Interfacial tension and mechanism of liquid-liquid phase separation in aqueous media.

The organization of multiple subcellular compartments is controlled by liquid-liquid phase separation. Phase separation of this type occurs with the emergence of interfacial tension. Aqueous two-phase systems formed by two non-ionic polymers can be used to separate and analyze biological macromolecules, cells and viruses. Phase separation in these systems may serve as the simple model of phase separation in cells also occurring in aqueous media. To better understand liquid-liquid phase separation mechanisms, interfacial tension was measured in aqueous two-phase systems formed by dextran and polyethylene glycol and by polyethylene glycol and sodium sulfate in the presence of different additives. Interfacial tension values depend on differences between the solvent properties of the coexisting phases, estimated experimentally by parameters representing dipole-dipole, ion-dipole, ion-ion, and hydrogen bonding interactions. Based on both current and literature data, we propose a mechanism for phase separation in aqueous two-phase systems. This mechanism is based on the fundamental role of intermolecular forces. Although it remains to be confirmed, it is possible that these may underlie all liquid-liquid phase separation processes in biology.

Ultralow interfacial tensions of aqueous two-phase systems measured using drop shape.

Aqueous solutions of different polymers can separate and form aqueous two-phase systems (ATPS). ATPS provide an aqueous, biocompatible, and mild environment for separation and fractionation of biomolecules. The interfacial tension between the two aqueous phases plays a major role in ATPS-mediated partition of biomolecules. Because of the structure of the two aqueous phases, the interfacial tensions between the phases can be 3-4 orders of magnitude smaller than conventional fluid-liquid systems: ∼1-100 µJ/m(2) for ATPS compared to ∼72 mJ/m(2) for the water-vapor interface. This poses a major challenge for the experimental measurements of reproducible interfacial tension data for these systems. We address the need for precise determination of ultralow interfacial tensions by systematically studying a series of polymeric ATPS comprising of polyethylene glycol (PEG) and dextran (DEX) as the phase-forming polymers. Sessile and pendant drops of the denser DEX phase are formed within the immersion PEG phase. An axisymmetric drop shape analysis (ADSA) is used to determine interfacial tensions of eight different ATPS. Specific criteria are used to reproducibly determine ultralow interfacial tensions of the ATPS from pendant and sessile drops. Importantly, for a given ATPS, pendant drop and sessile drop experiments return values within 0.001 mJ/m(2) indicating reliability of our measurements. Then, the pendant drop technique is used to measure interfacial tensions of all eight ATPS. Our measured values range from 0.012 ± 0.001 mJ/m(2) to 0.381 ± 0.006 mJ/m(2) and vary with the concentration of polymers in equilibrated phases of ATPS. Measurements of ultralow interfacial tensions with such reproducibility will broadly benefit studies involving partition of different biomolecules in ATPS and elucidate the critical effect of interfacial tension.

Line tension and line entropy associated with the monolayer/trilayer boundary of smectic liquid crystal at the air-water interface.

Molecularly thin films of the smectic liquid crystal 4'-octyl-4-biphenylcarbonitrile (8CB) at the air-water interface phase separate into regions with different numbers of layers, in analogy with freestanding smectic liquid crystalline films. This paper reports the line tension associated with the boundary of coexisting trilayer and monolayer phases of in Langmuir films of 8CB at the air-water interface as a function of temperature and humidity and infers information on the boundary profile between the coexisting phases. Two complementary techniques are used to characterize the 8CB thin films: surface pressure-area isotherm and Brewster angle microscopy (BAM). We determine the line tension by stretching isolated domains from their equilibrium circular shape and analyzing the free relaxation with a hydrodynamic model. Then, we interpret the line tension vs temperature data in terms of an excess line entropy for the domain boundary, which requires careful consideration of the thermodynamics of inhomogeneous monolayer systems.

Surface Tension of Two Near-Ideal Binary Liquid Mixtures and the Influence of Adjacent Vapors.

The measured surface tension of a binary liquid is found to depend strongly on the constituents of the adjacent vapor and on whether equilibrium has been achieved, giving insight into the complex interfacial configuration. This dependence is quantified by three techniques that offer complementary insights: surface tension measurements with a constrained sessile drop surrounded by different vapors, surface tension measurements by surface light scattering spectroscopy in a sealed cell at equilibrium, and molecular dynamics simulations of the equilibrium surface tension and excess surface concentration. Ensuring homogeneity of the binary liquid, which is essential for surface light scattering, was found to be nontrivial and was assured by high-sensitivity Schlieren imaging. Two pairs of liquids, n-pentane with 2-methylpentane and n-pentane with n-hexane, were investigated. The first pair was motivated by the observed improvement in the effectiveness of binary fluids versus a single constituent in wickless heat pipes studied in microgravity. The second pair was used for comparison. Experimental evaluation of different volume fractions of the two liquids showed strong dependence of surface tension on the relative concentration of different molecules near the interfacial region. For the above pairs of liquids, which appear to form ideal mixtures in bulk, we present sufficiently precise surface tension measurements to indicate unexpectedly complex behaviors at interfaces.

A robust polynomial fitting approach for contact angle measurements.

