Motion of a Colloidal Sphere Covered by a Layer of Adsorbed Polymers Normal to a Plane Surface

A combined analytical–numerical study is presented for the slow motion of a spherical particle coated with a layer of adsorbed polymers perpendicular to an infinite plane, which can be either a solid wall or a free surface. The Reynolds number is assumed to be vanishingly small, and the thickness of the surface polymer layer is assumed to be much smaller than the particle radius and the spacing between the particle and the plane boundary. A method of matched asymptotic expansions in a small parameter λ incorporated with a boundary collocation technique is used to solve the creeping flow equations inside and outside the adsorbed polymer layer, where λ is the ratio of the characteristic thickness of the polymer layer to the particle radius. The results for the hydrodynamic force exerted on the particle in a resistance problem and for the particle velocity in a mobility problem are expressed in terms of the effective hydrodynamic thickness (L) of the polymer layer, which is accurate to O(λ²). The O(λ) term forLnormalized by its value in the absence of the plane boundary is found to be independent of the polymer segment distribution and the volume fraction of the segments. The O(λ²) term forL, however, is a sensitive function of the polymer segment distribution and the volume fraction of the segments. In general, the boundary effects on the motion of a polymer-coated particle can be quite significant.     

Thermophoretic force acting on an evaporating particle suspended in a rarefied plasma

Analytical results of the thermophoretic force on an evaporating spherical particle immersed in a rarefied plasma with a large temperature gradient are presented for the extreme case of free-molecule regime and thin plasma sheath. It has been shown that the existence of a temperature gradient in the plasma causes a nonuniform distribution of the local heat flux density on the sphere surface with its maximum value at the fore-stagnation point of the sphere, although the total heal flux to the whole particle is independent of the temperature gradient existing in the plasma. This nonuniform-distribution of the local heat flux density causes a nonuniform distribution of the. local evaporated-mass flux and related reaction force around the surface of an evaporating particle, and thus causes an additional force on the particle. Calculated results show that the thermophoretic force on an evaporating particle may substantially exceed that on a nonevaporating one, especially for the case of a metallic particle (with infinite electric conductivity). The effect of evaporation on the thermophoretic force is more pronounced as the evaporation latent heat of the particle material is comparatively low and as high plasma temperatures are involved.     

Experimental Study of Fibrin/Fibrin-Specific Molecular Interactions Using a Sphere/Plane Adhesion Model

Fibrin, the biopolymer produced in the final step of the coagulation cascade, is involved in the resistance of arterial thrombi to fragmentation under shear flow. However, the nature and strength of specific interactions between fibrin monomers are unknown. Thus, the shear-induced detachment of spherical monodispersed fibrin-coated latex particles in adhesive contact with a plane fibrin-coated glass surface has been experimentally studied, using an especially designed shear stress flow chamber. A complete series of experiments for measuring the shear stress necessary to release individual particles under various conditions (various number of fibrin layers involved in the adhesive contact, absence or presence of plasmin, the main physiological fibrinolytic enzyme) has been performed. The nonspecific DLVO interactions have been shown to be negligible compared to the interactions between fibrin monomers. A simple adhesion model based on the balance of forces and torque on particles, assuming an elastic behavior of the fibrin polymer bonds, to analyze the experimental data in terms of elastic force at rupture of an elementary intermonomeric fibrin bond has been used. The results suggested that this force (of order 400 pN) is an intrinsic quantity, independent of the number of fibrin layers involved in the adhesive contact. Copyright 2001 Academic Press.     

Interaction of Dissimilar Plane Parallel Double Layers at Arbitrary Potential

The elliptic integrals related to the interaction between two dissimilar parallel plates (the potentials on two plates have the opposite sign) are expanded in the series for the smaller surface potential y₀ (or ¦y _d ¦) and the smaller integration constant C as well as the larger surface potential and the larger integration constant, respectively. The number of series terms required to obtain the interaction with six significant digits is not more than 5 when the surface potential is less than or equal to 20 if the series being fit for smaller y₀ and C is combined with the series being fit for larger y₀ and C. The approximate expressions with different precision can be obtained by retaining different number of series terms. The results of Devereux O. F. and de Bruyn P. L. are discovered to be incorrect when absolute value of the surface potential is very large or the integration constant is very large or very small.     

