Anisotropic fluctuation model for surfactant-laden liquid-liquid crystal interfaces

A model for thermal fluctuations on surfactant-laden liquid-liquid crystal interfaces is formulated and used to derive the expression of the mean square displacement as a function of four elastic moduli of the interface. The measurable liquid crystal contributions to thermal roughness include the average molecular orientation, the interfacial anchoring modulus, and the bulk elasticity modulus. Surfactant-driven interfacial orientation transitions provide an additional means to extract interfacial elastic moduli parameters in surfactant-laden liquid-liquid crystal interfaces in conjunction with thermal roughness measurements.     

New highly anisotropic liquid crystal materials for high-frequency applications

We report on the developed liquid crystal (LC) compositions with large optical anisotropy and low melting point on the basis of synthesised quaterphenyl and quinquiphenyl LC compounds containing lateral substituents. Optical and dielectric anisotropies of synthesised compounds were studied to select the most optimal compounds for high-frequency applications. As a result of the research, base matrices with a wide range of the nematic phase were developed and their mesomorphic and physicochemical properties were investigated. Based on the experimental data, the influence of various fragments of molecules on the magnitude of permittivity in the high-frequency region, as well as on the loss tangent of LCs was established.     

Theory of curved interfaces and membranes: Mechanical and thermodynamical approaches

The mechanical and thermodynamical approaches to the theory of the general curved interfaces are presented and compared. In the mechanical approach a curved interface or membrane is characterized by the tensors of surface stresses and moments. They are connected by the surface balances of the linear and angular momentum. On the other hand, in the thermodynamical approach the surface is characterized by the scalar dilation and shear tensions as well as by the bending and torsion moments. In this review we investigate the problem about the relationships connecting the mechanical and thermodynamical approaches. We find that these two approaches are in a good agreement, that they are complementary to each other and represent the two parts of a self-consistent theory. The latter can be applied to any system where curved interfaces, thin films or membranes are present: microemulsions, lamellar and sponge phases, lipid vesicles and cell membranes, capillary waves at interfaces, undulation and peristaltic surface forces, lateral capillary forces between particles in thin liquid films, etc.     

One-step in situ synthesis of NHx-adsorbed rhodium nanocrystals at liquid-liquid interfaces for possible electrocatalytic applications

Nearly monodisperse rhodium nanoparticles with adsorbed NH(x) were synthesized at the CCl(4)-water interface. The presence of NH(x)-adsorbed species was confirmed by energy-dispersive X-ray analysis (EDX) and X-ray photoelectron spectroscopy (XPS) studies. The synthesis of controlled size 2-38 nm rhodium particles was studied as a function of reducing agent concentration by transmission electron microscopy (TEM). HRTEM confirmed the formation of rhodium nanoparticles having fringe spacing consistent with reported Rh (111) planes. The continuity of these films over an area of 1×1 μm was revealed by atomic force microscopy (AFM) studies. The electrocatalytic application of these nanostructure Rh-NH(x) thin films for formaldehyde oxidation in 0.5M NaOH was investigated by cyclic voltammetry. The Rh nanoparticles formed by the present strategy are expected to be useful for other catalytic applications also.     

Adsorption of colloidal particles to curved interfaces

As a simple model for a Pickering emulsion droplet, we consider the adsorption of spherical particles to a spherical liquid-liquid interface in order to investigate the curvature effect on the particle adsorption. By taking into account both the surface and the volume energies due to the presence of a particle, we show that the equilibrium contact angle is determined by the classical Young's equation although the adsorption energy depends on the curvature. We also calculate the partitioning of the colloidal particles among the two liquids and the interface. The distribution of colloidal particles is expressed in terms of the interfacial curvature as well as the relative wettability of the particle.     

Adsorption of Janus particles to curved interfaces

We investigate the adsorption of a spherical Janus particle to a spherically curved liquid-liquid interface. We show that the equilibrium contact angle is determined by the geometry of the particle, its wettability, and also the interfacial curvature. In contrast with a homogeneous particle, there is a preferred interfacial curvature (spontaneous curvature) due to the Janus particle when the particle satisfies certain conditions.     

A new anisotropic soft-core model for the simulation of liquid crystal mesophases

A new anisotropic soft-core model is presented, which is suitable for the rapid simulation of liquid crystal mesophases. The potential is based on a soft spherocylinder, which can be easily tuned to favor different liquid crystal mesophases. The soft-core nature of the potential makes it suitable for long-time step molecular dynamics or dissipative particle dynamics simulations, particularly as a reference model for mesogens or as an anisotropic solvent for use in combination with atomistic models. Results are presented for two variants of the new potential, which show different mesophase behaviors. Variants of the potential can also be linked together to produce more complicated molecular structures. Here, as an example, results are provided for a model multipedal liquid crystal, which has eight liquid crystalline groups linked to a central core via semiflexible chains. Here, despite the complexity of molecular structure, the model succeeds in showing the spontaneous formation of a liquid crystal phase. The results also demonstrate that there is a very strong coupling between the internal structure of the multipedal mesogen and the molecular order of the phase, with the mesogen spontaneously undergoing major structural rearrangement at the transition to the liquid crystal phase.     

