Computation of constant mean curvature surfaces: Application to the gas-liquid interface of a pressurized fluid on a superhydrophobic surface

The interface shape separating a gas layer within a superhydrophobic surface consisting of a square lattice of posts from a pressurized liquid above the surface is computed numerically. The interface shape is described by a constant mean curvature surface that satisfies the Young-Laplace equation with the three-phase gas-liquid-solid contact line assumed pinned at the post outer edge. The numerical method predicts the existence of constant mean curvature solutions from the planar, zero curvature solution up to a maximum curvature that is dependent on the post shape, size and pitch. An overall force balance between surface tension and pressure forces acting on the interface yields predictions for the maximum curvature that agree with the numerical simulations to within one percent for convex shapes such as circular and square posts, but significantly over predicts the maximum curvature for non-convex shapes such as a circular post with a sinusoidal surface perturbation. Changing the post shape to increase the contact line length, while maintaining constant post area, results in increases of 2 to 12% in the maximum computable curvature for contact line length increases of 11 to 77%. Comparisons are made to several experimental studies for interface shape and pressure stability.     

Structure of DNA-cationic surfactant complexes at hydrophobically modified and hydrophilic silica surfaces as revealed by neutron reflectometry

In this article, we discuss the structure and composition of mixed DNA-cationic surfactant adsorption layers on both hydrophobic and hydrophilic solid surfaces. We have focused on the effects of the bulk concentrations, the surfactant chain length, and the type of solid surface on the interfacial layer structure (the location, coverage, and conformation of the DNA and surfactant molecules). Neutron reflectometry is the technique of choice for revealing the surface layer structure by means of selective deuteration. We start by studying the interfacial complexation of DNA with dodecyltrimethylammonium bromide (DTAB) and hexadecyltrimethylammonium bromide (CTAB) on hydrophobic surfaces, where we show that DNA molecules are located on top of a self-assembled surfactant monolayer, with the thickness of the DNA layer and the surfactant-DNA ratio determined by the surface coverage of the underlying cationic layer. The surface coverages of surfactant and DNA are determined by the bulk concentration of the surfactant relative to its critical micelle concentration (cmc). The structure of the interfacial layer is not affected by the choice of cationic surfactant studied. However, to obtain similar interfacial structures, a higher concentration in relation to its cmc is required for the more soluble DTAB surfactant with a shorter alkyl chain than for CTAB. Our results suggest that the DNA molecules will spontaneously form a relatively dense, thin layer on top of a surfactant monolayer (hydrophobic surface) or a layer of admicelles (hydrophilic surface) as long as the surface concentration of surfactant is great enough to ensure a high interfacial charge density. These findings have implications for bioanalytical and nanotechnology applications, which require the deposition of DNA layers with well-controlled structure and composition.     

Shapes and Sizes of Linear and Circular Multiple-ring Macromolecules

The shapes and sizes of linear and circular multiple-ring macromolecules in the framework of the Gaussian model have been numerically investigated in terms of shape factors, asphericity and prolateness factors and parameters, and shrinking factors. Simple analytic expressions for the eigenpolynomials of the Kirchhoff or architecture matrices for both linear and circular multi-rings in the limit of an infinitely large individual ring have been obtained via a new recursion method. It is found that for both types of multiple rings, shape asymmetry increases while size decreases as the number of rings increases, and that asphericity and prolateness parameters for a circular 99-ring macromolecule or a doubly stranded closed random walk have stronger dependence on dimensionality of the space in which the molecule is embedded than those of its linear counterpart. © 1997 John Wiley & Sons, Ltd.     