Polynomial fitting to drop profile offers an alternative to well-established drop shape techniques for contact angle measurements from sessile drops without a need for liquid physical properties. Here, we evaluate the accuracy of contact angles resulting from fitting polynomials of various orders to drop profiles in a Cartesian coordinate system, over a wide range of contact angles. We develop a differentiator mask to automatically find a range of required number of pixels from a drop profile over which a stable contact angle is obtained. The polynomial order that results in the longest stable regime and returns the lowest standard error and the highest correlation coefficient is selected to determine drop contact angles. We find that, unlike previous reports, a single polynomial order cannot be used to accurately estimate a wide range of contact angles and that a larger order polynomial is needed for drops with larger contact angles. Our method returns contact angles with an accuracy of <0.4° for solid-liquid systems with θ < ~60°. This compares well with the axisymmetric drop shape analysis-profile (ADSA-P) methodology results. Above about 60°, we observe significant deviations from ADSA-P results, most likely because a polynomial cannot trace the profile of drops with close-to-vertical and vertical segments. To overcome this limitation, we implement a new polynomial fitting scheme by transforming drop profiles into polar coordinate system. This eliminates the well-known problem with high curvature drops and enables estimating contact angles in a wide range with a fourth-order polynomial. We show that this approach returns dynamic contact angles with less than 0.7° error as compared to ADSA-P, for the solid-liquid systems tested. This new approach is a powerful alternative to drop shape techniques for estimating contact angles of drops regardless of drop symmetry and without a need for liquid properties.

Gasous hole closing in a polymer Langmuir monolayer.

The hole-closing phenomenon is studied in a polymer Langmuir film with coexisting gaseous and liquid phases both as a test of hydrodynamic theories of a two-dimensional fluid embedded in a three-dimensional one and as a means to accurately determine line tension, an important parameter determining size, shape, and dynamics within these and other membrane model systems. The hole-closing curve consists of both a universal linear regime and a history-dependent nonlinear one. Improved experimental technique allows us to explore the origin of the nonlinear regime. The linear regime confirms previous theoretical work and yields a value lambda = (0.69 +/- 0.02) pN for the line tension of the boundary between the gaseous and liquid phases. The observed hole closing also demonstrates that the two-dimensional polymer gas must be taken as having a small, probably negligible elasticity, so that line-tension measurements assuming that both phases are incompressible should be re-evaluated.

Determination of interphase line tension in Langmuir films.

A Langmuir film is a molecularly thin film on the surface of a fluid; we study the evolution of a Langmuir film with two coexisting fluid phases driven by an interphase line tension and damped by the viscous drag of the underlying subfluid. Experimentally, we study a 4{'} -8-alkyl[1, 1{'} -biphenyl]-4-carbonitrile (8CB) Langmuir film via digitally imaged Brewster angle microscopy in a four-roll mill setup which applies a transient strain and images the response. When a compact domain is stretched by the imposed strain, it first assumes a bola shape with two tear-drop shaped reservoirs connected by a thin tether which then slowly relaxes to a circular domain which minimizes the interfacial energy of the system. We process the digital images of the experiment to extract the domain shapes. We then use one of these shapes as an initial condition for the numerical solution of a boundary-integral model of the underlying hydrodynamics and compare the subsequent images of the experiment to the numerical simulation. The numerical evolutions first verify that our hydrodynamical model can reproduce the observed dynamics. They also allow us to deduce the magnitude of the line tension in the system, often to within 1%. We find line tensions in the range of 200-600pN; we hypothesize that this variation is due to differences in the layer depths of the 8CB fluid phases.

Technique for characterization of the wettability properties of gas diffusion media for proton exchange membrane fuel cells.

In this paper, a measurement technique based on the capillary penetration method is presented for use in estimating the wettability properties of gas diffusion media (GDM), a component for proton exchange membrane fuel cells (PEMFCs). The present method solves several critical issues, including the formation of an external meniscus and the evaporation of imbibed solvent, both of which greatly affect the apparent rate of solvent imbibition. Solvent evaporation is prevented by inserting a GDM sample between two thin stainless steel plates to form a tri-layer structure having non-porous evaporation covers on each side of the porous GDM sample. The presence of stainless steel plates in contact with the GDM sample was demonstrated to have a negligible impact on the evaluation of the Washburn material constant.

Surface response functions for a thin-film between fluids with infinite boundaries and for a fluid-fluid interface between finite boundaries.

Measuring the surface response function of a fluid allows us to ascertain many of its properties. Simplified surface response functions are presented for several interface conditions, including (a) a thin-film between two fluids of infinite extent, (b) the newly derived fluid-fluid interface between finite boundaries, and (c) the traditional fluid-fluid interface between infinite boundaries. The finite-boundary derivation indicates that wall effects are very short range. This portends that the effects of external vibrations, which traditionally make this measurement challenging, can be mitigated by scattering from thin fluid layers.

Near-field microwave microscope and electron-spin-resonance detection: ruby crystal surface.

Microwave photons can image a surface by using near-field geometry with spatial resolution close to the nanometer-length scale. We detected electron-spin resonance (ESR) on ruby surfaces by using microwave photons at the S-band frequency (3.73 GHz). The spatial locations of the electron-spin centers were pinpointed with localized incident microwave photons generated by using evanescent microwave microscopy (EMM). We show that the EMM probe is capable of resolving 20,000 spin transitions, compared with the approximately 10(10) minimum detectable spins of the conventional continuous-wave ESR spectrometer. This represents roughly a 6-order-of-magnitude enhancement in sensitivity. Our ultimate goal is to achieve the minimum detectable spin transition of a single electron and nanometer-level spatial resolution by using microfabricated atomic force microscopy-EMM probes.