Thermodynamic model of surfactant adsorption on soft liquid crystal interfaces

The Gibbs adsorption isotherm for planar liquid crystal/fluid interfaces is derived using the anisotropic Gibbs-Duhem equation. The Gibbs adsorption isotherm for planar interfaces is used to analyze the adsorption-driven orientation transition in aqueous solutions of anionic surfactants in contact with rodlike uniaxial nematic liquid crystal films. In qualitative agreement with experiments, the model predicts that, as the surfactant concentration increases, the tangential (planar) average molecular orientation of the liquid crystal with respect to the interface undergoes a transition to a normal (homeotropic) orientation. The anchoring coefficient or strength of anisotropic component of the interfacial tension is shown to depend on the surfactant's concentration. Analyzing the response to addition of a co-cation, the model reveals that, as the fractional coverage of the surfactant's chains increases, the interpenetration of liquid crystal molecules between the adsorbed surfactant tails promotes the orientation transition; at even higher surfactant chain concentrations, interpenetration is hindered because of lack of available space and a random surface orientation emerges. Thus, for aqueous surfactant solutions in contact with nematic liquid crystals, increasing the surfactant concentration leads to the following interfacial liquid crystal orientation transition cascade, planar orientation --> homeotropic orientation --> random orientation, which can lead to new sensor capabilities and surface structuring processes.     

Renewable dehydrogenase-based interfaces for bioelectronic applications

Bioelectronic interfaces that establish electrical communication between redox enzymes and electrodes have potential applications as biosensors, biocatalytic reactors, and biological fuel cells. However, these interfaces contain labile components, including enzymes and cofactors, which have limited lifetimes and must be replaced periodically to allow long-term operation. Current methods to fabricate bioelectronic interfaces do not allow facile replacement of these components, thus limiting the useful lifetime of the interfaces. In this paper we describe a versatile new fabrication approach that binds the enzymes and cofactors using reversible ionic interactions. This approach allows the interface to be removed via a simple pH change and then replaced to fully regenerate the biocatalytic activity. The positively charged polyelectrolyte poly(ethylenimine) was used to ionically bond a dehydrogenase enzyme and its cofactor to a gold electrode that was functionalized with 3-mercaptopropionic acid and the electron mediator toluidine blue O. By reducing the pH, the surface-bound 3-mercaptopropionic acid was protonated, disrupting the ionic bonds and releasing the enzyme-modified polyelectrolyte. After neutralization, fresh enzyme and cofactor were bound, regenerating the bioelectronic interface. Cyclic voltammetry, chronoamperometry, constant potential amperometry, electrochemical impedance spectroscopy, and Fourier transform infrared spectroscopy analyses were used to characterize the bioelectronic interfaces. For the two enzymes tested (secondary alcohol dehydrogenase and sorbitol dehydrogenase) and their respective cofactors (beta-nicotinamide adenine dinucleotide phosphate and beta-nicotinamide adenine dinucleotide), the reconstituted interface exhibited a surface coverage, an electron-transfer coefficient, and a turnover rate similar to those of the original interface.     

Liquid-vapor isotherm in a closed single-component system with curved interfaces

A thermodynamic model to obtain the radius of bubbles or droplets in a single-component system for a given temperature, total volume, and phase distribution is developed. The general formulation of the model includes bubbles or droplets in the form of spheres, truncated spheres on a flat solid surface or inside conical walls. In these three geometries the liquid-vapor curvature radius is positive but in the case of conical walls it can be also negative. States with different dispersed-phase distributions are compared using the total free energy of the system. When the curvature radius is positive, it has a minimum nonvanishing value and the occurrence of the Ostwald ripening is energetically favorable. On the other hand, when the curvature radius is negative, it is energetically more favorable to find the dispersed phase even in the expected single-phase region, and the occurrence of an anti-ripening phenomenon. The PV isotherms obtained from the model and the applicability of the results to the nucleation process are discussed.     

Helfrich model of membrane bending: From Gibbs theory of liquid interfaces to membranes as thick anisotropic elastic layers

Helfrich model of membrane bending elasticity has been most influential in establishment and development of Soft-Matter Physics of lipid bilayers and biological membranes. Recently, Helfrich theory has been extensively used in Cell Biology to understand the phenomena of shaping, fusion and fission of cellular membranes. The general background of Helfrich theory on the one hand, and the ways of specifying the model parameters on the other, are important for quantitative treatment of particular biologically relevant membrane phenomena. Here we present the origin of Helfrich model within the context of the general Gibbs theory of capillary interfaces, and review the strategies of computing the membrane elastic moduli based on considering a lipid monolayer as a three-dimensional thick layer characterized by trans-monolayer profiles of elastic parameters. We present the results of original computations of these profiles by a state-of-the-art numerical approach.     