Adsorption of Diblock Copolymers of Poly(ethylene oxide) and Polylactide at Hydrophobized Silica from Aqueous Solution

The adsorption of a series of amphiphilic diblock copolymers of poly(ethylene oxide) (PEO) and poly(DL-lactide) (PL) at hydrophobized silica from aqueous solution was studied using time-resolved ellipsometry and reflectometry. The adsorbed amounts only display a weak dependence on the copolymer composition in both water and phosphate-buffered solution. For the short copolymers, the layer thickness decreases slightly with increasing length of the hydrophobic block. Furthermore, in comparison with the short copolymers, the layer thickness of the long copolymers is substantially higher. Upon degradation of the PL block, the adsorbed amount is found to decrease and approach that of the corresponding PEO homopolymer. Protein rejection studies indicate that the adsorption of fibrinogen is inhibited by copolymer preadsorption. The protein rejection is enhanced with increasing surface coverage of the preadsorbed copolymer, but largely independent of the length of the PL block and the PEO block. For all polymers investigated, essentially complete protein rejection is obtained above a critical surface coverage that is significantly lower than the saturation coverage of the copolymers. Removing the copolymer from bulk solution after preadsorption causes a partial desorption, resulting in reduced protein rejection. However, the protein rejection capacity with and without copolymer in the bulk solution is found to be similar at a given surface coverage. Contrary to the behavior of the intact copolymers, fibrinogen adsorption is found to be significant at surfaces pretreated with an extensively degraded copolymer and, in fact, quantitatively comparable to that at the hydrophobic surface in the absence of preadsorption. This finding, together with that of the effect of the copolymer composition on protein rejection, suggests that an efficient protein rejection is maintained until only a few L units remain in the copolymer, i.e., until nearly completed degradation. Copyright 2000 Academic Press.     

Adsorption of plasmid DNA to a natural organic matter-coated silica surface: kinetics, conformation, and reversibility

A quartz crystal microbalance with dissipation (QCM-D) has been used to determine the adsorption rate of ampicillin-resistant linear and supercoiled plasmid DNA onto a silica surface coated with natural organic matter (NOM). The structure of the resulting adsorbed DNA layer was determined by analyzing the viscoelastic properties of the adsorbed DNA layers as they formed and were then exposed to solutions of different ionic composition. The QCM-D data were complemented by dynamic light scattering measurements of diffusion coefficients of the DNA molecules as a function of solution ionic composition. The obtained results suggest that electrostatic interactions control the adsorption and structural changes of the adsorbed plasmid DNA on the NOM-coated silica surface. The adsorption of DNA molecules to the NOM layer took place at moderately high monovalent (sodium) electrolyte concentrations. A sharp decrease in solution ionic strength did not result in the release of the adsorbed DNA, indicating that DNA adsorption on the NOM-coated silica surface is irreversible under the studied solution conditions. However, the decrease in electrolyte concentration influenced the structure of the adsorbed layer, causing the adsorbed DNA to adopt a less compact conformation. The linear and supercoiled DNA had similar adsorption rates, but the linear DNA formed a thicker and less compact adsorbed layer than the supercoiled DNA.     

Monte Carlo simulation for the adsorption of symmetric triblock copolymers II. Adsorption layer information

By using Monte Carlo simulation, adsorption of both end-adsorbed and middle-adsorbed symmetric triblock copolymers from a non-selective solvent on an impenetrable surface has been studied. Influences of the adsorption energy, the bulk concentration, the chain composition and the chain length on the adsorption behavior including the surface coverage, the adsorption amount and the layer thickness are presented. It is shown that the total surface coverage for both end-adsorbed and middle-adsorbed copolymers increases monotonically as the bulk concentration increases. The higher the adsorption energy and the more the attractive segments, the higher the total surface coverage is exhibited. Surface coverage θ decreases with increasing the length of the non-attractive segments, but the product of θ and the proportion of the non-attractive segments in a triblock copolymer chain is nearly independent of the chain length. The adsorption amount increases almost monotonically with the bulk concentration. The logarithm of the adsorption amount is a linear function of the reciprocal of the reduced temperature. When the adsorption energy is large, the adsorption amount exhibits a maximum as the composition of the attractive segment increases. The adsorption isotherms of copolymers with different length of the non-attractive segments can be mapped onto a single curve under certain energy indicating that copolymers with different chain length have the same adsorption amount. The adsorption layer thickness for the end-adsorbed copolymers decreases as the energy and the number of adsorbing segments increases. The longer non-attractive segments, the larger adsorbed layer thickness is found. The tails mainly governs the adsorption layer thickness.     

