PubMed Health⌕ Search

Biomedical subjects

Eli Ruckenstein

Publications and source records attributed to Eli Ruckenstein.

At least 19 recordsLinked to original sources
PubMed2005

Thermodynamically stable dispersions induced by depletion interactions.

When small particles are added to a colloidal dispersion of large particles, a depletion interaction between large particles occurs because the small ones are depleted from the gaps between the former particles. In the present paper, a cell model is employed to examine the behavior of a dispersion of large particles immersed in an electrolyte solution containing small particles. In this model, each cell consists of one large particle in its center and an associated atmosphere. Double-layer, van der Waals, and depletion interactions, as well as entropic effects, have been taken into account. When the change of the free energy with respect to that of the electrolyte solution is negative (and this happens in most cases), the dispersions of large particles are stable from a thermodynamic point of view. With increasing volume fraction of the small particles, the free energy change becomes more negative. The formation of gels observed experimentally in concentrated emulsions is explained through the formation of a thermodynamically stable dispersion.

Journal Article↗
PubMed2005

Efficient surface grafting of luminescent silicon quantum dots by photoinitiated hydrosilylation.

We suggest a method for efficient (high-coverage) grafting of organic molecules onto photoluminescent silicon nanoparticles. High coverage grafting was enabled by use of a modified etching process that produces a hydrogen-terminated surface on the nanoparticles with very little residual oxygen and by carefully excluding oxygen during the grafting process. It had not previously been possible to produce such a clean H-terminated surface on free silicon nanoparticles or, subsequently, to produce grafted particles without significant surface oxygen. This allowed us to (1) prepare air-stable green-emitting silicon nanoparticles, (2) prepare stable dispersions of grafted silicon nanoparticles in a variety of organic solvents from which particles can readily be precipitated by addition of nonsolvent, dried, and redispersed, (3) separate these nanoparticles by size (and therefore emission color) using conventional chromatographic methods, (4) protect the particles from chemical attack and photoluminescence quenching, and (5) provide functional groups on the particle surface for further derivatization. We also show, using 1H NMR, that the photoinitiated hydrosilylation reaction does not specifically graft the terminal carbon atom to the surface but that attachment at both the first and second atom occurs.

Journal Article↗
PubMed2005

Microscopic treatment of a barrel drop on fibers and nanofibers.

The microscopic approach of Berim and Ruckenstein (J. Phys. Chem. B 108 (2004) 19330, 19339) regarding the shape and stability of a liquid drop on a planar bare solid surface is extended to a liquid barrel drop on the bare surface of a solid cylinder (fiber) of arbitrary radius. Assuming the interaction potentials of the liquid molecules between themselves and with the molecules of the solid of the London-van der Waals form, the potential energy of a liquid molecule with an infinitely long fiber was calculated analytically. A differential equation for the drop profile was derived by the variational minimization of the total potential energy of the drop by taking into account the structuring of the liquid near the fiber. This equation was solved in quadrature and the shape and stability of the barrel drop were analyzed as functions of the radius of the fiber and the microscopic contact angle theta(0) which the drop profile makes with the surface of the fiber. The latter angle is dependent on the fiber radius and on the microscopic parameters of the model (strength of the intermolecular interactions, densities of the liquid and solid phases, hard core radii, etc.). Expressions for the evaluation of the microcontact angle from experimentally measurable characteristics of the drop profile (height, length, volume, location of inflection point) are obtained. All drop characteristics, such as stability, shape, are functions of theta(0) and a certain parameter a which depends on the model parameters. In particular, the range of drop stability consists of three domains in the plane theta(0)-a, separated by two critical curves a=a(c)(theta(0)) and a=a(c1)(theta(0)) [a(c)(theta(0)) h(m1) cannot exist, whereas in the third domain (between those curves) the drop can have values of h(m) either smaller than h(m1) or larger than h(m2), where h(m2)>h(m1) is a second critical height. For sufficiently large fiber radii, R(f)1 >/= microm, the critical curves almost coincide and only two domains, the first and the second, remain. The smaller the radius, the larger is the difference between the critical curves and the larger is the second domain of drop stability. The shape of the drop depends on whether the point (theta(0),a) on the theta(0)-a plane is far from the critical curve or near it. In the first case the drop profile has generally a large circular part, while in the second case the shape is either almost planar or contains a long manchon that is similar to a film on the fiber.