Directed assembly of carbon nanotubes at liquid-liquid interfaces: nanoscale conveyors for interfacial biocatalysis

We report that single-walled carbon nanotubes (SWNTs) can be directed to aqueous-organic interfaces with the aid of surfactants. This phenomenon can also be used to transport enzymes to the interface to effect biphasic biotransformations. Consequently, SWNT-enzyme conjugates enhance the rate of catalysis by up to 3 orders of magnitude relative to the rates obtained with native enzymes in similar biphasic systems. Furthermore, we demonstrate that this concept can be extended to other nanomaterials and other enzymes, thereby providing a general strategy for efficient interfacial biocatalysis. The ability to direct the assembly of nanotubes at the interface also provides an attractive route to organizing these nanomaterials into 2D architectures.     

Configurational temperature and local properties of the anisotropic Gay-Berne liquid crystal model: applications to the isotropic liquid/vapor interface and isotropic/nematic transition

Molecular simulations in the isothermal statistical ensembles require that the macroscopic thermal and mechanical equilibriums are respected and that the local values of these properties are constant at every point in the system. The thermal equilibrium in Monte Carlo simulations can be checked through the calculation of the configurational temperature, k(B)T(conf)=<|?(r)U(r(N))|(2)>/, where ?(r) is the nabla operator of position vector r. As far as we know, T(conf) was never calculated with the anisotropic Gay-Berne potential, whereas the calculation of T(conf) is much more widespread with more common potentials (Lennard Jones, electrostatic, ...). We establish here an operational expression of the macroscopic and local configurational temperatures, and we investigate locally the isotropic liquid phase, the liquid?/?vapor interface, and the isotropic-nematic transition by Monte Carlo simulations.     

Residence time model for assessing liquid-liquid extraction systems

A model based on the residence time of solvent in the extraction system may be used to describe the dynamic operation of a continuous liquid-liquid extractor. It is proposed that optimum performance occurs when the extract exiting from the contactor is near equilibrium with the solution being extracted. This approach was tested on two commercially available continuous extraction systems. The difference in their performance was found to be related to the level of agitation of the two contactor vessels: the stirred system was approximately six times more efficient than the simple column continuous extractor. The stirred system achieved a near equilibrium analyte distribution between the solvent and sample and could be described accurately in terms of residence time theory. This was in marked contrast to its unmixed counterpart where the analyte distribution between solvent and sample reached 14% of its equilibrium value during its residence in the contactor. The effect of dead volume of solvent within the extraction assembly on the extraction rate was also apparent; its main effect was to delay the extraction process.     

Mechanical properties of hexadecane-water interfaces with adsorbed hydrophobic bacteria

This study focuses on how intact, hydrophobic bacteria in their stationary (i.e., non-dividing) phase could adsorb onto the hexadecane–water interface and alter its mechanical properties. The two strains of bacteria used in forming the interfacial films were Acinetobacter venetianus RAG-1 and Rhodococcus erythropolis 20S-E1-c. Using the dynamic pendant drop technique, the film interfacial tension was monitored as the surface area was made to undergo transient changes. Under static conditions, both types of bacteria had no effect on the interfacial tension. When subjected to transient excitations, however, the two bacterial films exhibited clear and qualitatively similar rheological properties: they responded as two-dimensional Maxwellian materials when the interfacial areas were dilated suddenly, but appeared to be purely elastic upon rapid area compression. Such rheological behaviours are “non-linear” in that the responses of the tension to area dilation and contraction are not mirror images of one another. Despite their qualitative similarities, the two types of film had very distinct film elasticities and relaxation times. The most striking difference between the two bacterial films was revealed under continuous reduction of area, when the A. venetianus RAG-1 system displayed a “paper-like” interface, whereas the interface of the R. erythropolis 20S-E1-c system was “soap film-like”. These macroscopic observations could be explained by the surface ultrastructures of the two cell strains determined using transmission electron microscopy.     

