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A method has been proposed for determining interfacial free energy from the data of molecular dynamics simulation. The method is based on the thermodynamic integration procedure and is distinguished by applicability to both planar interfaces and those characterized by a high curvature. The workability of the method has been demonstrated by the example of determining the surface tension for critical nuclei of water droplets upon condensation of water vapor. The calculation has been performed at temperatures of 273-373 K and a pressure of 1 atm, thus making it possible to determine the temperature dependence of the surface tension for water droplets and compare the results obtained with experimental data and the simulation results for a 'planar' vapor-liquid interface. [ABSTRACT FROM AUTHOR]

A new two-scale computational model is proposed to construct the constitutive law of the swelling pressure which appears in the modified form of the macroscopic effective stress principle for expansive clays saturated by an aqueous electrolyte solution containing multivalent ionic species. The microscopic non-local nanoscale model is constructed based on a coupled Poisson-Fredholm integral equation arising from the thermodynamics of inhomogeneous fluids in nanopores (Density Functional Theory), which governs the local electric double layer potential profile coupled with the ion-particle correlation function in an electrolytic solution of finite size ions. The local problem is discretized by invoking the eigenvalue expansion of the convolution kernel in conjunction with the Galerkin method for the Gauss-Poisson equation. The discretization of the Fredholm equation is accomplished by a collocation scheme employing eigenfunction basis. Numerical simulations of the local ionic profiles in rectangular cell geometries are obtained showing considerable discrepancies with those computed with Poisson-Boltzmann based models for point charges, particularly for divalent ions in calcium montmorillonite. The constitutive law for the disjoining pressure is reconstructed numerically by invoking the contact theorem within a post-processing approach. The resultant computational model is capable of capturing ranges of particle attraction characterized by negative values of the disjoining pressure overlooked by the classical electric double layer theory. Such results provide further insight in the role the swelling pressure plays in the modified macroscopic effective stress principle for expansive porous media. [ABSTRACT FROM AUTHOR]

In classical semi-infinite Coulomb fluids, two-point correlation functions exhibit a slow inverse-power law decay along a uniformly charged wall. In this work, we concentrate on the corresponding amplitude function which depends on the distances of the two points from the wall. Recently Šamaj (J Stat Phys 161:227-249 ), applying a technique of anticommuting variables to a 2D system of charged rectilinear wall with 'counter-ions only', we derived a relation between the amplitude function and the density profile which holds for any temperature. In this paper, using the Möbius conformal transformation of particle coordinates in a disc, a new relation between the amplitude function and the density profile is found for that model. In all exactly solvable cases, the amplitude function factorizes itself in the two distances from the wall. Presupposing this factorization property at any temperature and using specific sum rules for semi-infinite geometries, a relation between the amplitude function of the charge-charge structure function and the charge profile is derived for many-component Coulomb fluids in any dimension. [ABSTRACT FROM AUTHOR]

Nanoporous silver (NPS) with a ligament size ranging from 15 to 40 nm was fabricated by de-alloying (CuZr)Ag ( x = 10at%, 20at%, 30at%, and 40at%) amorphous ribbons in a mixed aqueous solution of hydrofluoric (HF) acid and nitric acid under free corrosion conditions. Nanoporous silver ligaments and pore sizes were able to be fine-tuned through tailoring the chemical composition, corrosion conditions, and de-alloying time. The ligament size increases with an increase in Ag content and de-alloying time, but decreases with an increase in HF concentration. This phenomenon may be attributed to the dissolution of Zr/Cu and the diffusion, aggregation, nucleation, and recrystallization of Ag, leading to an oriented attachment of adjacent nanocrystals as revealed by TEM analysis. [ABSTRACT FROM AUTHOR]

We carried out a series of experiments of metal sulfide deposition on glass and copper substrates by the successive ionic layer adsorption and reaction (SILAR) technique. This technique based on the cations adsorption process involves the presence of the van der Waals and electrostatic forces. According to the theoretical study discussed herein, the equilibrium separation between cations and the substrate surface was lower in the case of a copper substrate than that of a glass one confirming the observed experiments results obtained by the SILAR technique. The surface charge of the glass substrate is strongly dependent on the solution pH. In the absence of the surface charge, the dominant forces between cations in solution and the glass substrate were repulsive in contrast with the case of the copper substrate in which attractive forces dominate even if the surface is somewhat positively charged. This study enriches the knowledge on the optimization parameters for fabricating thin films of metal chalcogenide of good adherence. [ABSTRACT FROM AUTHOR]

