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Eli Ruckenstein

Publications and source records attributed to Eli Ruckenstein.

At least 37 records · Page 2Linked to original sources
PubMed2005

Bond order bond polarizability model for fullerene cages and nanotubes.

It is still a challenge to accurately calculate the polarizabilities of large fullerene cages and nanotubes. In this paper, a simple bond order bond polarizability relationship for carbon was found, which allowed us to apply the bond polarizability model to any pentagon isolation rule (PIR) fullerene (cage or nanotube). Following this approach, the following simple equation, alpha=1.262n, was obtained relating the static dipole polarizability (alpha) of PIR fullerenes (cages or closed nanotubes) to their number (n) of carbon atoms. Furthermore, it was shown that the polarizabilities of C60 and C70, calculated on the basis of this model, are in excellent agreement with those obtained experimentally and by density-functional theory calculations.

Journal Article↗
PubMed2005

On the interactions of ions with the air/water interface.

In the vicinity of a charged interface, the Poisson-Boltzmann approach considers that the ions obey Boltzmann distributions in a mean electrical field that satisfies the Poisson equation. However, the boundary between two dielectrics generates additional interactions between ions and the interface. The traditional models of ion hydration interactions, that assume that water is a homogeneous dielectric, predict that these interactions are repulsive for all kinds of ions, since all ions should prefer the medium with a larger dielectric constant, where they are better hydrated. In reality, the interactions between the ions and the neighboring water molecules can generate additional short-range ion-hydration interactions, which are either repulsive (for structure-making ions) or attractive (for structure-breaking ions). In the present paper, various models for the ion-hydration forces are examined and compared with the results of molecular dynamics simulations. At large ionic strengths, the latter results could be reproduced qualitatively only when short-ranged attractions between the structure-breaking ions and the interface were taken into account.

Journal Article↗
PubMed2005

Relationship between preferential interaction of a protein in an aqueous mixed solvent and its solubility.

The present paper is devoted to the derivation of a relation between the preferential solvation of a protein in a binary aqueous solution and its solubility. The preferential binding parameter, which is a measure of the preferential solvation (or preferential hydration) is expressed in terms of the derivative of the protein activity coefficient with respect to the water mole fraction, the partial molar volume of protein at infinite dilution and some characteristics of the protein-free mixed solvent. This expression is used as the starting point in the derivation of a relationship between the preferential binding parameter and the solubility of a protein in a binary aqueous solution. The obtained expression is used in two different ways: (1) to produce a simple criterion for the salting-in or salting-out by various cosolvents on the protein solubility in water, (2) to derive equations which predict the solubility of a protein in a binary aqueous solution in terms of the preferential binding parameter. The solubilities of lysozyme in aqueous sodium chloride solutions (pH=4.5 and 7.0), in aqueous sodium acetate (pH=8.3) and in aqueous magnesium chloride (pH=4.1) solutions are predicted in terms of the preferential binding parameter without any adjustable parameter. The results are compared with experiment, and for aqueous sodium chloride mixtures the agreement is excellent, for aqueous sodium acetate and magnesium chloride mixtures the agreement is only satisfactory.

Chemical Phenomena↗
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

Density functional theory calculations for endohedral complexes of non-pi C60H60 cage with small guest molecules.

Hybrid density-functional theory (B3LYP) calculations were carried out to determine the structures and energies of endohedral complexes of non-pi C(60)H(60) with H(2), CO, and LiH. It was demonstrated that the endohedral complexes of C(60)H(60) with the above three guest molecules are more stable than the corresponding complexes with C(60). Furthermore, the interaction between C(60)H(60) and the inside H(2) or CO is negligible, but the formation of the LiH-C(60)H(60) complex is exothermic with a stabilization energy of -6.0 kcal/mol. While the bond lengths of H(2) and CO changed a little when placed inside the cages, that of the LiH molecule increased and decreased inside C(60)H(60) and C(60), respectively.

Journal Article↗
PubMed2005

Endohedral chemistry of C60-based fullerene cages.