Corrosion studies of a chromium steel in imitated seawater

A series of in-door experiments was performed to get some insight into the corrosion behavior of a commercial alloy Fe-12% Cr (3CR12) exposed to imitated seawater. Applying different analytical methods, the main corrosion process was found to be the formation of flakes on the surface which, peel off after they have reached a certain size. Some Cr is dissolved in the solution, its relative concentration with respect to Fe is higher than in the bulk material. The flakes consist mainly of mixed oxihydroxides of the type FeOOH containing some Cr and Mg. The oxidic layer on the interface is very thin, behaves essentially stationary with a slight growth of about 0.05 nm/day. It consists of Cr oxide with some inclusions of Fe and Mg and is not of a chromite type. Immediately below this oxidic layer, the metallic substrate exhibits a thin layer depleted in Cr and behaving like a-Fe (bcc). As compared with stainless steel, potentiostatic current vs. time records at anodic potentials below the pitting potential indicate a very different stability of the surface films for 3CR12. The kinetics of the passive layer formation on 3CR12 was found to follow a parabolic law initially and to change later (after 10...100 seconds in deaerated solution and even earlier in aerated solution) to a linear law. After some time, pitting corrosion and/or cracks due to internal stresses play the dominant role. Cr does not form a protective oxidic layer. The surface morphology of samples exposed at -200 mV for 20 and 80 minutes has been studied by scanning electron microscopy and scanning Auger microprobe. The results reflect the competing formation of oxidic layers and pitting, the participation of Cr in the dissolution process. They also suggest that Mg, which is a component of the solution was incorporated into the rust and some Mg was also found on the metallic surface.     

Determination of the surface pK of carboxylic- and amine-terminated alkanethiols using surface plasmon resonance spectroscopy

When using self-assembled monolayers (SAMs) with ionizable functional groups, such as COOH and NH2, the dissociation constant (pKd) of the surface is an important property to know, since it defines the charge density of the surface for a given bulk solution pH. In this study, we developed a method using surface plasmon resonance (SPR) spectroscopy for the direct measurement of the pKd of a SAM surface by combining the ability of SPR to detect the change in mass concentration close to a surface and the shift in ion concentration over the surface as a function of surface charge density. This method was then applied to measure the pKd values of both COOH- and NH2-functionalized SAM surfaces using solutions of CsCl and NaBr salts, respectively, which provided pKd values of 7.4 and 6.5, respectively, based on the bulk solution pH. An analytical study was also performed to theoretically predict the shape of the SPR plots by calculating the excess mass of salt ions over a surface as a function of the difference between the solution pH and surface pKd. The analytical relationships show that the state of surface charge also influences the local hydrogen ion concentration, thus resulting in a substantial local shift in pH at the surface compared to the bulk solution as a function of the difference between the bulk solution pH and the pKd of the surface.     

New scenarios of protein folding can occur on the ribosome

Identifying and understanding the differences between protein folding in bulk solution and in the cell is a crucial challenge facing biology. Using Langevin dynamics, we have simulated intact ribosomes containing five different nascent chains arrested at different stages of their synthesis such that each nascent chain can fold and unfold at or near the exit tunnel vestibule. We find that the native state is destabilized close to the ribosome surface due to an increase in unfolded state entropy and a decrease in native state entropy; the former arises because the unfolded ensemble tends to behave as an expanded random coil near the ribosome and a semicompact globule in bulk solution. In addition, the unfolded ensemble of the nascent chain adopts a highly anisotropic shape near the ribosome surface and the cooperativity of the folding-unfolding transition is decreased due to the appearance of partially folded structures that are not populated in bulk solution. The results show, in light of these effects, that with increasing nascent chain length folding rates increase in a linear manner and unfolding rates decrease, with larger and topologically more complex folds being the most highly perturbed by the ribosome. Analysis of folding trajectories, initiated by temperature quench, reveals the transition state ensemble is driven toward compaction and greater native-like structure by interactions with the ribosome surface and exit vestibule. Furthermore, the diversity of folding pathways decreases and the probability increases of initiating folding via the N-terminus on the ribosome. We show that all of these findings are equally applicable to the situation in which protein folding occurs during continuous (non-arrested) translation provided that the time scales of folding and unfolding are much faster than the time scale of monomer addition to the growing nascent chain, which results in a quasi-equilibrium process. These substantial ribosome-induced perturbations to almost all aspects of protein folding indicate that folding scenarios that are distinct from those of bulk solution can occur on the ribosome.     

