Molecular Dynamics Simulation of the Electrical Double Layer of Spherical Macroion

The structure of the electrical double layer (EDL) of a spherical macroion with a total charge of 60 elementary charges is studied by molecular dynamics methods. In calculations we used two models: continuous and discrete. In the continuous model, the total charge was concentrated in the center of the macroion; in the discrete model, elementary charges were randomly distributed over the surface of the macroion. The radial profiles of local densities and electric potential in EDL, as well as the degree of counterion binding by the macroion, are calculated with allowance for the Lennard-Jones and electrostatic interactions. It is established that the character of charge distribution significantly affects the EDL structure near the macroion, whereas its effect is much weaker at larger distances. The results obtained are compared with the experimental data on the surface potential and the diffuse part of EDL of sodium dodecyl sulfate micelles in aqueous solution, as well as on the micelle-bound charge. It is shown that even weak specific interaction between counterions and a macroion can substantially influence the structure of its EDL.     

Comparison of methods for point‐charge representation of electrostatic fields

The calculation of the electrostatic potential resulting from an infinite or extended array of charges in the interior of a region of interest is a frequent task in computational chemistry. In case of a periodic potential this can, for example, be done by Ewald summation or by multipole methods. An important alternative are those methods where arrays of auxiliary point charges are optimized with respect to charge and/or position to reproduce the original electrostatic potential. In the literature different variations are reported. We compare the performance of some of these with respect to their ability to reproduce the original potential and the computational effort required. Between (1) surface charges determined by the conductor‐boundary condition, (2) optimized surface charges, and (3) surface charges floating on the surface we find that (2) offers good quality with small computational costs involved. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2004     

The zeta potential of PMMA in contact with electrolytes of various conditions: Theoretical and experimental investigation

Many unit operations required in microfluidics can be realised by electrokinetic phenomena. Electrokinetic phenomena are related to the presence of electrical surface charges of microfluidic substrates in contact with a liquid. As surface charges cannot be directly measured, the zeta potential is considered as the relevant parameter instead. PMMA is an attractive microfluidic substrate since micron‐sized features can be manufactured at low costs. However, the existence of PMMA surface charges is not well understood and the zeta potential data found in the literature show significant disagreement. In this article, we present a thorough investigation on the zeta potential of PMMA. We use computations of the potential distribution in the electrical double layer to predict the influence of various electrolyte parameters. The generated knowledge is compared to extensive experiments where we investigate the influence of ionic strength, pH, temperature and the nature of the electrolyte. Our findings imply that two different mechanisms influence the zeta potential depending on the pH value. We propose pure shielding in the acidic and neutral milieus while adsorption of co‐ions occurs along with shielding in the alkaline milieu.     

The impact of the modified Poisson–Boltzmann model on protein bound to a lipid coated silicon nanowire field effect transistor biosensor in an electrolyte environment

The aim of this work was to analyse the electrostatic potential profile, various effects of electrolyte concentrations, and the influences of surface charge on a protein bound to a lipid coated Silicon nanowire field effect transistor (Si-NW FET) biosensor by implementing the modified Poisson–Boltzmann (MPB) model. In this work, we modelled a lipid monolayer-coated Si-NW FET for the sensing of proteins, which consisted of variable amounts of aspartic acid. The electrostatic potential profile, protein charge distributions, the response to various electrolyte concentration, and the impacts of various surface charge were studied by implementing the MPB model with the Si-NW FET biosensor. Additionally, a comparison between the use of the MPB and the Poisson–Boltzmann model in studying the effects of various surface charges was carried out. Taken together, it was found that the MPB model showed a higher resolution in studying the Si-NW FET biosensor model when higher concentrations and surface charges were administered.     