Macromolecules, when immersed in a polar solvent like water, become charged by a fixed surface charge density which is compensated by 'counter-ions' moving out of the surface. Such classical particle systems exhibit poor screening properties at any temperature and the trivial bulk regime (far away from the charged surface) with no particles, so the validity of standard Coulomb sum rules is questionable. In the present paper, we concentrate on the two-dimensional version of the model with the logarithmic interaction potential. We go from the finite disc to the semi-infinite planar geometry. The system is exactly solvable for two values of the coupling constant $$\varGamma $$ : in the Poisson-Boltzmann mean-field limit $$\varGamma \rightarrow 0$$ and at the free-fermion point $$\varGamma =2$$ . We show that the finite-size expansion of the free energy does not contain universal term as is usual for Coulomb fluids. For the coupling constant being an arbitrary positive even integer, using an anticommuting representation of the partition function and many-body densities we derive a sequence of sum rules. As a result, the contact density of counter-ions at the wall is available for the disc. The amplitude function, which characterizes the asymptotic inverse-power law behavior of the two-body density along the wall, is found to be related to the particle density profile. The dielectric susceptibility tensor, calculated exactly for an arbitrary coupling and the particle number, exhibits the anticipated disc value in the thermodynamic limit, in spite of zero contribution from the bulk region. Some of the results obtained in the Poisson-Boltzmann limit are generalized to an arbitrary Euclidean dimension. [ABSTRACT FROM AUTHOR]

The paper presents measurements of friction of any ultra-thin film entrained into the contact of a pair of very smooth specimen subjected to entrainment in a converging micro-wedge of a special-purpose micro-tribometer. An ultra-thin film is expected to form at the boundary solids through adsorption of boundary active molecules. Fluids with linear and branched molecules are used in the investigation. It is found that the frictional characteristics of these films can be adequately described through use of Eyring thermal activation energy and a potential energy barrier to sustain conjunctional sliding motion. The combined experimental measurement and the simple activation energy approach shows that the thin molecular adsorbed films act like hydro Langmuir-Blodgett layers, the formation and frictional characteristics of which are affected by the competing mechanisms of adsorption, forced molecular re-ordering and discrete-fashion drainage through the contact by the solvation effect. This process is a complex function of the contact sliding velocity as well as a defined Eyring activation density (packing density of the molecules within the conjunction). It is shown that the contribution of solvation to friction is in the form of energy expended to eject layers of lubricant out of the contact, which unlike the case of micro-scale hydrodynamic films, is not a function of the sliding velocity. [ABSTRACT FROM AUTHOR]

Histone deacetylase (HDAC) inhibitors are emerging as promising anticancer drugs. Because aberrant activity and expression of HDACs have been implicated in various cancer types, a wide range of HDAC inhibitors are being investigated as anticancer agents. Furthermore, due to the demonstrable anticancer activity in both in vitro and in vivo studies, numerous HDAC inhibitors have undergone a rapid phase of clinical development in various cancer types, either as a monotherapy or in combination with other anticancer agents. Although preclinical trials show that HDAC inhibitors have a variety of biological effects across multiple pathways, including regulation of gene expression, inducing apoptosis and cell cycle arrest, inhibiting angiogenesis, and regulation of DNA damage and repair, the mechanism by which the clinical activity is mediated remains unclear. Understanding the mechanisms of anticancer activity of HDAC inhibitors is essential not only for rational drug design for targeted therapies, but for the design of optimized clinical protocols. This paper describes the links between HDACs and cancer, and the underlying mechanisms of action of HDAC inhibitors against hematological malignancies and solid tumors. Further, this review presents the clinical outcomes of vorinostat, romidepsin, and belinostat, which are approved by the United States Food and Drug Administration for the treatment of lymphomas. [ABSTRACT FROM AUTHOR]

Liquids are known to slip past non-wetting channel walls. The degree of slippage can be patterned locally through engineered variations in topography and/or chemistry. Electro-osmotic flow through a thin slit-like nanochannel with walls of sinusoidally varying slippage is studied through an asymptotic theory that uses the ratio of pattern amplitude to the average slip as a small parameter. The direction of patterning is perpendicular to the applied electric field. No restrictions are placed on the relative magnitudes of the channel height, wavelength of the pattern, the average slip length and the phase shift between the patterns on the walls. A closed-form analytical expression is provided for the effective slip length and tested against limits known from the literature. The results are also generalized for applicability to any unidirectional flow field that might originate from other driving forces such as pressure differential. The asymptotic results are compared with numerical simulations and are found to be in good mutual agreement even for moderate magnitudes of the small parameter in the asymptotic theory. [ABSTRACT FROM AUTHOR]

The process of material removal of single crystal copper with rough surfaces subjected to nanoscale scratching is studied in the present paper. We explore the key material removal mechanism by means of the observed variation of material removal under different surface roughnesses, tool speeds, scratching directions, tip shapes, feeds, double tip, and single tip. The investigation reveals that a higher peak on the surface reduces the local area roughness, and a higher valley enhances the stability of surface structure. The plastic deformation by means of dislocation loop transfers from the surface of substrate to the interior of workpiece with the rough or smooth surface during scratching process. A higher scratching velocity results in the increasing surface smoothness and reducing the impact on the rough surface atoms. The scratching along the critical angle 45° between scratching direction and surface texture orientation makes the surrounding atoms produce the minimal variation structure, helps to improve the structural stability, and plays an important role in protecting the scratching surface. The double-tip and single-tip scratching under different scratching feeds makes the rough surface perpendicular to the scratching direction substantially covered by chips or side flow. For different tip shapes, a cone diamond tip causes less plastic deformation in the subsurface than a prismatic diamond tip due to using different diamond tips with a contact area unequal. [ABSTRACT FROM AUTHOR]

