desorption to the aqueous acceptor phase. It is shown by numerical simulations that the proposed mechanism may account for the observed oscillations and for the species distribution throughout the system as found experimentally. This four-phase system behaves like two coupled oscillators.     

Hydrodynamically induced chemical oscillation at a water/nitrobenzene interface

By measuring a time course of interfacial tension and interfacial electrical potential, we successfully observed oscillatory phenomena that were based on alternatively appearing adsorption and desorption processes of anionic surfactant molecules (sodium dodecyl sulfate (SDS)) at the water/nitrobenzene interface. These oscillation patterns were drastically modified by slightly changing the rate of SDS aqueous solution injection into the water phase. When 10 mM of SDS aqueous solution was injected at a low rate, for example, at less than 1 microl/min, abrupt adsorption was repeatedly followed by slow desorption of DS- ions; in other words, the sequence of the oscillation and relaxation processes was repeated. However, when it was injected at a higher rate, no remarkable periodic phenomenon occurred after the first oscillation. In addition, the rapid adsorption process was observed to be accompanied by a flip motion of the liquid/liquid interface and a flow along the interface. This is caused by a Marangoni convection that is brought about by the generation of heterogeneity of interfacial tension. Furthermore, by estimating the flow speed, it was determined that the faster flow tends to quench the periodic oscillation patterns.     

A novel method to study particle–air/liquid surface interactions

A novel method to study the dynamics of hydrophilic solid particle interactions with the gas/aqueous surface has been developed; the gas/liquid surface oscillation was monitored using light reflection microscopy. Two modes of gas/liquid surface oscillation are observed: a high mode of oscillation during the first 0.1 s and a low mode of oscillation during the last 0.4 s. It has been shown that the two modes of oscillation are related with the two-stage process of particle–gas/liquid interactions; during the first stage, the particle and gas/liquid surface interact via a long-range hydrodynamic interaction. The liquid film between the particle and the gas/liquid surface decreases its thickness. During the second stage, the particle is adhered (via liquid film) to the air/aqueous surface, and the air/aqueous surface oscillates with the particle. Effects of particle size and surface tension on the frequency of oscillation of the gas/liquid surface were also studied. Two theoretical models are used to predict the high frequency and low frequency of the air/aqueous surface oscillation.     

Computational study of ion distributions at the air/liquid methanol interface

Molecular dynamic simulations with polarizable potentials were performed to systematically investigate the distribution of NaCl, NaBr, NaI, and SrCl(2) at the air/liquid methanol interface. The density profiles indicated that there is no substantial enhancement of anions at the interface for the NaX systems, in contrast to what was observed at the air/aqueous interface. The surfactant-like shape of the larger more polarizable halide anions, which is part of the reason they are driven to air/aqueous interfaces, was compensated by the surfactant nature of methanol itself. These halide anions had on average an induced dipole of moderate magnitude in bulk methanol. As a consequence, methanol hydroxy groups donated hydrogen bonds to anions where the negatively charged side of the anion induced dipole pointed, and methyl groups interacted with anions where the positively charged side of the anion-induced dipole pointed. Furthermore, salts were found to disrupt the surface structure of methanol. For the neat air/liquid methanol interface, there is relative enhancement of methyl groups at the outer edge of the air/liquid methanol interface in comparison with hydroxy groups, but with the addition of NaX this enhancement was reduced somewhat. Finally, with the additional of salts to methanol, the computed surface potentials decreased, which is in contrast to what is observed in corresponding aqueous systems, where the surface potential increases with the addition of salts. Both of these trends have been indirectly observed with experiments. The surface potential trends were found to be due to the greater propensity of anions for the air/water interface that is not present at the air/liquid methanol interface.     

Study on the oscillating phenomena of electrical potential across a liquid membrane

The electrical oscillations across a liquid membrane in water/oil/water system was studied with octanol as oil phase by introducing two opposite charged surfactants in oil and aqueous phase, respectively. The sustained and rhythmic oscillation was observed. To a certain extent, the features of the oscillation (e.g. induction time, frequency, life time and orientation of the pulse pikes) strongly depend on the property of surfactant, dissolved in octanol. The mechanism may be explained by the formation and destruction of dual-ion surfactant membrane accompanying with emulsification at the interface and considering the coupling effect of diffusion and associated reaction in the vicinity of the interface.     