Numerical Study of Electroconvective Instability of Binary Electrolyte in a Cell with Plane Parallel Electrodes

Electroconvective instability of a binary electrolyte in a cell with plane parallel electrodes is studied using a numerical method. When a direct current is passed through the cell, a space charge and an electrical force acting upon the solution form under certain conditions. If the electric force density reaches a critical value, convective instability emerges in the cell, leading to the formation of nonequilibrium dissipative structures similar to Rayleigh–Benard cells in a nonuniformly heated liquid. The critical parameter _crit, at which instability emerges in the system, is determined. Dependences of _crit on the ratio between the diffusion coefficients for electrolyte cations and anions and on the current passed through solution are determined.     

Thermophoretic motion of a solid spherical particle near a solid planar surface

The thermophoretic motion of a solid spherical aerosol particle directed normally to an infinite planar solid surface is analyzed. The solution is performed in a bispherical coordinate system with allowance for linear corrections in the Knudsen number. The finite thermal conductivity of a solid body is taken into account in the analysis.     

An Exact Solution to the Electrostatic Interaction between an Ion-Penetrable Sphere and an Ion-Penetrable Rod

No exact solution for the free energy of electrostatic interaction for a charged sphere and rod geometry in an electrolyte solution has yet been proposed. This geometry is interesting because it can be applied to describe macromolecules interacting with a random fiber-matrix for modeling of hindered transport in diffusional systems. Here we present an analytical approach that yields an exact solution to the problem for ion-penetrable-also called "soft"-sphere and infinitely long rod. This solution is compared to a published finite-element analysis of the same system with nonpenetrable-also called "hard"-sphere and infinitely long rod maintaining a constant surface charge density restriction. For any ionic strength or ratio of rod radius to sphere radius the ion-penetrable method yields an electrostatic free energy of interaction which is lower than that given by the analysis for hard bodies. This free energy is significantly lower for most parameter value combinations and therefore suggests that one should carefully examine the system being modeled to determine if it is approximated better by a hard body or ion-penetrable body approach. Copyright 2000 Academic Press.     

Thermophoretic Velocity of a Small Nonevaporating or Evaporating Particle in a High-Temperature Diatomic Gas

Kinetic-theory analytical results concerning the thermophoretic velocity of a spherical nonevaporating or evaporating particle suspended in a high-temperature diatomic gas with appreciable dissociation degree (e.g., for oxygen with temperatures greater than 3000 K or for nitrogen with temperatures greater than 5500 K) are presented for the free-molecule regime. Molecular dissociation in the bulk gas and atomic recombination at the surface of the cold particle are included in the analysis. It is shown that the thermophoretic velocity of the suspended particle is directly proportional to the temperature gradient and approximately inversely proportional to the gas pressure. The thermophoretic velocities of both nonevaporating and evaporating particles are independent of the particle radius and increase slightly with increase in the specular-reflection fraction. For a nonevaporating particle, the thermophoretic velocity almost does not depend on the recombination fraction of atoms at the particle surface. For an intensely evaporating particle, the thermophoretic velocity (UTV) increases with increasing thermal accommodation factor (a) and decreases with increasing atomic recombination fraction (alpha) at high gas temperatures with appreciable molecular dissociation, while UTV almost does not depend on a and alpha at low gas temperatures. Copyright 1999 Academic Press.     

From an Icosahedron to a Plane: Flattening Dodecaiodo‐dodecaborate by Successive Stripping of Iodine

It has been shown by electrospray ionization–ion‐trap mass spectrometry that B₁₂I₁₂^2? converts to an intact B₁₂ cluster as a result of successive stripping of single iodine radicals or ions. Herein, the structure and stability of all intermediate B₁₂I_n^? species (n=11 to 1) determined by means of first‐principles calculations are reported. The initial predominant loss of an iodine radical occurs most probably via the triplet state of B₁₂I₁₂^2?, and the reaction path for loss of an iodide ion from the singlet state crosses that from the triplet state. Experimentally, the boron clusters resulting from B₁₂I₁₂^2? through loss of either iodide or iodine occur at the same excitation energy in the ion trap. It is shown that the icosahedral B₁₂ unit commonly observed in dodecaborate compounds is destabilized while losing iodine. The boron framework opens to nonicosahedral structures with five to seven iodine atoms left. The temperature of the ions has a considerable influence on the relative stability near the opening of the clusters. The most stable structures with five to seven iodine atoms are neither planar nor icosahedral.     