This work reports an experimental study of the thermal effect on the deposition of microparticles onto a solid surface in a microfluidic system, which allows a precise control of the solution temperature and enables the real-time monitoring of the deposition kinetics at the increased temperature. The static particle deposition rate (Sherwood number) has been measured over a range of temperatures between 20 and 70 °C. It is found that the Sherwood number is monotonically increased up to 265 %, with the solution temperature within the test range. A model including the Derjaguin-Landau-Verwey-Overbeek theory-based colloidal surface forces and gravity force is employed, taking into account temperature effects, to qualitatively interpret the experimental findings. The model shows that, by increasing the solution temperature, the attraction energy (van der Waals force) between the particles and the solid surface is increased while the repulsive energy (electric double layer force) is decreased. These findings demonstrate the importance of thermal effects in various thermally driven deposition processes, such as the fouling of bacteria and milk proteins in microscale milk pasteurization units. [ABSTRACT FROM AUTHOR]

Hydrophobic particles in water and hydrophilic particles in oil aggregate, but can form colloidal dispersions if their surfaces are chemically camouflaged with surfactants, organic tethers, adsorbed polymers or other particles that impart affinity for the solvent and increase interparticle repulsion. A different strategy for modulating the interaction between a solid and a liquid uses surface corrugation, which gives rise to unique wetting behaviour. Here we show that this topographical effect can also be used to disperse particles in a wide range of solvents without recourse to chemicals to camouflage the particles' surfaces: we produce micrometre-sized particles that are coated with stiff, nanoscale spikes and exhibit long-term colloidal stability in both hydrophilic and hydrophobic media. We find that these 'hedgehog' particles do not interpenetrate each other with their spikes, which markedly decreases the contact area between the particles and, therefore, the attractive forces between them. The trapping of air in aqueous dispersions, solvent autoionization at highly developed interfaces, and long-range electrostatic repulsion in organic media also contribute to the colloidal stability of our particles. The unusual dispersion behaviour of our hedgehog particles, overturning the notion that like dissolves like, might help to mitigate adverse environmental effects of the use of surfactants and volatile organic solvents, and deepens our understanding of interparticle interactions and nanoscale colloidal chemistry. [ABSTRACT FROM AUTHOR]

The thermodynamic properties of gases have been understood primarily through phase diagrams of bulk gases. However, observations of gases confined in a nanometer space have posed a challenge to the principles of classical thermodynamics. Here, we investigated interfacial structures comprising either O2 or N2 between water and a hydrophobic solid surface by using advanced atomic force microscopy techniques. Ordered epitaxial layers and cap-shaped nanostructures were observed. In addition, pancake-shaped disordered layers that had grown on top of the epitaxial base layers were observed in oxygen-supersaturated water. We propose that hydrophobic solid surfaces provide low-chemical-potential sites at which gas molecules dissolved in water can be adsorbed. The structures are further stabilized by interfacial water. Here we show that gas molecules can agglomerate into a condensed form when confined in a sufficiently small space under ambient conditions. The crystalline solid surface may even induce a solid-gas state when the gas-substrate interaction is significantly stronger than the gas-gas interaction. The ordering and thermodynamic properties of the confined gases are determined primarily according to interfacial interactions. [ABSTRACT FROM AUTHOR]

Pretreatment has been viewed as the most efficient strategy for lignocellulosic biomass-to-fermentable sugars conversion. In this study a novel pretreatment with acidic electrolyzed water (AEW) and FeCl was proposed and tested to deconstruct the recalcitrance of corn stover and enhance its subsequent cellulose-to-sugar conversion. The effects of AEW pH and FeCl concentration on hemicellulose degradation were investigated, and the results showed the highest hemicellulose removal (93.40 %) and recovery (93.04 %) were achieved at AEW pH 2.30 and FeCl concentration 0.05 mol/L. Further research on the properties of AEW solutions with FeCl, including their pH, ORP, and DO revealed the synergistic effects of strong acidity and high oxidizing capacity of the solution could boost hemicellulose breakup and enhance the enzymatic hydrolysis of cellulose (92.00 %) by removing most of hemicellulose and increasing the accessibility and digestibility of cellulose. Therefore, these studies prove AEW coupled with FeCl pretreatment is an effective and promising approach in biomass-to-biofuel process. [ABSTRACT FROM AUTHOR]