Electrochemical Investigation for Cu2+ Oscillatory Phenomena at the Liquid/Liquid Interface with a Specific Adsorption of Ion Pair Model

In this paper, a novel current oscillatory phenomenon for Cu²⁺ at the water/1,2‐dichloroethane interface is reported with cyclic voltammetry and potential‐step chronoamperometry. The small irregular current spikes were only observed near the site of the oxidation peak of CuCl₂^? and were mainly related to the Cu²⁺concentration in the aqueous phase. Our experimental results demonstrated that the current oscillation is caused by specific adsorption of ion pairs at the W/DCE interface between Cu²⁺ in the aqueous phase and TPB^? in the organic phase. Therefore, a specific adsorption of ion pair model has been formulated for the current oscillation at the liquid/liquid interface. The DFT calculation method was used to explain the mechanism of ion pair formation. The calculation results suggested that the TPB^?Cu²⁺TPB^? ion pair has the lowest‐energy state, thus providing qualitative support for the ion pair model. A probable mechanism for the observed current oscillation was also discussed in this paper. At the same time, a spectrophotometric experiment was performed to evidence a strong attractive interaction between Cu²⁺ and TPB^?.     

Surface-enhanced Raman scattering from oleate-stabilized silver colloids at a liquid/liquid interface.

Oleate-stabilized silver colloids of 5-nm-diameter were adsorbed to a toluene/water interface, and surface enhanced Raman scattering (SERS) spectra from these colloids were measured under the total internal reflection (TIR) condition. From the observed spectra, we examined the states of oleate ions and toluene molecules on silver colloids at the liquid/liquid interfacial region. The TIR-SERS spectra of oleate ions showed stronger peaks of the carboxylate group and the ethylene group than those of alkyl chains. From these results, it was found that the oleate ions were adsorbed on the silver surface in two different ways at the liquid/liquid interface; the carboxylate group adsorbed in the organic phase side, while the ethylene group adsorbed in the aqueous phase side. The shifts of the toluene in the interfacial SERS spectra were identical to those of bulk toluene, though the relative intensities among the peaks were not same. This result suggested that the toluene was adsorbed with a weak interaction, but was significantly enhanced by the local electromagnetic field at the colloid surface.     

Electric field enhanced spreading of partially wetting thin liquid films

Equilibrium and dynamic electrowetting behavior of ultrathin liquid films of surfactant (SDS) laden water over silicon substrate (with native oxide) is investigated. A nonobtrusive optical method, namely, image analyzing interferometry, is used to measure the meniscus profile, adsorbed film thickness, and the curvature of the capillary meniscus. Significant advancement of the contact line of the liquid meniscus, as a result of the application of electric field, is observed even at relatively lower values of applied voltages. The results clearly demonstrate the balance of intermolecular and surface forces with additional contribution from Maxwell stress at the interline. The singular nature of Maxwell stress is exploited in this analysis to model the equilibrium meniscus profile using the augmented Young-Laplace equation, leading to the in situ evaluation of the dispersion constant. The electrowetting dynamics has been explored by measuring the velocity of the advancing interline. The interplay of different forces at the interface is modeled using a control volume approach, leading to an expression for the interline velocity. The model-predicted interline velocities are successfully compared with the experimentally measured velocities. Beyond a critical voltage, contact line instability resulting in emission of droplets from the curved meniscus has been observed.     

Electron transfer mediated by glucose oxidase at the liquid/liquid interface

In order to establish an experimental basis for exploring the reactivity of membrane-bound redox enzymes using electrochemistry at an organic/aqueous interface, the reactivity of glucose oxidase adsorbed at the dichloroethane/water interface has been studied. Turnover of glucose in the aqueous phase mediated by dimethyl ferricenium electrogenerated in the organic phase was measured by measuring the feedback current caused by recycling the mediator as the generator electrode approached close to the interface from the organic side. An unexpected self-exchange reaction of the ferrocene at the interface was suppressed by adsorption of a surfactant. The interfacial enzyme reaction could be distinguished from reaction within the bulk of the aqueous phase. Reaction within a protein-surfactant film formed at the interface is conjectured.     

Wetting-Dewetting oscillations of liquid films during solution-mediated vacuum deposition of rubrene

We found a novel oscillating phenomenon associated with surface wetting during the vacuum deposition of an organic semiconductor (rubrene) on a liquid film (bis(2-ethylhexyl)sebacate, B2EHS). In-situ observations by an optical microscope revealed that the oscillation was associated with the growth of the rubrene crystals. The oscillation frequency was proportional to the evaporation rate of rubrene. On the basis of the contact angle measurements, it was concluded that the oscillation is probably due to the change in the contact angle of the liquid caused by the formation of ultrathin rubrene films on the liquid surface.     