A coupled two-compartment model for immobilized enzyme electrodes

The effect of stirring on the transient and pseudo steady-state behavior of potentiometric and amperometric immobilized enzyme electrodes is accurately modelled by a coupled two-compartment system of nonlinear differential equations. In the first compartment, the enzyme layer, the chemistry is governed by enzyme kinetics and diffusion. This is coupled to the second compartment, the bulk solution, which is controlled only by molecular diffusion. Several results of analytical significance can be obtained by using this model: for example, it is shown how the stirring rate can be used to increase the linear dynamic range.     

Phase separation of polymer solutions on a solvent surface

Study of the dynamics of liquid droplets of dilute and semidilute polymer solutions on the surfaces of liquid subphases representing solvents for corresponding polymers has shown that a spot of a rather stable layer is formed on an air–liquid interface. The spot spreads over a liquid subphase surface to yield a monomolecular polymer layer. At the same time, the solvent passes into the solution, so that the polymer or its concentrated solution remains on the subphase surface. The polymer does not dissolve in the bulk subphase for several hours. The stability of the polymer spot has been explained under the assumption that the interfacial surface possesses elastic properties and hinders the penetration of macromolecules into the bulk subphase. Desolvation of macromolecules followed by phase separation occurs on the surface. The initial rate of the phase separation of the solution is rather high, while the time dependence of the diameter of the spreading spot is described by a scaling law with an exponent almost equal to 2/3.     

Modulating surface rheology by electrostatic protein/polysaccharide interactions

There is a large interest in mixed protein/polysaccharide layers at air-water and oil-water interfaces because of their ability to stabilize foams and emulsions. Mixed protein/polysaccharide adsorbed layers at air-water interfaces can be prepared either by adsorption of soluble protein/polysaccharide complexes or by sequential adsorption of complexes or polysaccharides to a previously formed protein layer. Even though the final protein and polysaccharide bulk concentrations are the same, the behavior of the adsorbed layers can be very different, depending on the method of preparation. The surface shear modulus of a sequentially formed beta-lactoglobulin/pectin layer can be up to a factor of 6 higher than that of a layer made by simultaneous adsorption. Furthermore, the surface dilatational modulus and surface shear modulus strongly (up to factors of 2 and 7, respectively) depend on the bulk -lactoglobulin/pectin mixing ratio. On the basis of the surface rheological behavior, a mechanistic understanding of how the structure of the adsorbed layers depends on the protein/polysaccharide interaction in bulk solution, mixing ratio, ionic strength, and order of adsorption to the interface (simultaneous or sequential) is derived. Insight into the effect of protein/polysaccharide interactions on the properties of adsorbed layers provides a solid basis to modulate surface rheological behavior.     