Numerical approaches to determine the interface tension of curved interfaces from free energy calculations

A recently proposed method to obtain the surface free energy σ(R) of spherical droplets and bubbles of fluids, using a thermodynamic analysis of two-phase coexistence in finite boxes at fixed total density, is reconsidered and extended. Building on a comprehensive review of the basic thermodynamic theory, it is shown that from this analysis one can extract both the equimolar radius R(e) as well as the radius R(s) of the surface of tension. Hence the free energy barrier that needs to be overcome in nucleation events where critical droplets and bubbles are formed can be reliably estimated for the range of radii that is of physical interest. It is found that the conventional theory of nucleation, where the interface tension of planar liquid-vapor interfaces is used to predict nucleation barriers, leads to a significant overestimation, and this failure is particularly large for bubbles. Furthermore, different routes to estimate the effective radius-dependent Tolman length δ(R(s)) from simulations in the canonical ensemble are discussed. Thus we obtain an instructive exemplification of the basic quantities and relations of the thermodynamic theory of metastable droplets/bubbles using simulations. However, the simulation results for δ(R(s)) employing a truncated Lennard-Jones system suffer to some extent from unexplained finite size effects, while no such finite size effects are found in corresponding density functional calculations. The numerical results are compatible with the expectation that δ(R(s) → ∞) is slightly negative and of the order of one tenth of a Lennard-Jones diameter, but much larger systems need to be simulated to allow more precise estimates of δ(R(s) → ∞).     

Renewable nanocomposite layer-by-layer assembled catalytic interfaces for biosensing applications

A novel, easily renewable nanocomposite interface based on layer-by-layer (LbL) assembled cationic/anionic layers of carbon nanotubes customized with biopolymers is reported. A simple approach is proposed to fabricate a nanoscale structure composed of alternating layers of oxidized multiwalled carbon nanotubes upon which is immobilized either the cationic enzyme organophosphorus hydrolase (OPH; MWNT-OPH) or the anionic DNA (MWNT-DNA). The presence of carbon nanotubes with large surface area, high aspect ratio and excellent conductivity provides reliable immobilization of enzyme at the interface and promotes better electron transfer rates. The oxidized MWNTs were characterized by thermogravimetric analysis and Raman spectroscopy. Fourier transform infrared spectroscopy showed the surface functionalization of the MWNTs and successful immobilization of OPH on the MWNTs. Scanning electron microscopy images revealed that MWNTs were shortened during sonication and that LbL of the MWNT/biopolymer conjugates resulted in a continuous surface with a layered structure. The catalytic activity of the biopolymer layers was characterized using absorption spectroscopy and electrochemical analysis. Experimental results show that this approach yields an easily fabricated catalytic multilayer with well-defined structures and properties for biosensing applications whose interface can be reactivated via a simple procedure. In addition, this approach results in a biosensor with excellent sensitivity, a reliable calibration profile, and stable electrochemical response.     

Surface electron screening theory and its applications to metal-electrolyte interfaces

The modern theory of the static electron response of a metal surface is reviewed. The basic motive of the survey, originated from the analysis of the contradictions between the widely accepted sharp boundary models and experiment, is self-consistency. Applications of the various versions of the density functional formalism to the surface response calculations are considered. In particular, the screening of the uniform electrostatic field is discussed on the basis of the local (Thomas-Fermi type) and nonlocal statistical models, within the Kohn-Sham scheme (in the linear response approximation and beyond it) and using sum rules. The results of the self-consistent analysis of a number of phenomena at the metal-vacuum interphase (e.g. electron and ion field emission or ionization and polarization of a minute metal particle) are briefly described. The main attention is given to the effect of a metal on the electrical properties ( the bilayer capacity first of all) of the metal-electrolyte interphases. The results obtained in this field aggravated the question about the possibility of the negative capacity values, sharply arised in connection with the “Cooper-Harrison catastrophe”. This question and the associated problem of the bilayer instability are discussed in the survey applying the results to the model microscopical calculations and the “gedanken experiments” with the electro-mechanical “catastrophe machines”.     

Compact model for multi-phase liquid-liquid flows in micro-fluidic devices

We present a compact model describing the laminar flow of viscous multiphase fluids in micro-channel networks. We apply this model to the flow of 2 immiscible fluids representing typically oil and water, in a network of micro-channels comprising one inlet for each fluid splitting into 2 branches meeting at a T-junction, where the 2 phases are combined before exiting the network through two outlets. This network is akin to an electrical "Wheatstone bridge" and represents a simplified interdigital micro-reactor, where the fluids to be mixed are separated into smaller branches and later re-combined together. We show from an analytical solution and a computational modelling that fluid flow inside this network is very sensitive to small differences in fluid resistance between the various branches of the network, which may lead to catastrophic error in fluid distribution between the various branches that can have a profound effect on mixing. These errors depend on the viscosity difference between the fluids, on the processing conditions, and also on the geometric resistance parameters of the various channels. Increasing the resistance of the distribution channels upstream of the fluid junctions allows minimisation of the distribution errors. Interaction between the fluids can also lead to transients that are orders of magnitude longer than the flooding time of the channels. This may be exploited to provide impedance-like terms in flui-logic operations.