X-ray microscopy studies of protein adsorption on a phase segregated polystyrene/polymethylmethacrylate surface. 2. Effect of pH on site preference

X-ray photoemission electron microscopy (XPEEM) using synchrotron radiation illumination has been used to study the adsorption of human serum albumin (HSA) onto a phase segregated polystyrene/polymethylmethacrylate (PS/PMMA) blend surface from solutions of five different pH values. The absolute coverage of albumin on each of three chemically distinct components of the surface, PS domains, PMMA domains, and the interface between the domains, was determined from a quantitative analysis of C 1s image sequences. At all pH values, the preferred adsorption site is the interface. At neutral pH (7.0), albumin showed a slight preference for PS regions relative to PMMA. At strongly acidic pH (2.0) and strongly basic pH (10.0), similar amounts of albumin adsorb on the PS and PMMA regions. However, at pH 4.0, the amount of albumin adsorbed on PMMA domains is approximately 1.6 times greater than that on PS domains, while at pH 8.6 the amount of albumin adsorbed on PMMA is one-half that adsorbed on PS domains. The pH dependence of the site preference is rationalized in terms of the known changes of albumin conformation with pH [Peters, T., Jr. All About Albumin: Biochemistry, Genetics, and Medical Applications; Academic Press: New York, 1995]. We infer from our results that the site preference of albumin adsorption on PS/PMMA blends is related mainly to changes in hydrophobic interactions, which are driven by pH-dependent electrostatic effects, that is, changes to the protein surface structure as the charge on the protein changes. The results provide insight into changes in the secondary structure of albumin in acid and basic media.     

The equipotential surfaces of cubic lattices

The areas of zero electrostatic potential within an array of electric charges in an ionic crystal can be represented as a zero equipotential surface (ZEPS), which separates space into domains of positive and negative potential. ZEPS are conventionally expressed in terms of nodal surfaces. We express the coordinates and charge distribution of several ZEPS in terms of the Jacobi theta functions, and provide their graphical visualisation.     

Particle charging and charge screening in nonpolar dispersions with nonionic surfactants

The electrostatic stabilization of colloidal dispersions is usually considered the domain of polar media only because of the high energetic cost associated with introducing electric charge in nonpolar environments. Nevertheless, some surfactants referred to as "charge control agents" are known to raise the conductivity of liquids with low electric permittivity and to mediate charge stabilization of nonpolar dispersions. Here we study an example of the particularly counterintuitive charging and electrostatic interaction of colloidal particles in a nonpolar solvent caused by nonionic surfactants. PMMA particles in hexane solutions of nonionic sorbitan oleate (Span) surfactants are found to exhibit a field-dependent electrophoretic mobility. Extrapolation to zero field strength yields evidence for large electrostatic surface potentials that decay with increasing surfactant concentration in a fashion reminiscent of electrostatic screening caused by salt in aqueous solutions. The amount of surface charge and screening ions in the nonpolar bulk is further characterized via measurements of the particles' pair interaction energy. The latter is obtained by liquid structure analysis of quasi-2-dimensional equilibrium particle configurations studied with digital video microscopy. In contrast to the behavior reported for systems with ionic surfactants, we observe particle charging and a screened Coulomb type interaction both above and below the surfactant's critical micelle concentration.     

Surface properties of fluids of charged platelike colloids

Surface properties of mixtures of charged platelike colloids and salt in contact with a charged planar wall are studied within density functional theory. The particles are modeled by hard cuboids with their edges constrained to be parallel to the Cartesian axes corresponding to the Zwanzig model [J. Chem. Phys. 39, 1714 (1963)] and the charges of the particles are concentrated at their centers. The density functional applied is an extension of a recently introduced functional for charged platelike colloids. It provides a qualitative approach because it does not determine the relation between the actual and the effective charges entering into the model. Technically motivated approximations, such as using the Zwanzig model, are expected not to influence the results qualitatively. Analytically and numerically calculated bulk and surface phase diagrams exhibit first-order wetting for sufficiently small macroion charges and isotropic bulk order as well as first-order drying for sufficiently large macroion charges and nematic bulk order. The asymptotic wetting and drying behaviors are investigated by means of effective interface potentials which turn out to be asymptotically the same as for a suitable neutral system governed by isotropic nonretarded dispersion forces. Wetting and drying points as well as predrying lines and the corresponding critical points have been located numerically. A crossover from monotonic to nonmonotonic electrostatic potential profiles upon varying the surface charge density has been observed. Nonmonotonic electrostatic potential profiles are equivalent to the occurrence of charge inversion. Due to the presence of both the Coulomb interactions and the hard-core repulsions, the surface potential and the surface charge do not vanish simultaneously, i.e., the point of zero charge and the isoelectric point of the surface do not coincide.     