Influence of DNA adsorption and DNA/cationic surfactant coadsorption on the interaction forces between hydrophobic surfaces

The forces between hydrophobic surfaces with physisorbed DNA are markedly and irreversibly altered by exposure to DNA/cetyltrimethylammonium bromide (CTAB) mixtures. In this colloidal probe atomic force microscopy study of the interactions between a hydrophobic polystyrene particle and an octadecyltrimethylethoxysilane-modified mica surface in sodium bromide solutions, we measure distinct changes in colloidal forces depending on the existence and state of an adsorbed layer of DNA or CTAB-DNA complexes. For bare hydrophobic surfaces, a monotonically attractive approach curve and very large adhesion are observed. When DNA is adsorbed at low bulk concentrations, a long-range repulsive force dominates the approach, but on retraction some adhesion persists and DNA bridging is clearly observed. When the DNA solution is replaced with a CTAB-DNA mixture at relative low CTAB concentration, the length scale of the repulsive force decreases, the adhesion due to hydrophobic interactions greatly decreases, and bridging events disappear. Finally, when the surface is rinsed with NaBr solution, the length scale of the repulsive interaction increases modestly, and only a very tiny adhesion remains. These pronounced changes in the force behavior are consistent with CTAB-induced DNA compaction accompanied by increased DNA adsorption, both of which are partially irreversible.     

A population distribution model for the alignment of nematic liquid crystals

In polymer aligned liquid crystal cells, a surface layer exists. In this surface layer the in-plane distribution of the mesogens, the shape of the mesogens, and their average angle with the surface determine the pretilt angle in the bulk of the sample. A model to incorporate those effects has been proposed. This model gives quantitative agreement with a number of experiments for thick cells, where the optical effects of the surface layer can be neglected. By introducing a linear variation of the optical axis through the surface layer we get qualitative agreement between the model and the pretilt found in thin cells. The thickness of the surface layer is of the order 0·1-1·0 μm.     

DNA translocation through polyelectrolyte‐modified nanopores: An analytical approximation

An analytical model for the electrophoretic speed of DNA translocating through nanopore functionalized with polyelectrolyte (PE) brush is developed for the first time. The electrophoretic speed depends on DNA surface potential, applied electric field, viscosity, and permittivity of solution along with velocity and electrostatic potential at liquid–polyelectrolyte layer (PEL) interface where the interface seemed to behave similar to that of a solid‐state nanopore wall. Under the limit of Debye–Hückel linearization, the electrostatic potential at liquid–PEL interface and at DNA surface have been calculated. Velocity at liquid–PEL interface has been estimated by assuming a linear variation of hydrodynamic frictional force within the PEL. It is observed that velocity and electrostatic potential at liquid–PEL interface strongly depend on PE charge density and softness parameter. Present analytical results show excellent agreement with exact numerical results (i.e., without any approximation) at a higher salt concentration where Debye–Hückel linearization is applicable.     

Electrokinetic flow in a capillary with a charge-regulating surface polymer layer

An analytical study of the steady electrokinetic flow in a long uniform capillary tube or slit is presented. The inside wall of the capillary is covered by a layer of adsorbed or covalently bound charge-regulating polymer in equilibrium with the ambient electrolyte solution. In this solvent-permeable and ion-penetrable surface polyelectrolyte layer, ionogenic functional groups and frictional segments are assumed to distribute at uniform densities. The electrical potential and space charge density distributions in the cross section of the capillary are obtained by solving the linearized Poisson-Boltzmann equation. The fluid velocity profile due to the application of an electric field and a pressure gradient through the capillary is obtained from the analytical solution of a modified Navier-Stokes/Brinkman equation. Explicit formulas for the electroosmotic velocity, the average fluid velocity and electric current density on the cross section, and the streaming potential in the capillary are also derived. The results demonstrate that the direction of the electroosmotic flow and the magnitudes of the fluid velocity and electric current density are dominated by the fixed charge density inside the surface polymer layer, which is determined by the regulation characteristics such as the dissociation equilibrium constants of the ionogenic functional groups in the surface layer and the concentration of the potential-determining ions in the bulk solution.     

Amphiphilic treelike rods at interfaces: layered stems and circular aggregation

Amphiphilic dendron-rod molecules with three hydrophilic poly(ethylene oxide) (PEO) branches attached to a hydrophobic octa-p-phenylene rod stem were investigated for their ability to form two-dimensional micellar structures on a solid surface. A treelike shape of the molecules was reported to be a major factor in the formation of nonplanar micellar structures in solution and in the bulk state (cylindrical and spherical). We observed that in these treelike amphiphilic molecules the hydrophilic terminated dendron branches assemble themselves in surface monolayers with the formation of two-dimensional layered or circular micellar structures. We suggested the formation of the planar ribbon-like structures with interdigitated layering within the loosely packed monolayers and circular, ringlike structures (2D circular aggregates) in the precollapsed state.     

