Adhesion hysteresis from interdependent capillary and electrostatic forces

Adhesion hysteresis commonly occurs at the nanoscale in humid atmospheres, yet mechanisms are not entirely understood. Here, the adhesion forces between silicon (111) oxide surfaces and tungsten oxide probes have been examined using interfacial force microscopy. The results show that the adhesion forces during surface approach and separation differ not only in magnitude but also in mechanism, arising mainly from capillary and electrostatic forces, respectively. Surface contact leads to a transient intersurface potential on dewetting. This mechanism of adhesion hysteresis differs in not relying singly on hysteretic wetting. Furthermore, by biasing the surfaces, nonadditivity is demonstrated between the capillary and electrostatic forces at the onset of condensation. These results hold important implications on the interpretation of force in nanoprobe geometries in humid atmospheres.     

芯片毛细管电泳及其在生命科学中的应用

芯片毛细管电泳 (Chip CE)技术在近几年已取得了很大的进展。本文着重介绍芯片毛细管区带电泳技术 ,对等电聚焦、等速电泳、自由溶液电泳及胶束电动色谱等其它芯片电泳模式也有所提及。讨论了芯片材料和制作技术、芯片的几何形状、样品的操作和衍生、检测及芯片毛细管电泳技术的应用 ,特别是在核酸和蛋白质的分离分析中的进展     

Capillary electrophoresis on microchip

Capillary electrophoresis and related techniques on microchips have made great strides in recent years. This review concentrates on progress in capillary zone electrophoresis, but also covers other capillary techniques such as isoelectric focusing, isotachophoresis, free flow electrophoresis, and micellar electrokinetic chromatography. The material and technologies used to prepare microchips, microchip designs, channel geometries, sample manipulation and derivatization, detection, and applications of capillary electrophoresis to microchips are discussed. The progress in separation of nucleic acids and proteins is particularly emphasized.     

Adsorption hysteresis in ordered mesoporous silicas

We review some recent progress in experimental studies of the adsorption hysteresis of simple molecules in ordered mesoporous silicas. We show that the nature of the adsorption hysteresis due to capillary condensation can be examined with less ambiguity by measuring the hysteresis loop for the ordered mesoporous silicas with three types of pore geometries (cylindrical, interconnected cylindrical, and interconnected spherical) over a wide temperature range. The adsorption hysteresis arises from the metastability of a confined phase and the temperature at which the hysteresis disappears is lower than the critical temperature of vapor-liquid equilibrium in pores. The hysteresis occurs mainly on the desorption rather than adsorption branch, irrespective of the pore geometries.     

Effect of capillary geometry on predicting electroosmotic volumetric flowrates in porous or fibrous media

Electrokinetic-based methods are used in a variety of applications including drug delivery and separation of biomolecules, among others. Many of these applications feature a fibrous or a porous medium that can be modeled by using capillary bundle models to predict the behavior of the electroosmotic flow within the particular system. The role of geometry in predicting volumetric flowrates in porous media is investigated by modeling the electroosmotic flow in idealized capillaries of rectangular, cylindrical, and annular geometries. This is achieved by the coupling of electrostatics and continuum hydrodynamics to obtain analytical expressions that govern the electrokinetically - driven volumetric flow within these idealized capillary geometries. A previous study developed a model to compare the cylindrical and annular capillary geometries by utilizing two methods that compare the areas of the two geometries. The methods used in this previous work will also be used in the present contribution to compare the volumetric flowrates in the cylindrical and annular capillaries with a rectangular capillary. Illustrative results will be presented to aid in the understanding of the influence of the various geometrical and electrostatic parameters that arise from the analysis of these volumetric flowrates. It was found that the electroosmotic volumetric flowrates are significantly affected by the capillary geometry.     

Interfacial slip on rough,patterned and soft surfaces: A review of experiments and simulations

Advancements in the fabrication of microfluidic and nanofluidic devices and the study of liquids in confined geometries rely on understanding the boundary conditions for the flow of liquids at solid surfaces. Over the past ten years, a large number of research groups have turned to investigating flow boundary conditions, and the occurrence of interfacial slip has become increasingly well-accepted and understood. While the dependence of slip on surface wettability is fairly well understood, the effect of other surface modifications that affect surface roughness, structure and compliance, on interfacial slip is still under intense investigation. In this paper we review investigations published in the past ten years on boundary conditions for flow on complex surfaces, by which we mean rough and structured surfaces, surfaces decorated with chemical patterns, grafted with polymer layers, with adsorbed nanobubbles, and superhydrophobic surfaces. The review is divided in two interconnected parts, the first dedicated to physical experiments and the second to computational experiments on interfacial slip of simple (Newtonian) liquids on these complex surfaces. Our work is intended as an entry-level review for researchers moving into the field of interfacial slip, and as an indication of outstanding problems that need to be addressed for the field to reach full maturity.     