Triboelectricity: macroscopic charge patterns formed by self-arraying ions on polymer surfaces

Tribocharged polymers display macroscopically patterned positive and negative domains, verifying the fractal geometry of electrostatic mosaics previously detected by electric probe microscopy. Excess charge on contacting polyethylene (PE) and polytetrafluoroethylene (PTFE) follows the triboelectric series but with one caveat: net charge is the arithmetic sum of patterned positive and negative charges, as opposed to the usual assumption of uniform but opposite signal charging on each surface. Extraction with n-hexane preferentially removes positive charges from PTFE, while 1,1-difluoroethane and ethanol largely remove both positive and negative charges. Using suitable analytical techniques (electron energy-loss spectral imaging, infrared microspectrophotometry and carbonization/colorimetry) and theoretical calculations, the positive species were identified as hydrocarbocations and the negative species were identified as fluorocarbanions. A comprehensive model is presented for PTFE tribocharging with PE: mechanochemical chain homolytic rupture is followed by electron transfer from hydrocarbon free radicals to the more electronegative fluorocarbon radicals. Polymer ions self-assemble according to Flory-Huggins theory, thus forming the experimentally observed macroscopic patterns. These results show that tribocharging can only be understood by considering the complex chemical events triggered by mechanical action, coupled to well-established physicochemical concepts. Patterned polymers can be cut and mounted to make macroscopic electrets and multipoles.     

Fluorescence depolarization and contact angle investigation of dynamic and static interfacial tension of liquid crystal display materials

Interfacial interactions control two processes empirically known to be critical for molecular anchoring in twisted nematic liquid crystal displays technology (TN-LCDs): surface treatment and filling procedure. Static and dynamical interfacial tensions (Gamma(SL)) between liquids and several substrates with similar roughness were observed respectively by contact angle (theta(c)) of sessile drops and by fluorescence depolarization of thin liquid films flowing at high velocity. Gamma(SL) decreased when glass was coated with tin dioxide and increased with polyvinyl alcohol (PVA) deposition. Drops were circular for all substrates except rubbed PVA, where they flowed spontaneously along the rubbing direction, reaching an oblong form that had theta(c) parallel and perpendicular to the rubbing direction respectively greater and smaller than theta(c) for non-rubbed PVA. This is attributed to polar group alignment generating an asymmetric Gamma(SL) distribution with nanometric preferential direction, inducing a capillary-like flow. Polarization and anisotropy maps for high-velocity flow parallel to the PVA rubbing direction showed an increase in the net alignment of molecular domains and a widening of the region where it occurred. This is attributed to preferential anchoring in the downstream direction, instead of in several directions, as for non-rubbed PVA. This explains why filling direction is crucial for TN-LCDs homogeneous behavior.     

Dynamic modification of poly(methyl methacrylate) chips using poly(vinyl alcohol) for glycosaminoglycan disaccharide isomer separation

We describe a microchip electrophoresis (MCE) method for the assay of unsaturated disaccharides of chondroitin sulfates, dermatan sulfates, and hyaluronic acid (HA). Poly(vinyl alcohol) (PVA) could be irreversibly adsorbed onto poly(methyl methacrylate) (PMMA) substrates and this approach was applicable for dynamic coating. The characteristics of the PMMA surface with PVA coating were evaluated in terms of the wettability, EOF, and adsorption of 2-aminoacridone (AMAC)-labeled disaccharide. The water contact angle decreased from 73 degrees on a pristine PMMA surface to 37.5 degrees on a PVA-coated surface, indicating that the PVA coating increased hydrophilicity. EOF was reduced approximately twofold and was relatively stable. Scanning electron microscopy and fluorescence microscopy images showed that adsorption of AMAC-labeled disaccharides was dramatically suppressed. Using the PVA coating, baseline separation of two pairs of glycosaminoglycan (GAG) disaccharide isomers, DeltaDi-diS(B)/DeltaDi-diS(D) and DeltaDi-0S/DeltaDi-HA, was achieved in Tris-borate buffer within 130 s by MCE.     