Reversing the Stereoselectivity of a Palladium‐Catalyzed O‐Glycosylation through an Inner‐Sphere or Outer‐Sphere Pathway

An efficient and concise method for the construction of various O‐glycosidic bonds by a palladium‐catalyzed reaction with a 3‐O‐picoloyl glucal has been developed. The stereochemistry of the anomeric center derives from either an inner‐sphere or outer‐sphere pathway. Harder nucleophiles, such as aliphatic alcohols and sodium phenoxides give β‐products, and α products result from using softer nucleophiles, such as phenol.     

Migration Reaction of a Silyl Group from a Phosphorus to a Carbonyl Oxygen in a Molybdenum Coordination Sphere

The reaction of Cp anion, [C 5 H 4 CH 2 CH 2 P(TMS)Mes] m with (CH 3 CN) 3 Mo(CO) 3 leads to the formation of [( m 5 --C 5 H 4 CH 2 CH 2 --P(TMS)Mes)Mo(CO) 3 ] m , which then reacts with MeI to give a metallaphosphacyclopropane complex with silyl migration.     

Adhesive Contact Deformation of a Single Microelastomeric Sphere

This paper reports on an experimental study of the adhesive contact of a single microscopic (about 300 μm) elastomer sphere compressed between two smooth parallel glass platens at small imposed deformations. An experimental arrangement that allows the simultaneous measurement of the compressive displacements and the reaction forces is described. A number of interesting phenomena, including the pull-off separation and the “jump” contact phenomena of the microsphere and the moving platen supported by a cantilever, are shown in the experimental force-displacement curve of a loading and unloading cycle. The pull-off forces are demonstrated to not depend upon the applied dimensionless approach (compressive displacement/initial particle diameter), while they increase with the increasing rate at which the interfaces are separated. The predictions of an established contact mechanical adhesive theory, Johnson–Kendall–Roberts (JKR) theory, in which the influence of the surface energy on the contact has been taken into account, are in good agreement with these experimental results. An application of the JKR analysis to the pull-off force provides a reasonable estimate of the interfacial free energy of the contact.     

Numerical Study of Rayleigh–Benard Instability of a Binary Electrolyte in a Cell with Plane Parallel Electrodes Taking into Account the Space Charge

An electrochemical system consisting of two plane horizontal electrodes of the same metal and the interelectrode space filled with solution of a salt of this metal is considered. The conditions of emergence of Rayleigh–Benard convective instability in this system are investigated using a numerical method. Two reasons for the instability are taken into account: the buoyant force and the electrical force caused by a very small space charge formed near the electrode, at which the electrochemical reaction proceeds at the limiting diffusion current. The instability emergence conditions are characterized by critical values of two parameters corresponding to the aforementioned forces. The mutual effect of these forces on the instability emergence and an essential role of the ratio between the diffusion coefficients of electrolyte cations and anions are revealed.     

Rapidly Convergent Series for the Computation of the Interaction Energy between Dissimilar Plane Parallel Double Layers

Several rapidly convergent series for the computation of the interaction energy between dissimilar plane double layers (y₀ > y_d > 0) are derived by expanding the interaction energy in the power series of ω ₀ < tanh(y₀/64), the series terms required to obtain the interaction energy with six significant digits do not exceed 1 except C = 2 when the dimensionless surface potential y₀ ≤ 20. The results of Devereux and de Bruyn are discovered to be incorrect when y₀ and y_d are larger, and ξ _d is very large or close to ?2.00000.     

Motion of a drop on a solid surface due to a wettability gradient

The hydrodynamic force experienced by a spherical-cap drop moving on a solid surface is obtained from two approximate analytical solutions and used to predict the quasi-steady speed of the drop in a wettability gradient. One solution is based on approximation of the shape of the drop as a collection of wedges, and the other is based on lubrication theory. Also, asymptotic results from both approximations for small contact angles, as well as an asymptotic result from lubrication theory that is good when the length scale of the drop is large compared with the slip length, are given. The results for the hydrodynamic force also can be used to predict the quasi-steady speed of a drop sliding down an incline.     