Grand canonical Monte Carlo simulation study of capillary condensation between nanoparticles

Capillary condensation at the nanoscale differs from condensation in the bulk phase, because it is a strong function of surface geometry and gas-surface interactions. Here, the effects of geometry on the thermodynamics of capillary condensation at the neck region between nanoparticles are investigated via a grand canonical Monte Carlo simulation using a two-dimensional lattice gas model. The microscopic details of the meniscus formation on various surface geometries are examined and compared with results of classical macromolecular theory, the Kelvin equation. We assume that the system is composed of a lattice gas and the surfaces of two particles are approximated by various shapes. The system is modeled on the basis of the molecular properties of the particle surface and lattice gas in our system corresponding to titania nanoparticles and tetraethoxy orthosilicate molecules, respectively. This system was chosen in order to reasonably emulate our previous experimental results for capillary condensation on nanoparticle surfaces. Qualitatively, our simulation results show that the specific geometry in the capillary zone, the surface-surface distance, and the saturation ratio are important for determining the onset and broadening of the liquid meniscus. The meniscus height increases continuously as the saturation ratio increases and the meniscus broadens faster above the saturation ratio of 0.90. The change of the radius of curvature of the particle surface affects the dimensions of the capillary zone, which drives more condensation in narrow zones and less condensation in wide zones. The increase of surface-surface distance results in the decrease of the meniscus height or even the disappearance of the meniscus entirely at lower saturation ratios. These effects are significant at the nanoscale and must be carefully considered in order to develop predictive relationships for meniscus height as a function of saturation conditions.     

Microscale liquid dynamics and the effect on macroscale propagation in pillar arrays

Liquid dynamics in micropillar arrays have received significant fundamental interest and have offered opportunities for the development of advanced microfluidic, thermal management, and energy-harvesting devices. However, a comprehensive understanding of complex liquid behavior and the effect on macroscopic propagation rates in micropillar arrays is needed. In this work, we investigated the microscopic sweeping behavior of the liquid front along the spreading direction in micropillar arrays where the sweeping distance scales with the one-fifth power of time. We explain the scaling with a simplified model that captures the capillary pressure gradient at the liquid front. Furthermore, we show that such microscopic dynamics is the mechanism that decreases the macroscopic propagation rate. This effect is a result of the reduction in the interfacial energy difference used to generate the capillary pressure, which is explained with an energy-based model and corroborated with experiments. The results indicate the importance of accounting for the microscopic dynamics of the liquid on microstructured surfaces, particularly in sparse geometries.     

Polymer wall coatings for capillary electrophoresis

This review article describes the preparation of dynamic and static polymeric wall coatings for capillary electrophoresis. Properties of bare fused-silica surfaces and methods for the characterization of capillary coatings are summarized. The preparation and basic properties of neutral and charged wall coatings are considered. Finally, advantages and potential applications of various coatings are discussed.     

A generalized analysis of capillary flows in channels

Investigations on the motion of a fluid in capillary geometries have been extensively reported in the literature using both experimental and theoretical approaches. In this paper, the theories for capillary flow are generalized to a unified nonlinear second-order differential equation which takes the effects of the entrance, the inertial forces, and the dynamic contact angle into account. An analytical solution of the differential equation is obtained in the form of a double Dirichlet series. The readily evaluated analytical solution is compared with experimental and numerical results in the literature, which shows a good agreement. It is demonstrated that this analytical approach can be used to predict capillary flows for a wide range of fluids and parallel-plate and tube geometries in a unified manner.     

Simulations of novel nanostructures formed by capillary effects in lithography

High aspect ratio three-dimensional nanostructures are of tremendous interest to a wide range of fields such as photonics, plasmonics, fluid mechanics, and biology. Recent developments in capillary force lithography (CFL) have focused on taking advantage of the formation of menisci to enhance the functionality of small size-scale structures. In this study, simulations of the three-dimensional shapes of equilibrium menisci formed in capillaries with various cross-section geometries are studied. The capillary cross sections include regular polygons and equilateral star-shapes with sharp and rounded corners. The characteristic dimension of the physical lithography systems which are simulated is on the order of 100nm. At such size-scale, surface-tension-effects are predominant, and as a consequence, our simulations demonstrate that nanometer-sized structures with great application potentials can be fabricated. Specifically, this study demonstrates that surfaces with three-dimensional nanoscale structures can be fabricated from templates with micron or sub-micron features through the development of cusps in the corners of the polygonal capillaries. Quantitatively, the effects of contact angle, corner angle, meniscus confinement, and corner rounding radius are examined and scaling analyses are presented to describe the dependencies of the height variation across the meniscus on these parameters. These simulations serve as useful guides for extending the development and implementation of capillary force lithography.     

Capillary electrochromatography using polyelectrolyte multilayer coatings

This review covers recent progress in polyelectrolyte multilayer (PEM) coatings applied to analytical separations using open-tubular capillary electrochromatography (OT-CEC). The simple preparation procedure involved in the PEM approach has provided some attractive features over other modes of capillary electrophoresis-based separations including packed column capillary electrochromatography (PC-CEC) and micellar electrokinetic chromatography (MEKC). PEM coatings have been used to alleviate the adsorption of basic analytes, to improve separations, and to improve the stability of the electroosmotic flow. Fundamental aspects of PEM coatings on surfaces and analytical separation platforms are briefly outlined in this review. In addition, applications of PEM coatings to fused-silica capillaries or microchip separation devices for the separation of small achiral or chiral analytes, as well as large biomolecules, are discussed.     