Fullerenes have unique chemistry owing to their cage structure, their richness in pi-electrons, and their large polarizabilities. They can trap atoms and small molecules to generate endohedral complexes as superconductors, drug carriers, molecular reactors, and ferroelectric materials. An important goal is to develop effective methods that can affect the behavior of the atoms and small molecules trapped inside the cage. In this paper, the quantum chemical density functional theory was employed to demonstrate that the stability and position of a guest molecule inside the C60 cage can be changed, and its orientation controlled, by modifying the C60 cage shell. The outside attachment of two hydrogen atoms to two adjacent carbon atoms located between two six-membered rings of the C60 cage affects the orientation of the LiF molecule inside and increases the stability of LiF inside the cage by 45%. In contrast, when 60 hydrogen atoms were attached to the outside surface of the C60 cage, thus transforming all C=C double bonds into single bonds, the stability of the LiF inside was reduced by 34%. If two adjacent carbon atoms were removed from C60, the stability of LiF inside this defect C60 was reduced by 41%.

Journal Article↗
PubMed2005

Microscopic interpretation of the dependence of the contact angle on roughness.

The macroscopic contact angle theta(m) of a liquid drop on a rough solid surface in the presence of a gas is calculated microscopically on the basis of a variational minimization of the total potential energy of the drop. Two limiting cases are considered: the liquid penetrates into the space between asperities (Wenzel regime) and the liquid resides on the top of asperities (Cassie-Baxter regime). Long-range as well as short-range interactions between the molecules of liquid, solid, and gas are taken into account. It was also assumed that small portions of insoluble gas are accumulated near the edges of the asperities during the formation of the droplet. The contact angle depends on several parameters involved in the microscopic interactions as well as on the fractions of solid surface between asperities, and of the surface of the asperities themselves, that are in contact with the liquid. It is shown that the theory can explain the nonlinear dependence of cos theta(m) on roughness observed by Krupenkin et al. [Krupenkin, T. N.; Taylor, J. A.; Schneider, T. M.; Yang, S. Langmuir 2004, 20, 3824].(1).

Chemical Phenomena↗
PubMed2005

A protein molecule in an aqueous mixed solvent: fluctuation theory outlook.

In the present paper a procedure to calculate the properties of proteins in aqueous mixed solvents, particularly the excesses of the constituents of the mixed solvent near the protein molecule and the preferential binding parameters, is suggested. Expressions for the Kirkwood-Buff integrals in ternary mixtures and for the preferential binding parameter were derived and used to calculate various properties of infinitely dilute proteins in aqueous mixed solvents. The derived expressions and experimental information regarding the partial molar volumes and the preferential binding parameters were used to calculate the excesses (deficits) of water and cosolvent (in comparison with the bulk concentrations of protein-free mixed solvent) in the vicinity of ribonuclease A, ribonuclease T1, and lysozyme molecules. The calculations showed that water was in excess in the vicinity of ribonuclease A for water/glycerol and water/trehalose mixtures, and the cosolvent urea was in excess in the vicinity of ribonuclease T1 and lysozyme. The derivative of the activity coefficient of the protein with respect to the mole fraction of water was also calculated. This derivative was negative for the water/glycerol and water/trehalose mixed solvents and positive for the water/urea mixture. The mixture of lysozyme in the water/urea solvent is of particular interest, because the lysozyme at pH 7.0 is in its native state up to 9.3M urea, while at pH 2.0 it is denaturated between 2.5 and 5M and higher concentrations of urea. Our results demonstrated a striking similarity in the hydration of lysozyme at both pHs. It is worthwhile to note that the excesses of urea were only weakly composition dependent on both cases.

Dose-Response Relationship, Drug↗
PubMed2005

Cylindrical droplet on nanofibers: a step toward the clam-shell drop description.