In this paper, we show that large connected slip patches (hydrophobic patches) are a necessity to induce macroscopic slip effects of water flow in microchannels. For this purpose, the 2D fluid flow between a planar stationary surface with alternating stick and slip patches and a parallel planar surface moving with a constant relative velocity has been studied by computer simulations based on Navier-Stokes equations. A slip patch is defined as the slipping length in a 2D system or a slip area of the surface in a 3D system. The simulations reveal that the ratio (size of each slip patch)/(distance between the two parallel interfaces) has profound effect on the viscous stress on the moving surface when this ratio is around and above one. However, when the ratio is much below one, the effect of the slip patches are minor, even if the area fraction of slip patches are higher than 50 %. Obviously, the stick patches adjacent to the slip patches act as effective barriers, preventing the fluid velocity to increase near the surface with alternating stick and slip patches. The obtained results are scalable and applicable on all length scales, with an exception for narrow channels in the subnano regime, i.e. <1 nm where specific effects as the atomistic composition and the nanostructure of the wall as well as the interactions between the wall and the water molecules have an effect. [ABSTRACT FROM AUTHOR]

Nanoscale roughness in combination with surface chemistry modification can achieve large liquid slippage due to entrapment of air pockets in the surface asperities (superhydrophobic Cassie state). However, pressure increase may result in the collapse of the gaseous enclaves into the fully wet Wenzel state, and in the irreversible loss of the desirable superhydrophobic features. In order to explain the subtle effects of pressure, an extensive simulative campaign based on full-atoms molecular dynamics and aimed at reproducing a realistic superhydrophobic system comprising water, solid walls, and hydrophobic coating with octadecyltrichlorosilane is addressed in comparison with a continuum approach. The dramatic impact of pressure on slippage is twofold: on the one hand, it influences the shape of the liquid/vapor interface, thus indirectly affecting the flow. This is a purely geometrical effect well captured in principle by the continuum description. On the other hand, pressure controls the complex interplay between water and hydrophobic chains close to the triple line where it significantly alters the liquid structure, thus modifying apparent slippage. This is an intrinsically atomistic phenomenology that cannot be predicted at the continuum level. The combination of the two effects is found to explain the peculiar response of slippage to the applied pressure at the nanoscale, that may look at first sight in contradiction with most microscale literature results. [ABSTRACT FROM AUTHOR]

The recently developed modified Donnan (mD) model provides a simple and useful description of the electrical double layer in microporous carbon electrodes, suitable for incorporation in porous electrode theory. By postulating an attractive excess chemical potential for each ion in the micropores that is inversely proportional to the total ion concentration, we show that experimental data for capacitive deionization (CDI) can be accurately predicted over a wide range of applied voltages and salt concentrations. Since the ion spacing and Bjerrum length are each comparable to the micropore size (few nanometers), we postulate that the attraction results from fluctuating bare Coulomb interactions between individual ions and the metallic pore surfaces (image forces) that are not captured by mean-field theories, such as the Poisson-Boltzmann-Stern model or its mathematical limit for overlapping double layers, the Donnan model. Using reasonable estimates of the micropore permittivity and mean size (and no other fitting parameters), we propose a simple theory that predicts the attractive chemical potential inferred from experiments. As additional evidence for attractive forces, we present data for salt adsorption in uncharged microporous carbons, also predicted by the theory. [ABSTRACT FROM AUTHOR]

Silicon dioxide films are extensively used in nano and micro-electromechanical systems. Here we studied the influence of an external electric field on the mechanical properties of a SiO2 film by using nanoindentation technique of atomic force microscopy (AFM) and friction force microscopy (FFM). Agiant augmentation of the relative elastic modulus was observed by increasing the localized electric field. A slight decrease in friction coefficients was also clearly observed by using FFM with the increase of applied tip voltage. The reduction of the friction coefficients is consistent with the great enhancement of sample hardness by considering the indentation-induced deformation during the friction measurements. [ABSTRACT FROM AUTHOR]

Liquid/vapour interfaces govern the behaviour of a wide range of systems but remain poorly understood, leaving ample margin for the exploitation of intriguing functionalities for applications. Here, we systematically investigate the role of liquid/vapour interfaces in the transport of water across apposing liquid menisci in osmosis membranes comprising short hydrophobic nanopores that separate two fluid reservoirs. We show experimentally that mass transport is limited by molecular reflection from the liquid/vapour interface below a certain length scale, which depends on the transmission probability of water molecules across the nanopores and on the condensation probability of a water molecule incident on the liquid surface. This fundamental yet elusive condensation property of water is measured under near-equilibrium conditions and found to decrease from 0.36 ± 0.21 at 30 °C to 0.18 ± 0.09 at 60 °C. These findings define the regime in which liquid/vapour interfaces govern nanofluidic transport and have implications for understanding mass transport in nanofluidic devices, droplets and bubbles, biological components and porous media involving liquid/vapour interfaces. [ABSTRACT FROM AUTHOR]

Summary: In this paper we present an overview of some key theoretical tools employed for the investigations of the equilibrium structure and thermodynamics of complex fluids. We place our focus on the most common systems of soft-matter science, namely dispersions of colloidal particles, which may be hard or soft, and which may carry electric charge. The concept of the effective Hamiltonian, which plays the key role in these coarse-grained approaches is introduced, and it is given a precise mathematical definition. Its properties as well as key approximations involved in deriving effective potentials are discussed. Thereafter, the ways in which the effective interactions can be combined with tools from the theory of fluids and statistical mechanics are presented, putting emphasis on Density Functional Theory. The general principles are combined with extensive exposures from currently active research fields, and applications to interfacial and wetting behavior of complex mixtures as well as to crystallization and cluster formation are discussed. Appendix A serves as a mini-course on functionals and functional differentiation. [ABSTRACT FROM AUTHOR]