Molecular simulation of adsorption and intrusion in nanopores

This paper reports Monte Carlo simulations of the adsorption or intrusion in cylindrical silica nanopores. All the pores are opened at both ends towards an external bulk reservoir, so that they mimic real materials for which the confined fluid is always in contact with the external phase. This realistic model allows us to discuss the nature of the filling and emptying mechanisms. The adsorption corresponds to the metastable nucleation of the liquid phase, starting from a partially filled pore (a molecular thick film adsorbed at the pore surface). On the other hand, the desorption occurs through the displacement at equilibrium of a gas/liquid hemispherical interface (concave meniscus) along the pore axis. The intrusion of the non-wetting fluid proceeds through the invasion in the pore of the liquid/gas interface (convex meniscus), while the extrusion consists of the nucleation of the gas phase within the pore. In the case of adsorption, our simulation data are used to discuss the validity of the modified Kelvin equation (which is corrected for both the film adsorbed at the pore surface and the curvature effect on the gas/liquid surface tension).     

Probing non-polarizable liquid/liquid interfaces using scanning ion conductance microscopy

The study of microscopic structure of a liquid/liquid interface is of fundamental importance due to its close relation to the thermodynamics and kinetics of interfacial charge transfer reactions.In this article,the microscopic structure of a non-polarizable water/nitrobenzene(W/NB) interface was evaluated by scanning ion conductance microscope(SICM).Using SICM with a nanometer-sized quartz pipette filled with an electrolyte solution as the probe,the thickness of this type of W/NB interface could be measured at sub-nanometer scale,based on the continuous change of ionic current from one phase to another one.The effects for thicknesses of the non-polarizable W/NB interfaces with different electrolyte concentrations,the Galvani potentials at the interface and the applied potentials on the probe were measured and systematically analyzed.Both experimental setups,that is an organic phase up and an aqueous down,and a reverse version,were employed to acquire the approach curves.These data were compared with those of an ideal polarizable interface under the similar experimental conditions,and several characteristics of non-polarizable interfaces were found.The thickness of a non-polarizable interface increases with the decrease of electrolyte concentration and the increase of applied potential,which is similar to the situation of a polarizable liquid/liquid interface.We also find that the Galvani potential across a non-polarizable interface can also influence the interfacial thickness,this phenomenon is difficult to observe when using polarizable interface.Most importantly,by the comparison of two kinds of liquid/liquid interfaces,we experimentally proved that much more excess ions are gathered in the space charge layer of non-polarizable interfaces than in that of polarizable interfaces.These results are consistent with the predictions of molecular dynamic simulations and X-ray reflectivity measurements.     

Study on the liquid membrane oscillation of water/oil/water system containing TTAB and picric acid

The liquid membrane oscillation of a novel water （aqueous tetradecyl trimethyl ammoniumbromide, TTAB and alcohol solution）/oil （picric acid in chloroform solution）/water （aqueous glucose solution） system was investigated. By using homemade device, the curves of various liquid membranes oscillation with different concentration of TTAB and picric acid, types of alcohol and other organic solvents at different temperature were measured. The results show that the water （aqueous 7 mmol/L of TTAB and 0.5 mol/L of n-propanol solution）/oil （0.5 mmol/L of picric acid in chloroform solution）/water （aqueous glucose solution） system performed sustained and stable oscillation at 30 ℃. And the novel system can recognise added amino acid.     

Coupling of the orientations of thermotropic liquid crystals to protein binding events at lipid-decorated interfaces

We report a study of the interactions of proteins with monolayers of phospholipids (D/L-alpha-dipalmitoyl phosphatidylcholine and L-alpha-dilauroyl phosphatidylcholine) spontaneously assembled at an interface between an aqueous phase and a 20-microm-thick film of a nematic liquid crystal (4'-pentyl-4-cyanobiphenyl). Because the orientation of the liquid crystal is coupled to the organization of the lipids, specific interactions between phospholipase A2 and the lipids (binding and/or hydrolysis) that lead to reorganization of the lipids are optically reported (using polarized light) as dynamic orientational transitions in the liquid crystal. In contrast, nonspecific interactions between proteins such as albumin, lysozyme, and cytochrome-c and the lipid-laden interface of the liquid crystal are not reported as orientational transitions in the liquid crystals. Concurrent epifluorescence and polarized light imaging of labeled lipids and proteins at the aqueous-liquid crystal interface demonstrate that spatially patterned orientations of the liquid crystals observed during specific binding of phospholipase A2 to the interface, as well as during the subsequent hydrolysis of lipids by phospholipase A2, reflect the lateral organization (micrometer-sized domains) of the proteins and lipids, respectively, at the aqueous-liquid crystal interface.     