Journal Article↗
PubMed2005

On the restabilization of protein-covered latex colloids at high ionic strengths.

Recent experiments on restabilization of protein-covered latex colloids at high ionic strengths reported by Lopez-Leon et al.(1) revealed strong specific anion effects. The same authors also emphasized that a recent polarization model, which involves both hydration and double layer forces, can account only for some of their experimental results but are in disagreement with other experimental results. The aim of the present paper is to show that most experimental results of ref 1 can be described, more than qualitatively, when the association equilibria for all the ions (with both the acidic and basic sites of the protein) are taken into account. As the traditional Poisson-Boltzmann approach, the polarization model neglects additional interactions between ions, and ions and surfaces, not included in the "mean field" electrical potential; therefore, a complete quantitative agreement should not be expected. While many of the discrepancies between calculations and experiment occur at low ionic strengths (10(-)(4)-10(-)(2) M), in the range of validity of the traditional DLVO theory, the latter can neither explain them. It is suggested that the structural modifications of the protein configuration induced by the electrolyte are responsible for some of the disagreements between experiment and calculations.

Colloids↗
PubMed2004

The bridging force between two plates by polyelectrolyte chains.

The interaction between particles in a colloidal system can be significantly affected by their bridging by polyelectrolyte chains. In this paper, the bridging is investigated by using a self-consistent field approach which takes into account the van der Waals interactions between the segments of the polyelectrolyte molecules and the plates, as well as the electrostatic and volume exclusion interactions. A positive contribution to the force between two plates is generated by the van der Waals interactions between the segments and the plates. This positive (repulsive) contribution plays an important role in the force when the distances between the plates are small. With increasing van der Waals interaction strength between segments and plates, the force between the plates becomes more repulsive at small distances and more attractive at large distances. When the surfaces of the plates have a constant surface electrical potential and a charge sign opposite to that of the polyelectrolyte chains, the force between the two plates becomes less attractive as the bulk polyelectrolyte concentration increases. This behavior is due to a higher bulk counterion concentration dissociated from the polyelectrolyte molecules. At short distances, the force between plates is more repulsive for stiffer chains. A comparison between theoretical and experimental results regarding the contraction of the interlayer separation between the platelets of vermiculite clays against the concentration of poly(vinyl methyl ether) was made.

Journal Article↗
PubMed2004

The polarization model for hydration/double layer interactions: the role of the electrolyte ions.

The interactions between hydrophilic surfaces in water cannot be always explained on the basis of the traditional Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, and an additional repulsion, the "hydration force" is required to accommodate the experimental data. While this force is in general associated with the organization of water in the vicinity of the surface, different models for the hydration were typically required to explain different experiments. In this article, it is shown that the polarization-model for the double layer/hydration proposed by the authors can explain both (i) the repulsion between neutral lipid bilayers, with a short decay length ( approximately 2 A), which is almost independent of the electrolyte concentration, and, at the same time, (ii) the repulsion between weakly charged mica surfaces, with a longer decay length ( approximately 10 A), exhibiting not only a dependence on the ionic strength, but also strong ion-specific effects. The model, which was previously employed to explain the restabilization of protein-covered latex particles at high ionic strengths and the existence of a long-range repulsion between the apoferritin molecules at moderate ionic strengths, is extended to account for the additional interactions between ions and surfaces, not included in the mean field electrical potential. The effect of the disorder in the water structure on the dipole correlation length is examined and the conditions under which the results of the polarization model are qualitatively similar to those obtained by the traditional theory via parameter fitting are emphasized. However, there are conditions under which the polarization model predicts results that cannot be recovered by the traditional theory via parameter fitting.