This research focuses on the study of different electrokinetic parameters of carbon nanotubes (CNTs) and fullerene aggregates in liquid crystal (LC) host medium, which are investigated in the homogeneously aligned nematic LC cells driven by in-plane field. The colloidal CNTs in LC medium are observed to move towards the negative electrodes whereas the fullerenes in LC medium are observed to move towards positive electrode at low frequencies. We propose a model to estimate the charge and zeta potential of colloidal particles by incorporating both the dielectrophoresis and electrophoresis forces in order to probe the reason of moving the colloidal particles in opposite direction. Interestingly, charge and zeta potential values on CNTs and fullerenes estimated from given model were positive and negative, respectively. The CNTs and fullerenes at high frequency and field are found to stretch along the direction of electric field. The CNTs dispersed whereas fullerenes start to move in perpendicular direction to the applied electric field with increasing electric field at high frequency. [ABSTRACT FROM AUTHOR]

Adhesion can cause energy losses in asperities or particles coming into dynamic contact resulting in frictional dissipation, even if the deformation occurring is purely elastic. Such losses are of special significance in impact of nanoparticles and friction between surfaces under low contact pressure to hardness ratio. The objective of this work is to study the effect of adhesion during the normal impact of elastic spheres on a rigid half-space, with an emphasis on understanding the mechanism of energy loss. We use finite element method for modeling the impact phenomenon, with the adhesion due to van der Waals force and the short-range repulsion included as body forces distributed over the volume of the sphere. This approach, in contrast with commonly used surface force approximation, helps to model the interactions in a more precise way. We find that the energy loss in impact of elastic spheres is negligible unless there are adhesion-induced instabilities. Significant energy loss through elastic stress waves occurs due to jump-to-contact and jump-out-of-contact instabilities and can even result in capture of the elastic sphere on the half-space. [ABSTRACT FROM AUTHOR]

This paper presents analytical and numerical results for Poiseuille flow through microtubes patterned with superhydrophobic surfaces which consist of alternative ribs and grooves aligned longitudinally with the flow direction. The superhydrophobic surface prevents the flowing liquid from penetrating the grooves and the liquid-gas interface experiences deformation as a consequence of a pressure difference across the interface. Employing a domain perturbation technique, the effects of a small interface deformation on the effective slip behavior are analytically quantified. For large interface deformations, numerical studies are performed to predict the effects of interface protrusion on the effective slip behavior of the superhydrophobic microtube. Comparisons are made between the effective slip behavior for tube and channel flows patterned with superhydrophobic surfaces containing alternating longitudinal ribs and grooves. [ABSTRACT FROM AUTHOR]

The adhesion between two parallel solid surfaces is of great interest with the rapid development of micro-nano devices and instruments. The adhesion forces between a flat tip with a diameter ∼1.7 μm and some surface have been determined by recording the force-displacement curves with an atomic force microscope (AFM). The flat tip is used to prevent wear and mimic the adhesion between two parallel surfaces. The free energy of the solid surface is calculated by the contact angles between the probe liquids and the surface. The adhesion force between parallel solid surfaces cannot be predicted by the theory of thermodynamic surface free energy. The adhesion measurements were carried out under ambient conditions, in a nitrogen-filled glove box, under distilled water, and under potassium chloride (KCl) solution. The outcome shows that the real contact area without the applied load is only a small proportion of the apparent contact area. The measurement stability and repeatability of adhesion by the AFM depend on the surface characterization, measurement methods and the environment. Under different environments, there are different interactions and factors affecting the adhesion force, and the dominant interactions and factors may be different too. The various interactions and factors are mutually coupled to determine the final adhesion force. [ABSTRACT FROM AUTHOR]

This paper investigates the stability of nitrogen nanobubbles under different concentrations of nitrogen molecules by molecular dynamics simulations. It is found that the stability of nanobubbles is very sensitive to the concentration of nitrogen molecules in water. A sharp transition between disperse states and assemble states of nitrogen molecules is observed when the concentration of nitrogen molecules is changed. The relevant critical concentration of nitrogen molecules needed by the existing nitrogen nanobubbles is analyzed. [ABSTRACT FROM AUTHOR]

The so called 'bee phenomenon' in bitumen has been investigated by means of AFM quantitative nanomechanical property mapping. Bees are a phenomenon that can be observed by topography measurements using AFM. The characteristic 'bee' appearance comes from regions with alternating higher and lower bands in the surface topography of bitumen, which are surrounded by a flat area. The proposed mechanism for bee formation is phase separation and differential contraction during cooling from melt temperatures leading to wrinkling due to differences in the elastic modulus of the material phases. Using a laminate wrinkling model, the thickness of the bee laminate was calculated from the wavelengths and Young's moduli of the bee laminate and the matrix. It was found to vary between 70 and 140 nm for the five bitumen samples that contained significant amounts of wax. [ABSTRACT FROM AUTHOR]