The existence and shape of a cylindrical (infinitely long) liquid drop on a fiber of arbitrary radius are examined using a microscopic approach based on the interaction potentials between the molecules of the system. A differential equation for the drop profile was derived by the variational minimization of the total potential energy by taking into account the structuring of the liquid near the fiber. This equation was solved by quadrature, and the existence conditions and the shape of the drop were examined as functions of the radius of the fiber, microscopic contact angle theta(0), which the actual drop profile makes with the fiber, and a certain parameter, a, which depends on the interaction potential parameters. Angle theta(0) is defined in the nanoscale range near the leading edge where the interactions between the liquid and solid are strong. It differs from the macroscopically measured wetting angle (theta(m)) that represents the extrapolation of the profile outside the range of liquid-solid interaction to the solid surface. Expressions for both theta(0) and theta(m) are established in the paper. For any given fiber radius, the range of drop existence involves two domains in the plane theta(0) - a, separated by a critical curve a = a(c)(theta(0)). In the first domain, below the curve a = a(c)(theta(0)), the drop always exists and can have any height, h(m). In the second domain, above the curve a = a(c)(theta(0)), there is an upper limit of h, h(m1), such that drops with h(m) > h(m1) cannot exist. 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 to it. In the first case, the drop profile has generally a circular shape, with the center of the circle not located on the fiber axis, whereas in the second case the shape is "quasi planar", that is, most of the drop profile lies on a circle concentric with the fiber profile. Comparing the potential energies of a cylindrical drop on a fiber and a film of uniform thickness covering the fiber and having the same volume as the drop, the energetically preferred configuration was determined for various conditions. Considering the cylindrical drop as a limiting case of a clam-shell one, and the film as a limiting case of a barrel drop, the obtained analytical results could be employed to examine the barrel-drop-clam-shell-drop transformation (roll-up transition).

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

Treatment of dilute clusters of methanol and water by ab initio quantum mechanical calculations.

Large molecular clusters can be considered as intermediate states between gas and condensed phases, and information about them can help us understand condensed phases. In this paper, ab initio quantum mechanical methods have been used to examine clusters formed of methanol and water molecules. The main goal was to obtain information about the intermolecular interactions and the structure of methanol/water clusters at the molecular level. The large clusters (CH(4)O...(H(2)O)(12) and H(2)O...(CH(4)O)(10)) containing one molecule of one component (methanol or water) and many (12, 10) molecules of the other component were considered. Møller-Plesset perturbation theory (MP2) was used in the calculations. Several representative cluster geometries were optimized, and nearest-neighbor interaction energies were calculated for the geometries obtained in the first step. The results of the calculations were compared to the available experimental information regarding the liquid methanol/water mixtures and to the molecular dynamics and Monte Carlo simulations, and good agreement was found. For the CH(4)O...(H(2)O)(12) cluster, it was shown that the molecules of water can be subdivided into two classes: (i) H bonded to the central methanol molecule and (ii) not H bonded to the central methanol molecule. As expected, these two classes exhibited striking energy differences. Although they are located almost the same distance from the carbon atom of the central methanol molecule, they possess very different intermolecular interaction energies with the central molecule. The H bonding constitutes a dominant factor in the hydration of methanol in dilute aqueous solutions. For the H(2)O...(CH(4)O)(10) cluster, it was shown that the central molecule of water has almost three H bonds with the methanol molecules; this result differs from those in the literature that concluded that the average number of H bonds between a central water molecule and methanol molecules in dilute solutions of water in methanol is about two, with the water molecules being incorporated into the chains of methanol. In contrast, the present predictions revealed that the central water molecule is not incorporated into a chain of methanol molecules, but it can be the center of several (2-3) chains of methanol molecules. The molecules of methanol, which are not H bonded to the central water molecule, have characteristics similar to those of the methane molecules around a central water molecule in the H(2)O...(CH(4))(10) cluster. The ab initio quantum mechanical methods employed in this paper have provided detailed information about the H bonds in the clusters investigated. In particular, they provided full information about two types of H bonds between water and methanol molecules (in which the water or the methanol molecule is the proton donor), including information about their energies and lengths. The average numbers of the two types of H bonds in the CH(4)O...(H(2)O)(12) and H(2)O...(CH(4)O)(10) clusters have been calculated. Such information could hardly be obtained with the simulation methods.

Computer Simulation↗
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↗