Electrolytes↗
PubMed2004

On the monomer density of grafted polyelectrolyte brushes and their interactions.

Most of the modern theories of grafted polyelectrolyte brushes are valid only for moderate stretching of the polyelectrolyte. However, particularly at low ionic strength and high grafting densities, even a moderate charge of the polyelectrolyte can generate a strong stretching. A simple mean field model for strongly stretched grafted polyelectrolyte brushes is suggested, based on an approximate calculation of the partition function of a polyelectrolyte chain. It is shown that the average Boltzmann factor of a possible chain configuration can be approximated by the Boltzmann factor of a configuration with a constant monomer distribution, for which the free energy can be readily obtained. The monomer density in the brush and the interaction between two surfaces with grafted polyelectrolyte brushes could be calculated as a statistical average over all possible configurations. Some simple analytical results are derived, and their accuracy is examined. The dependence of the brush thickness on the electrolyte concentration is investigated, and it is shown that the trapping of a fraction of counterions in the brush influences strongly the thickness of the brush. When two surfaces with grafted polyelectrolyte brushes approach each other more rapidly than the ion diffusion parallel to the surface, the trapping of the counterions between the brushes can affect the interactions by orders of magnitude.

Electrolytes↗
PubMed2004

Specific ion and ph effects on supramolecular assembly of mesostructured V-Mg oxides.

Mesostructured V-Mg oxides were synthesized using the surfactant cetyltrimethylammonium bromide (CTAB) as template, V2O5, V(acac)3 (vanadium acetylacetonate), or NH4VO3 as vanadium source, and Mg(NO3)2, MgCl2, MgSO4, (MgCO3)4.Mg(OH)2, Mg(CH3CO2)2, or Mg(C2H5O)2 as magnesium source. The factors that influence the formation of mesostructured V-Mg oxides, such as the pH, the natures of magnesium and vanadium sources, and the ionic strength, were identified. The formation of mesophases could be related to the presence of anionic vanadium species, to the electrostatic interactions between the oppositely charged vanadates and micellar headgroups, and to the nature of the counterion of Mg2+ in the magnesium source. The main role was played by the pH and only when the pH allowed the formation of vanadates was a mesostructure generated. The counterions of Mg2+ also played a role, which could be explained via specific ion effects and the formation of complexes between them and the vanadium-containing species, which are attracted by the headgroups of the micellar templates.

Journal Article↗
PubMed2004

Simple model for grafted polymer brushes.

The first theories of grafted polymer brushes assumed a step profile for the monomer density. Later, the real density profile was obtained from Monte Carlo or molecular dynamics simulations and calculated numerically using a self-consistent field theory. The analytical approximations of the solutions of the self-consistent field equations provided a parabolic dependence of the self-consistent field, which in turn led to a parabolic distribution for the monomer density in neutral brushes. As shown by numerical simulations, this model is not accurate for dense polymer brushes, with highly stretched polymers. In addition, the scaling laws obtained from the analytical approximations of the self-consistent field theory are identical to those derived from the earlier step-profile-approximation and predict a vanishing thickness of the brush at low graft densities, and a thickness exceeding the length of the polymer chains at high graft densities. Here a simple model is suggested to calculate the monomer density and the interaction between surfaces with grafted polymer brushes, based on an approximate calculation of the partition function of the polymer chains. The present model can be employed for both good and poor solvents, is compatible with a parabolic-like profile at moderate graft densities, and leads to an almost steplike density for highly stretched brushes. While the thickness of the brush depends strongly on solvent quality, it is a continuous function in the vicinity of the temperature. In good and moderately poor solvents, the interactions between surfaces with grafted polymer brushes are always repulsive, whereas in poor solvents the interactions are repulsive at small separations and become attractive at intermediate separation distances, in agreement with experiment. At large separations, a very weak repulsion is predicted.

Journal Article↗
PubMed2004

Double layer interaction between two plates with polyelectrolyte brushes.