Structured hydrophobic surfaces may present high wall slippage due to the microscopic details of wetting. This behavior can be exploited for reducing wall slippage in micro- and nanofluidic devices. In this work we focus on the influence of meniscus curvature and pressure on the slip length. We use realistic atomistic potentials in order to simulate liquid water ( TIP4P/2005) flowing on a smooth/patterned silane ( OTS) coated hydrophobic surface. Results confirm that even at the nanoscale the form of the meniscus has a strong influence on slippage. Continuum Navier-Stokes simulations show good agreement with the atomistic picture only if the shape of the meniscus and position of the triple line are correctly prescribed. [ABSTRACT FROM AUTHOR]

Self-organized multilayer films were formed by sequential addition of oppositely charged cellulose I nanoparticles. The all-cellulosic multilayers were prepared via adsorption of cationicially modified cellulose nanofibrils (cat NFC) and anionic short crystalline cellulose (CNC) at pH 4.5 and pH 8.3. The properties and build-up behavior of layer-by-layer-constructed films were studied with microgravimetry (QCM-D) and the direct surface forces in these systems were explored with colloidal probe microscopy to gain information about the fundamental interplay between cat NFC and anionic CNC. The importance of the first layer on the adsorption of the consecutive layers was demonstrated by comparing pure in situ adsorption in the QCM-D with multilayer films made by spin coating the first cationic NFC layer and then subsequently adsorbing the following layers in situ in the QCM-D chamber. Differences in adsorbed amount and viscoelastic behavior were observed between those two systems. In addition, a significant pH dependence of cat NFC charge was found for both direct surface interactions and layer properties. Moreover the underlying cellulose layer in multilayer film was established to influence the surface forces especially at lower pH, where the cat NFC chains extensions were facilitated and overall charge was affected by the cationic counterpart within the layers. This enhanced understanding the effect of charge and structure on the interaction between these renewable nanoparticles is valuable when designing novel materials based on nanocellulose. [ABSTRACT FROM AUTHOR]

In this work, we present a theoretical method to determine the line tension of nanodroplets on homogeneous substrates via decomposing the grand free energy into volume, interface and line contributions. With the obtained line tension, we check the viability of Young equation and find that the chemical potential dependence (or equivalently, droplet curvature dependence) of the interface tensions is crucial for the viability of modified Young equation at the nanometer scale. In particular, the linear relationship between the cosine of contact angle and the curvature of the contact line, which is often used to determine the line tension, is found to be incorrect at the nanometer scale. [ABSTRACT FROM AUTHOR]

A two-dimensional linear-elastic fracture mechanics analysis of asperity cracking induced by adhesive normal contact was performed with the finite element method. Normal contact between two elastic asperities was analyzed with the equivalent contact system of an elastic asperity with equivalent radius of curvature and effective elastic modulus compressed by a rigid plane. Surface adhesion was modeled by nonlinear springs obeying a constitutive force-distance law derived from the Lennard-Jones potential. The maximum ranges of the tensile and shear stress intensity factors were used to determine the crack-growth direction and the dominant mode of asperity fracture in terms of the Maugis parameter (a function of the equivalent radius of curvature, work of adhesion, effective elastic modulus, and intermolecular equilibrium distance), friction coefficient at the crack interface, maximum surface interference, and crack position. Finite element simulation results indicate that the direction and the rate of crack growth are mostly affected by the Maugis parameter and the maximum surface interference. A transition from shear to tensile dominant mode of crack growth is encountered with the increase of the Maugis parameter and/or the decrease of the maximum surface interference. Opening, slip, and stick between the crack faces during loading and unloading are discussed in the context of crack mechanism maps. [ABSTRACT FROM AUTHOR]

Tribological properties mapping is a new technique that extracts friction coefficient and adhesion maps obtained from lateral atomic force microscope (LAFM) images. By imaging the surface systematically as a function of load, a series of images can be tiled, and pixelwise fitted to a modified Amontons' Law to obtain friction coefficient and adhesion maps. This removes the ambiguity of friction contrast in LAFM imaging which can be a function of the load used for imaging. In ambient laboratory, air and tetradecane, a sample of Vancron40, commercial powder metallurgical tool alloy containing nitrogen, have been scanned using a standard silicon cantilever in order to obtain tribological data. The tribological properties mapping provides unique information regarding the heterogeneous alloy microstructure as well as shedding light on the tribological behavior of the alloy. [ABSTRACT FROM AUTHOR]

The aggregative stability of aerosil OX-50 sol in solutions of anionic surfactant, sodium dodecylsulfate (SDS), is studied. An intense aggregation process observed in SDS solutions (10-10 M) is analyzed from the viewpoint of balanced surface forces accounting for hydrophobic effects. [ABSTRACT FROM AUTHOR]