Effects of image charges, interfacial charge discreteness, and surface roughness on the zeta potential of spherical electric double layers

We investigate the effects of image charges, interfacial charge discreteness, and surface roughness on spherical electric double layer structures in electrolyte solutions with divalent counterions in the setting of the primitive model. By using Monte Carlo simulations and the image charge method, the zeta potential profile and the integrated charge distribution function are computed for varying surface charge strengths and salt concentrations. Systematic comparisons were carried out between three distinct models for interfacial charges: (1) SURF1 with uniform surface charges, (2) SURF2 with discrete point charges on the interface, and (3) SURF3 with discrete interfacial charges and finite excluded volume. By comparing the integrated charge distribution function and the zeta potential profile, we argue that the potential at the distance of one ion diameter from the macroion surface is a suitable location to define the zeta potential. In SURF2 model, we find that image charge effects strongly enhance charge inversion for monovalent interfacial charges, and strongly suppress charge inversion for multivalent interfacial charges. For SURF3, the image charge effect becomes much smaller. Finally, with image charges in action, we find that excluded volumes (in SURF3) suppress charge inversion for monovalent interfacial charges and enhance charge inversion for multivalent interfacial charges. Overall, our results demonstrate that all these aspects, i.e., image charges, interfacial charge discreteness, their excluding volumes, have significant impacts on zeta potentials of electric double layers.     

Effect of rubbing load on nanoscale charging characteristics of human hair characterized by AFM based Kelvin probe

The manageability and feel of human hair is significantly affected by its surface charge. Understanding and developing ways to control charge build up is hence highly beneficial. Previous studies have looked at static charging characteristics of hair on a macroscale. In this study, static charging characteristics of hair are studied on the nanoscale with an AFM. Hair is charged by rubbing a control area on its surface with an AFM tip, to which a small voltage bias is applied. The resulting charge distribution is characterized by measuring the surface potential of the control area in situ with AFM based Kelvin probe microscopy. The rubbing load is progressively increased, and the effect of this increase on the charge build up is assessed. Virgin, damaged and conditioner treated hair samples are studied for a better understanding of charge build up and dissipation. Relevant mechanisms are discussed.     

Experimental and theoretical evidence of overcharging of calcium silicate hydrate

Electrokinetic measurements such as electrophoresis may show an inversion of the effective surface charge of colloidal particle called overcharging. This phenomenon has been studied by various theoretical approaches but up to now very few attempts of confrontation between theory and experiment have been conducted. In this work we report electrophoretic measurements as well as Monte Carlo simulations of the electrokinetic potential for the surface of calcium silicate hydrate (CSH), which is the major constituent of hydrated cement. In the simulations, the surface charge of CSH nanoparticles in equilibrium with the ionic solution is determined by a single site characteristic and electrostatic interactions between all explicit charges at the surface and in the electric double layer. We will show that ordinary electrostatic interactions are enough to describe all experimental observations. Actually, an excellent agreement is found between experimental and simulated results without any fitting parameter, both with respect to surface titration and electrokinetic behaviour. The agreement extends over a wide range of electrostatic coupling, from a weakly charged surface with mainly monovalent counter-ions to a highly charged one with divalent counter-ions.     