When polyelectrolyte chains are grafted to colloidal particles, the electric field between particles is affected by the charges of the chains. In some previous theoretical attempts, the charge density of the polyelectrolyte chains per unit length was considered constant, and its effect was accounted for by introducing an additional constant charge density into the unidimensional Poisson-Boltzmann equation, which was evaluated assuming that it is uniformly distributed in the polyelectrolyte volume of the brush. In this paper, a more detailed model is employed for the calculation of the electrical potential between two plates on which polyelectrolyte brushes are present. In this model, the polyelectrolyte chain is viewed as a rigid cylinder, on the surface of which charges are generated through the dissociation of ionizable sites and adsorption of the cations of the electrolyte. To each of the chains an atmosphere is attached which for simplicity is assumed cylindrical. In the brush region, the electrical potential is described by a two-dimensional Poisson-Boltzmann equation, while in the region free of polyelectrolyte chains by a unidimensional Poisson-Boltzmann equation. Such a model is physically suitable when the charges of the chains are sufficiently large for the repulsion they generate to ensure that the chains are fully extended. Such cases are quite frequent, because relatively low charges lead to an almost complete extension of the chains. In this paper, both the plate surface and the surface of the cylinders are considered charged. The effects of electrolyte concentration, pH, brush thickness and chain coverage density on the repulsion between plates are examined.

Journal Article↗
PubMed2004

Long-range ordered structures in diblock copolymer melts induced by combined external fields.

The structure of diblock copolymer melts under a single external electric or shear field, as well as under combined orthogonal external fields was investigated using a cell dynamic system. The phase structure was determined by coupling the effects of the external fields with the original structure of the bulk free of external fields. The single electric or shear field generated long-range cylinders in asymmetric A4mB6m diblock copolymers and distorted lamellae in symmetric A5mB5m diblock copolymers. Successive orthogonal shear followed by an electric external field generated long-range lamellae in symmetrical A5mB5m systems. However, the simultaneous orthogonal electric and shear fields could more easily form long-range lamellae than the sequential orthogonal fields. The dynamical processes in diblock copolymer melts under orthogonal fields have been also examined.

Journal Article↗
PubMed2004

Interaction force between two charged plates immersed in a solution of charged particles. Coupling between double layer and depletion forces.

When two parallel plates are immersed in a solution of small charged particles, the center of the particles is excluded from a region of thickness D/2 near the plate, where D is their diameter. The approach which Langmuir developed for the double layer repulsion in the presence of an electrolyte with ions of negligible size is extended to the case in which one of the "ions" is a charged particle of finite, relatively small size. A general expression for the force generated between the two charged plates immersed in an electrolyte solution containing relatively small charged particles is derived. In this expression, only the electrical potential at the middle distance between the plates is required to calculate the force. A Poisson-Boltzmann equation which accounts for the volume exclusion of the charged particles in the vicinity of the surface is solved to obtain the electrical potential at the middle between the two plates. Starting from this expression, some results obtained previously for the depletion force acting between two plates or two spheres are rederived. For charged plates immersed in a solution of an electrolyte and charged small particles, the effects of the particle charge, particle charge sign, particle size, and volume fraction of the particles on the force acting between the two plates are examined.

Journal Article↗
PubMed2004

Kinetics of phase transformation on a Bethe lattice in the presence of spin exchange.

Kinetics of phase transformation on a Bethe lattice governed by single-spin-flip Glauber and spin-exchange Kawasaki dynamics is examined. For a general Glauber dynamics for which all processes (splitting and coagulation, growth and decay of clusters, as well as creation and annihilation of single-spin clusters) take place, the addition of the Kawasaki dynamics accelerates the transformation process without changing the qualitative behavior. In the growth-decay regime of the Glauber dynamics, regime in which the splitting and coagulation, and creation and annihilation processes due to single-spin flips are negligible, the Kawasaki dynamics strongly increases the fraction of transformed phase because of the splitting and coagulation of clusters induced by the spin-exchange processes. Acting alone, the Kawasaki dynamics leads to the growth of the clusters of each of the phases after the quenching of the temperature to a lower value. When the final temperature T(f) is smaller than a certain temperature T(f0), the average cluster radius grows linearly with time during both the initial and intermediate stages of the kinetic process, and diverges as log(2)(t(d)-t)(-1) when the time t approaches the value t(d) at which infinite clusters arise. It is shown that, among the various spin-exchange processes involved in Kawasaki dynamics, the main contribution is provided by those which decrease or increase the number of clusters by unity.