Physical properties of sodium carboxymethyl cellulose molecules adsorbed on a polyacrylonitrile ultrafiltration membrane

Ultrafiltration experiments showed that the graphical relationship between flux and pressure was a straight line through the origin, provided that the wall shear rate of the bulk fluid was higher than a certain critical value or the pressure was below a critical value. A higher critical shear rate corresponded to a higher critical pressure. For these conditions the total hydrodynamic resistance was only slightly greater than the resistance of a clean membrane for pure water. This additional resistance is attributed to a (mono-) molecular layer of macromolecules which is adsorbed on the membrane in the absence of both a concentration polarization layer and a conventional gel layer.At steady state ultrafiltration conditions, an increase of the flux was obtained after replacing the bulk solution by distilled water at constant experimental conditions, which is attributed to the removal of the concentration polarization layer whereas a mono-molecular layer of macromolecules remained adsorbed on the membrane. For these conditions the flux vs. pressure relationship showed a qualitatively similar behaviour as for ultrafiltration conditions.At a constant shear rate the flux vs. pressure relationship was a straight line through the origin for pressures below the critical pressure, the value of which increased with the shear rate. This linear relationship was reversible, showing no hysteresis. However, if the pressure was higher than its critical value, the flux vs. pressure relationship was no longer a straight line as a consequence of the occurrence of an additional hydrodynamic resistance which did not disappear entirely upon lowering the pressure below its critical value. For the explanation of these phenomena it is assumed that freely moveable parts of the adsorbed macromolecules can block the entrance region of the pores in the membrane if the pressure is beyond its critical value.On the other hand, for pressures below the critical pressure or shear rates beyond the critical shear rate, the pores of the membrane are deblocked. This blocking and deblocking of pores by parts of adsorbed macromolecules apparently takes place in a partly reversible way.     

Adsorption behavior of bis (2-ethylhexyl) sodium sulfosuccinate (AOT) at the mercury-electrolyte solution interface as a function of electrode potential and time

The dependence of the differential capacitance (C) of the electrode double layer of a hanging mercury drop electrode in bis (2-ethylhexyl) sodium sulfosuccinate (AOT) solutions on electrode potential (E) and time is measured using three-dimensional phase sensitive ac voltammetry. This methodology, possessing a very wide time window that permits a detailed study of the adsorption phenomena, is based on the reconstruction of C vs E curves, sampled after many phase-sensitive ac chronoamperometric experiments. The shape of these curves allows an estimation of the structure of the layer of AOT molecules absorbed at the electrode surface. AOT molecules form micelles in bulk solutions and they also associate in the charged interface under the strong influence of the electric field into surface aggregates which depend on their concentration and applied potential. The presence of AOT micelles in the bulk solution can be linked with the appearance of a surface film at potentials more negative than those corresponding to a condensed film linked with a capacitance value slightly higher than that normally attributed to a compact layer. The whole phenomenon is proved to be very dependant upon time.     

Electrostatic potential around charged finite rodlike macromolecules: nonlinear Poisson-Boltzmann theory

In this paper, we show that the far field electrostatic potential created by a highly charged finite size cylinder within the nonlinear Poisson-Boltzmann (PB) theory, is remarkably close to the potential created within the linearized PB approximation by the same object at a well-chosen fixed potential. Comparing the nonlinear electrostatic potential with its linear counterpart associated to a fixed potential boundary condition (called the effective surface potential), we deduce the effective charge of the highly charged cylinder. Values of the effective surface potential are provided as a function of the bare surface charge and Debye length of the ionic solution. This allows to compute the anisotropic electrostatic interaction energy of two distant finite rods.