Preparation of PMMA/acid-modified chitosan core-shell nanoparticles and their potential as gene carriers

The core-shell nanoparticles consisting of poly(methyl methacrylate) (PMMA) cores surrounded by various acid-modified chitosan shells were synthesized using a surfactant-free emulsion copolymerization, induced by a tert-butylhydroperoxide (TBHP) solution. Methyl methacrylate (MMA) was grafted onto four acid-modified chitosans (hydrochloric, lactic, aspartic, and glutamic acids) with MMA conversions up to 64%. The prepared nanoparticles had diameter ranging from 100 to 300 nm characterized by atomic force microscopy and displayed highly positive surface charges up to +77 mV. Transmission electron microscopic images clearly revealed well-defined core-shell morphology of the nanoparticles where PMMA cores were coated with acid-modified chitosan shells. The effect of acid-modified chitosans on particle size, intensity of surface charge, morphology, and thermal stability were determined systematically. The plasmid DNA/nanoparticles complexes were investigated with ζ-potential measurement. The results suggested that these nanoparticles can effectively complex with plasmid DNAs via electrostatic interaction and could be used as gene carriers.

Effect of a low-dielectric interior on DNA electrostatic response to twisting and bending

We study the effects of a low-dielectric core of rod-like macromolecules on their electrostatic persistence lengths. We use the exact solution of the linear Poisson-Boltzmann equation for the potential of a charge on the surface of a low-dielectric cylinder. We apply the results to the B-DNA molecule, modeled as a double helical array of discrete charges wound on the surface of a low-dielectric rod. For this charge geometry, we calculate the change in the electrostatic twist persistence as compared to DNA with a water-permeable core. We also discuss possible effects of the low-dielectric molecular core on DNA bending persistence.     

On the use of AM1 and MNDO wave functions to compute accurate electrostatic charges

A new strategy to evaluate accurate electrostatic charges from semiempirical wave functions is reported. The rigorous quantum mechanical molecular electrostatic potentials computed from both MNDO and AM1 wave functions are fitted to the point-charge molecular electrostatic potential to obtain the electrostatic charges. The reliability of this strategy is tested by comparing the semiempirical electrostatic charges for 21 molecules with the semiempirical Mulliken charges and with the ab initio STO-3G and 6-31G* electrostatic charges. The ability of the dipoles derived from the semiempirical electrostatic and Mulliken charges as well as from the SCF charge distributions to reproduce the ab initio 6-31G* electrostatic dipoles and the gas phase experimental values is determined. The statistical analysis clearly point out the goodness of the semiempirical electrostatic charges, specially when the MNDO method is used. The excellent relationships found between the MNDO and 6-31G* electrostatic charges permit to define a scaling factor which allows to accurately reproduce the 6-31G* electrostatic charge distribution as well as the experimental dipoles from the semiempirical electrostatic charges.     

Surface morphology at nanometer level and optical phase retardation of rubbed alignment films

The surface morphology of rubbed polyimide LC aligning films has been studied by scanning force microscopy. We examined three types of alignment film: HT-210, AL-1051 (main chain type) and AL-8044 (side chain type) polyimide surfaces. The rubbed polyimide surfaces show anisotropic alignment of the polymer chain cluster, and a microgroove between the ripple pattern streaks. Also, they are periodically oriented along the rubbing direction. The optical phase retardation of the rubbed surface does not increase with increased cumulative time of rubbing, On the other hand, it increases monotonically with increasing rubbing depth.     

Investigation of the effect of finite-sized ions on the nanowire field-effect transistor in electrolyte concentration using a modified Poisson–Boltzmann model

One-dimensional (1D) nanowire field-effect transistors (FETs) have recently played a major role in sensing applications. Due to charging of the surface functional chemical groups with protonation and deprotonation, the transport properties of these nanowire transistors affect the aqueous environment, altering the electrical double layer (EDL) potential drops and charge distributions in the electrolyte concentration. In this work, we have implemented the simple modified Poisson–Boltzmann (MPB) theory in a 1D silicon nanowire FET, and the effect of the various finite sizes of ions in z:z symmetric electrolyte concentration was investigated. For a given ionic concentration and surface charge, the EDL potential drop, accumulation of charges and the charge distributions of NaCl and CsCl ions were studied. From the MPB model results with the nanowire FET, it was observed that the potential drop of the EDL depends on the size of the ions in the electrolyte. The study of various electrostatic investigations of finite-sized ions was successfully done by implementing the MPB model on a silicon nanowire FET. It can be used in both chemical and biological sensors.