Journal Article↗
PubMed2004

Fluorescence study of aggregation in water of PEO-grafted polydiphenylamine.

Fluorescence spectra of water-soluble conducting poly(ethylene oxide)-grafted polydiphenylamines (PDPA-g-PEOs with the M(n)s of PEO 350, 750, and 2000) in water were determined and interpreted. The emissions of the PDPA-g-PEOs occurred in the range from 360 to 700 nm and were dependent on their concentrations, PEO chain length, extent of oxidation, pH, and temperature. An optimum concentration, above which the fluorescence intensity decreased dramatically because of quenching, was observed. This quenching was a result of the aggregation of PDPA-g-PEO macromolecules in water. The doped PDPA-g-PEO molecules provided a lower optimum concentration than the corresponding reduced-state macromolecules. A rod-shaped microstructure of nanoscale size was generated through the aggregation of the PDPA-g-PEO macromolecules. This microstructure was also confirmed by dynamic light scattering, atomic force microscopy, and surface elemental analysis.

Journal Article↗
PubMed2004

Double-layer interaction between two plates with hairy surfaces.

In most theoretical treatments of colloidal particles with hairy surfaces, only the steric effect is taken into account. The steric force is a short-range interaction and acts only when the chains on different particles begin to interpenetrate each other. However, since the hairy chains are extended into the continuous phase, they constrain the orientation of the water molecules near the surface and, as a result, the dielectric constant in that region can become very different from that in the bulk. The low dielectric constant affects the distributions of ion concentrations and the gradient of the electric field. Therefore, the double-layer interactions between two plates with hairy surfaces cannot be calculated on the basis of the classical Gouy-Chapman theory, which involves a uniform dielectric constant in the Poisson-Boltzmann equation. A model which accounts for the difference in dielectric constants in the hairy region and outside that region is therefore proposed. The ion specificity is also taken into account by using Born's expression for the free energy of hydration of ions. The repulsive forces calculated via the Gouy-Chapman theory and via the new model are compared. The hairy region can have a long range effect on the repulsive double-layer interactions.

Journal Article↗
PubMed2004

Quantum chemical density-functional theory calculations of the structures of defect C60 with four vacancies.

Quantum chemical density-functional theory (DFT) calculations have been carried out for the six isomers obtained by removing four adjacent atoms from C60. The most stable isomer consists of twelve 5-member and eighteen 6-member rings, indicating that the removal of some atoms from C60, which contains twelve 5-member rings and twenty 6-member rings, does not always generate larger holes. Each of the other five isomers contains at least one 4-member ring and one larger ring (7-, 8-, 9-, or 10-member ring) besides the 5- and 6-member rings. All isomers have similar structures for singlet and triplet spin multiplicities but with different stabilities. The ground states for two of the isomers are triplets, whereas the ground states for the other isomers are singlets. Furthermore, a comparison between the various isomers allowed one to examine the effect of the structure on the stability of fullerene cages.

Journal Article↗
PubMed2004

Attractive interactions in dispersions of identical charged colloidal particles: a Monte Carlo simulation.

Using the Debye-Hückel pair potential, the collective interactions between identical charged particles were examined via Monte Carlo simulations. The results have shown that when the number of charges per particle and the particle volume fraction were sufficiently large, the pair long-range electrostatic repulsion generated an effective attractive interaction between identical charged particles because of many-body effects. Disordered liquid-like structures, ordered crystal-like structures, ordered structures dispersed in disordered ones, and disordered structures dispersed in ordered ones have been found. The structures are dependent on the volume fraction and charge of the particles, as well as on the electrolyte concentration.

Journal Article↗