The characterization of reactive solid-liquid interfacial energies and solid surface energies is a pressing problem in materials science and surface science. Based on the concept that unbalanced forces doing work, a mathematical formulation between surface energies and interfacial energies for reactive wetting is presented. The resulting formalism has significant generality in which the equilibrium Young's equation for solid-liquid interfacial energies is just a special case. It is shown that a solid-liquid interfacial energy at non-equilibrium is always higher than that at equilibrium, and that the transformation of reactive interfaces to equilibrium interfaces is an inevitable, spontaneous process. The numerical range of solid-liquid interfacial energies γ for a limited, solid-liquid interfacial wetting system was calculated to be 0 ⩽ γ ⩽ γ. The calculation methods for reactive solid-liquid interfacial energies and solid surface energies are presented. They are significant for composite materials and weld, powder sinter, package of electronic devices, and other surface and interfacial issues in metallurgy. [ABSTRACT FROM AUTHOR]

Liquid-crystalline phases of stacked lipid bilayers represent a pervasive motif in biomolecular assemblies. Here we report that, in addition to the usual smectic order, multicomponent multilayer membranes can exhibit columnar order arising from the coupling of two-dimensional intralayer phase separation and interlayer smectic ordering. This coupling propagates across hundreds of membrane lamellae, producing long-range alignment of phase-separated domains. Quantitative analysis of real-time dynamical experiments reveals that there is an interplay between intralayer domain growth and interlayer coupling, suggesting the existence of cooperative multilayer epitaxy. We postulate that such long-range epitaxy is solvent-assisted, and that it originates from the surface tension associated with differences in the network of hydrogen-bonded water molecules at the hydrated interfaces between the domains and the surrounding phase. Our findings might inspire the development of self-assembly-based strategies for the long-range alignment of functional lipid domains. [ABSTRACT FROM AUTHOR]

This paper reports on simulations of electrokinetic transport in an electrolyte nanofilm in contact with a negatively charged substrate with discontinuous counter-charged patches. All-atom molecular dynamics simulations of an aqueous solution of chloride placed on a silica slab were conducted. The response of the system is investigated as it is subjected to different axial electric fields and as the surface electrostatics is modified by implementing different positive charge densities on the patches. Chloride and water density profiles reveal that the charged patches cause an enrichment of hydrated chloride ions near the surface. Therefore, the system with patches proved to be successful in trapping ions. Moreover, the number of chloride ions trapped on the surface increases as higher charge densities are imposed on the patches. It is observed that higher axial electric fields remove chloride ions from the surface; however, the amount removed decreases as higher charge densities are imposed on the patches. Velocity profiles show a stagnant water layer near the patches. The water and ion accumulation suggest the formation of a Stern layer with thickness of ca. 0.4 nm on the patches. Higher chloride density near the surface and increased surface-water affinity induced by the presence of charged patches result in smaller electroosmotic velocities. The simulation results compare well with velocities calculated using a continuum approach. This study shows that in a charged electrolyte solution in contact with a substrate, axial and normal ion distributions and consequently electroosmotic velocities can be controlled by modifying the electrostatics of the substrate. [ABSTRACT FROM AUTHOR]

An intein-driven protein splicing approach allowed for the covalent linkage between the N- and C-termini of a polypeptide chain to create circular variants of the endo-β-1,3-1,4-glucanase, LicA, from Bacillus licheniformis. Two circular variants, LicA-C1 and LicA-C2, which have connecting loops of 20 and 14 amino acids, respectively, showed catalytic activities that are approximately two and three times higher, respectively, compared to that of the linear LicA (LicA-L1). The thermal stability of the circular variants was significantly increased compared to the linear form. Whereas the linear glucanase lost half of its activity after 3 min at 65 °C, the two circular variants have 6-fold (LicA-C1) and 16-fold (LicA-C2) increased half-life time of inactivation. In agreement with this, fluorescence spectroscopy and differential scanning calorimetry studies revealed that circular enzymes undergo structural changes at higher temperatures compared to that of the linear form. The effect of calcium on the conformational stability and function of the circular LicAs was also investigated, and we observed that the presence of calcium ions results in increased thermal stability. The impact of the length of the designed loops on thermal stability of the circular proteins is discussed, and it is suggested that cyclization may be an efficient strategy for the increased stability of proteins. [ABSTRACT FROM AUTHOR]

In swelling porous media, the potential for flow is much more than pressure, and derivations for flow equations have yielded a variety of equations. In this article, we show that the macroscopic flow potentials are the electro-chemical potentials of the components of the fluid and that other forms of flow equations, such as those derived through mixture theory or homogenization, are a result of particular forms of the chemical potentials of the species. It is also shown that depending upon whether one is considering the pressure of a liquid in a reservoir in electro-chemical equilibrium with the swelling porous media, or the pressure of the vicinal liquid within the swelling porous media, a critical pressure gradient threshold exists or does not. [ABSTRACT FROM AUTHOR]