Selective In Situ Analysis of Mature microRNAs in Extracellular Vesicles Using a DNA Cage-Based Thermophoretic Assay

Mature microRNAs (miRNAs) in extracellular vesicles (EVs) are involved in different stages of cancer progression, yet it remains challenging to precisely detect mature miRNAs in EVs due to the presence of interfering RNAs (such as longer precursor miRNAs, pre-miRNAs) and the low abundance of tumor-associated miRNAs. By leveraging the size-selective ability of DNA cages and polyethylene glycol (PEG)-enhanced thermophoretic accumulation of EVs, we devised a DNA cage-based thermophoretic assay for highly sensitive, selective, and in situ detection of mature miRNAs in EVs with a low limit of detection (LoD) of 2.05 fM. Our assay can profile EV mature miRNAs directly in serum samples without the interference of pre-miRNAs and the need for ultracentrifugation. A clinical study showed that EV miR-21 or miR-155 had an overall accuracy of 90 % for discrimination between breast cancer patients and healthy donors, which outperformed conventional molecular probes detecting both mature miRNAs and pre-miRNAs. We envision that our assay can advance EV miRNA-based diagnosis of cancer.     

Trifluoromethylchlorosulfonylation of Alkenes: Evidence for an Inner‐Sphere Mechanism by a Copper Phenanthroline Photoredox Catalyst

A visible‐light‐mediated procedure for the unprecedented trifluoromethylchlorosulfonylation of unactivated alkenes is presented. It uses [Cu(dap)₂]Cl as catalyst, and contrasts with [Ru(bpy)₃]Cl₂, [Ir(ppy)₂(dtbbpy)]PF₆, or eosin Y that exclusively give rise to trifluoromethylchlorination of the same alkenes. It is assumed that [Cu(dap)₂]Cl plays a dual role, that is, acting both as an electron transfer reagent as well as coordinating the reactants in the bond forming processes.     

ChemInform Abstract: From an Icosahedron to a Plane: Flattening Dodecaiodo‐dodecaborate by Successive Stripping of Iodine.

Electrospray ionization‐ion‐trap mass spectrometry shows that B₂I₁₂^2‐ converts to an intact B₁₂ cluster by successive stripping of single iodine radicals or ions.     

Chemical Approach to a New Crystal Structure: Phase Control of Manganese Oxide on a Carbon Sphere Template

The stabilization and growth of a non‐native structure, hexagonal wurtzite MnO (h‐MnO), is explored via kinetic control of manganese precursor on a carbon sphere template. MnO is most stable in the cubic rock‐salt structure (c‐MnO), and a number of studies have focused on the synthesis and properties of this rock‐salt phase. However, h‐MnO has not been fully characterized before our work. Prolonged heating at a relatively low temperature yields c‐MnO, whereas rapid heating of the reaction mixture at reflux produces h‐MnO in the presence of carbon spheres. The effect of benzyl amine concentration on the formation of two different oxidation states (c‐MnO and t‐Mn₃O₄) was examined as well. Moreover, the structural stability of the manganese oxides and phase transition of MnO in terms of the wurtzite to rock‐salt structural transformation have been investigated.     

Faxen's Laws of a Composite Sphere under Creeping Flow Conditions

Under creeping flow conditions, Faxen's laws are derived for a composite sphere comprising a solid core covered by a permeable layer of arbitrary thickness. The derivations are carried out by applying reciprocal theorem in combination with fluid velocity and pressure distributions in certain simple flow as a comparison field. In this regard, the fluid velocity disturbances caused by a composite sphere subject to a simple shear flow and a rotational flow are solved individually. In the limiting case where the solid core vanishes, the resulting Faxen expressions for the drag force, torque, and stresslet compare very well with the existing Faxen's law for a porous sphere. It is found that when the porous layer is thick enough and its permeability is sufficiently low, the hydrodynamic behavior of a composite sphere can be approximated by that of a porous particle with equal permeability. This can be explained by the fact that the fluid cannot penetrate deeply into a porous layer of low permeability to flow through the pores near the core surface, and thereby the fluid can hardly feel the resistance from the core surface. Copyright 2000 Academic Press.