Capillary rise of a meniscus with phase change

The Lucas-Washburn equation, describing the motion of a liquid body in a capillary tube, is extended to account for the effect of phase change - evaporation or condensation. The system is found to always possess a stable equilibrium state when the temperature jump across the interface is confined to a certain range. We show that phase change affects the equilibrium height of the meniscus, the transition threshold from monotonic to oscillatory dynamics, and the frequency of oscillations, when present. At higher mass transfer rates and/or large capillary radii, vapor recoil is found to be the dominant factor. Evaporation lowers the equilibrium height, increases the oscillation frequency and lowers the transition threshold to oscillations. For condensation, two regimes are identified: at high mass transfer rates similar trends to those of evaporation are observed, whereas the opposite is found for low mass transfer rates, resulting in an increased equilibrium height, lower oscillation frequencies and a shift of the transition threshold toward monotonic dynamics.     

Step by Step Induced Growth of Zinc-Metal Interface on Graphdiyne for Aqueous Zinc-Ion Batteries

Rechargeable aqueous zinc ion batteries (AZIBs) promise high energy density, low redox potential, low cost and safety; however, their cycle performances are seriously insufficient to restrict the progress in this field. We propose a new concept of atomic electrode formed on the graphdiyne (GDY). This new idea electrode was synthesized by selectively, uniformly, and stably anchoring Zn atoms on GDY at the beginning of plating. The Zn atoms are induced to grow into larger size Zn clusters, which continue to grow into nanoflat. Finally, a new heterojunction interface is formed on GDY without any Zn dendrites and side reactions, even at high current densities. Such stepwise induction of growth greatly suppresses the formation of Zn dendrites, resulting in high electroplating/stripping reversibility and lifespan of AZIBs.     

侧链液晶聚硅氧烷langmuir膜的原子力显微镜观察

通过原子力显微镜观测了含手性基团侧链液晶聚硅氧烷在空气/水界面上的单层膜,观测了成膜物在界面形成微畴结构以及表面压力升高时微畴聚集、重排过程,分析了纳米级微畴形成、聚集和重排的机理和规律。     

Direct nanomechanical measurement of an anchoring transition in a nematic liquid crystal subject to hybrid anchoring conditions

We have used a surface forces apparatus to measure the normal force between two solid curved surfaces confining a film of nematic liquid crystal (5CB, 4'-n-pentyl-4-cyanobiphenyl) under hybrid planar-homeotropic anchoring conditions. Upon reduction of the surface separation D, we measured an increasingly repulsive force in the range D = 35-80 nm, reaching a plateau in the range D = 10-35 nm, followed by a short-range oscillatory force at D < 5 nm. The oscillation period was comparable to the cross-sectional diameter of the liquid crystal molecule and characteristic of a configuration with the molecules parallel to the surfaces. These results show that the director field underwent a confinement-induced transition from a splay-bend distorted configuration at large D, which produces elastic repulsive forces, to a uniform planar nondegenerate configuration with broken homeotropic anchoring, which does not produce additional elastic forces as D is decreased. These findings, supported by measurements of the birefringence of the confined film at different film thicknesses, provide the first direct observation of an anchoring transition on the nanometer scale.     

Experimental investigation of evaporation and condensation in the contact line region of a thin liquid film experiencing small thermal perturbations

Image-analyzing interferometry technique is successfully used to study microscale transport processes related to a curved microfilm on a solid substrate. Digital image processing is used to analyze the images of interference fringes, leading to the evaluation of liquid (heptane) film thickness and curvature profiles at different inclinations on a high refractive index glass surface. The curvature profiles obtained at different inclinations clearly demonstrate that there is a maximum in curvature near the junction of the adsorbed film (of uniform thickness) and the curved film, and then it becomes constant in the thicker portions of the film. The adsorbed film thickness is measured for horizontal as well as inclined positions. Experimentally obtained values of the dispersion constants are compared to those predicted from the Dzyaloshinskii-Lifshitz-Pitaevskii (DLP) theory, and reasonable agreements were obtained. A parameter alpha is defined and experimentally evaluated to quantify the closeness of the system to equilibrium. The nonequilibrium behavior of this parameter alpha is also observed with certain heat input at a particular inclination. A small thermal perturbation is used to force the liquid meniscus to undergo a cycle of alternating condensation and evaporation. High-speed video-microscopy and subsequent image analysis are used for data analysis. The numerical solution of a model that takes into account the balance between the suction and the capillary force is compared with the data to elicit new insights into the evaporation/condensation phenomena and to estimate the interfacial temperature differences for near-equilibrium situations.