Atomistic modeling of enantioselection in chromatography

A review of atomistic molecular modeling studies related to chromatographic separations of enantiomers is presented. Only those types of calculations where direct interactions between a selector and a selectand are involved are described in this review; omitted are regression models. An emphasis is placed on comparing methods used for sampling potential energy surfaces implementing different methodologies like quantum and molecular mechanics for energy calculations, and molecular dynamics and Monte Carlo sampling strategies for simulations. Type I-V chiral stationary phases and additives for capillary electrophoresis and ion-pair chromatography are covered in this review.     

Wall Slip Phenomena in Oil-in-Water Emulsions: Effect of Some Structural Parameters

The influence of some structural parameters on wall slip phenomena during the flow of oil-in-water model emulsions has been investigated using geometries with smooth and rough surfaces. A wall slip phenomenon has been quantified as the relative difference between the areas under the flow curves obtained using geometries with both types of surfaces. Experimental results demonstrate that wall slip effects phenomena vanish as the disperse phase fraction, the emulsifier content, or the agitation speed applied during the emulsification process increase. These influences have been related to changes in both droplet size and interparticle interactions. In addition to this, the shear stress range in which wall slip is more important coincides with the region at which a shear-induced deflocculation process occurs. In this region, low reproducible values of the flow curve were obtained by using geometries with smooth surfaces. Copyright 2001 Academic Press.     

Adsorption-entanglement layers in flowing high molecular weight polymer solutions III: Solution concentration and solvent power

Adsorption entanglement layers are thick, i. e. multimolecular layers formed at solid surfaces during the flow of high molecular weight polymer solutions. The present publication is concerned with the influence of solution concentration and solvent power on the formation of these layers. Three polymers have been used, polyethylene, polymethylmethacrylate and atactic polystyrene in various solvents. The formation and thickness of layers were monitored from their effect on flow behaviour. Two flow geometries were used: Couette flow — where the layers cause peaks in the shear stress during continuous shearing, and capillary flow where the layers reduce the flow rate. The results indicate that there is a critical concentration below which no layers form, and that this critical concentration is an order of magnitude less than the conventionally defined overlap concentration. It is also deduced that the layers form more quickly, and grow to be thicker when better solvents are used.     

Geometry-driven wetting transition

Wetting states are quantitatively described by the number of inflection points on the liquid-vapor interface and by the macroscopic contact angle. The number of inflection points required for complete, partial, and pseudopartial wetting is determined for geometries with positive, zero, and negative capillary pressures. The wetting state of a material system is not always independent of the magnitude of the capillary pressure; for example, the wetting state of a fluid inside a capillary tube may depend on the capillary radius. In particular, a fluid that pseudopartially wets the inside of a tube exhibits a transition to partial wetting (or complete wetting) as the capillary radius is decreased.     

Can a single-reference approach provide a balanced description of ground and excited states? A comparison of the completely renormalized equation-of-motion coupled-cluster method with multireference quasidegenerate perturbation theory near a conical intersection and along a photodissociation coordinate in ammonia

We calculated the two lowest electronically adiabatic potential energy surfaces of ammonia in the region of the conical intersection and at a sequence of geometries along which one of the N-H bonds is broken. We employed both a multireference (MR) method and a single-reference (SR) method. The MR calculations are based on multiconfiguration quasidegenerate perturbation theory (MC-QDPT) with a 6-311+G(3df,3pd) basis set. The SR calculations, carried out with the same basis, employ the completely renormalized equation-of-motion coupled-cluster method with singles and doubles, and a noniterative treatment of triples, denoted CR-EOMCCSD(T). At 91 geometries used for comparison, including geometries near a conical intersection, the surfaces agree to 7% on average.     

聚合物涂层在毛细管电泳分离蛋白中的研究进展

毛细管电泳具有分析时间短,分离效率高,样品消耗量少等优点,在生物样品分离,特别是蛋白质分析领域有重要应用。然而,毛细管内壁硅羟基的解离给分离结果带来诸多不良影响。聚合物涂层能够抑制蛋白质在毛细管内壁的吸附以及调控电渗流,故对毛细管内壁进行有效修饰能够提高其对蛋白质的分离效率及分离稳定性。该文主要综述了动态及静态聚合物涂层毛细管的最新研究进展,并概述了近些年基于多巴胺/聚多巴胺发展起来的涂层毛细管的研究进展,最后展望了聚合物涂层毛细管的发展趋势。     

Light scattering as a probe of liquid surfaces and interfaces

The field of quasi-elastic light scattering from thermally excited capillary waves at liquid surfaces is reviewed, with particular attention to scientific advances since 1992. These include surface-induced freezing in molecular fluids, the cross-over from capillary to elastic Rayleigh waves on the surfaces of gelling polymer solutions, the experimental demonstration of mixing of capillary and dilatational surface modes and the observation of effects due to processes tending to reduce the stability of the dilatational waves on surfactant solutions. The potential of this technique for surface and interface science is discussed.