The depletion potential between two colloid particles immersed in a hydrogen bonding fluid has been investigated by density functional theory. The study is motivated by the wide applications of hydrogen bonding fluids in the field of colloid science, and the effects of relevant factors on the depletion potential and depletion force between colloid particles have been studied. These factors include the size ratio of the colloid particle to the fluid molecule, the bulk density of the fluid, the functionality (the number of proton acceptors a and proton donors d) and hydrogen bonding strength as well as the colloid-fluid interaction energy. By comparing the depletion potential calculated under various conditions, it is shown that the effects of these factors on the depletion potential are very significant, and in particular in regulating the depletion force and its range. [ABSTRACT FROM AUTHOR]

The thiopurines azathioprine, 6-mercaptopurine and 6-thioguanine (6-TG) are important medications for cancer and inflammatory disorders. They are also widely prescribed as immunosuppressants in organ transplant patients. Their metabolism results in the incorporation of 6-TG into patients' DNA, and this increases skin sensitivity to incident UVA. Unlike the canonical DNA bases, which do not absorb UVA to a significant degree, DNA 6-TG is a strong UVA chromophore. It acts as a Type II UVA photosensitizer, and the combination of 6-TG and UVA treatment induces a synergistic toxicity in cultured human cells. Here, we review some of the damage that this interaction causes. Photochemical activation of DNA 6-TG triggers DNA and protein oxidation; it induces DNA breakage, DNA crosslinking, oxidation of DNA bases and the covalent attachment of proteins to DNA. Many of these photochemical DNA lesions are difficult for cells to deal with, and we review the evidence linking thiopurine immunosuppression with genome instability and the high incidence of skin cancer in organ transplant recipients. [ABSTRACT FROM AUTHOR]

The effect of rough-wall/fluid interaction on flow in nanochannels is investigated by NEMD. Hydrophobic and hydrophilic surfaces are studied for walls with nearly atomic-size rectangular protrusions and cavities. Our NEMD simulations reveal that the number of liquid atoms temporarily trapped in the cavities is affected by the strength of the potential energy inside the cavities. Regions of low potential energy are possible trapping locations. Fluid atom localization is also affected by the hydrophilicity/hydrophobicity of the surface. Potential energy is greater between two successive hydrophilic protrusions, compared to hydrophobic ones. Moreover, groove size and wall wettability are factors that control effective slip length. Surface roughness and wall wettability have to be taken into account in the design of nanofluidic devices. [ABSTRACT FROM AUTHOR]

The flow of Newtonian gassed liquids in porous media and capillaries accompanied by slip effect is considered. Based on an analysis of accumulated experimental data, the mechanism of the slip effect and models describing the observed phenomena are proposed. [ABSTRACT FROM AUTHOR]

In order to model the adhesive contact across different length scales, a multiscale approach is developed and used to study the adhesive contact behaviors between a rigid cylinder and an elastic face-centered cubic (FCC) substrate. The approach combines an atomistic treatment of the interfacial region with an elastic mechanics method description of the continuum region. The two regions are connected by a coupling region where nodes of the continuum region are refined to atoms of the atomistic region. Moreover, the elastic constants of FCC crystals are obtained directly from the Lennard-Jones potential to describe the elastic response characteristics of the continuum region, which ensures the consistency of material proprieties between atomistic and continuum regions. The multiscale approach is examined by comparing it with the pure MD simulation, and the results indicate that the multiscale modeling approach agrees well with the MD method in studying the adhesive contact behaviors. [ABSTRACT FROM AUTHOR]

In this article, we investigate the implications of electroosmosis with interfacial slip on electrohydrodynamic transport in microchannels having complex (yet symmetric) cross-sectional shapes, by employing a generic semi-analytical approach. We also devise an approximate technique of flow rate prediction under these conditions, using a combined consideration of electroosmotic slip (under thin electrical double layer limits) and Navier slip conditions (originating out of confinement-induced hydrophobic interactions) at the fluid-solid interface. We further assess the effectiveness of the approximate solutions in perspective of the exact solutions, as a parametric function of the relative thickness of the electrical double layer with respect to the channel hydraulic diameter. We illustrate the underlying consequences through examples of elliptic, polygonal, point star-shaped, and annular microchannel cross sections. [ABSTRACT FROM AUTHOR]

Image correlation spectroscopy (ICS) has been widely used to quantify spatiotemporal distributions of fluorescently labelled cell membrane proteins and receptors. When the membrane proteins are randomly distributed, ICS may be used to estimate protein densities, provided the proteins behave as point-like objects. At high protein area fraction, however, even randomly placed proteins cannot obey Poisson statistics, because of excluded area. The difficulty can arise if the protein effective area is quite large, or if proteins form large complexes or aggregate into clusters. In these cases, there is a need to determine the correct form of the intensity correlation function for hard disks in two dimensions, including the excluded area effects. We present an approximate but highly accurate algorithm for the computation of this correlation function. The correlation function was verified using test images of randomly distributed hard disks of uniform intensity convolved with the microscope point spread function. This algorithm can be readily modified to compute exact intensity correlation functions for any probe geometry, interaction potential, and fluorophore distribution; we show how to apply it to describe a random distribution of large proteins labeled with a single fluorophore. [ABSTRACT FROM AUTHOR]