We have used non-equilibrium molecular dynamics to simulate the flow of water molecules around a charged nanoparticle described at the atomic scale. These non-equilibrium simulations allowed us to compute the friction coefficient of the nanoparticle and then to deduce its hydrodynamic radius. We have compared two different strategies to thermostat the simulation box, since the low symmetry of the flow field renders the control of temperature non trivial. We show that both lead to an adequate control of the temperature of the system. To deduce the hydrodynamic radius of the nanoparticle we have employed a partial thermostat, which exploits the cylindrical symmetry of the flow field. Thereby, only a part of the simulation box far from the nanoparticle is thermostated. We have taken into account the finite concentration of the nanoparticle by using the result of Hasimoto (J. Fluid. Mech. {\bf 1959}, {\it 5}, 317-328 ) for the friction force in a periodic cubic array of spheres. We have focused on the case of polyoxometalate ions, which are inorganic charged nanoparticles. It appears that, for a given structure of the nanoparticle at the atomic level, the hydrodynamic radius significantly increases with the nanoparticle's charge, a phenomenon that had not been quantified so far using molecular dynamics. The presence of an added salt only slightly modifies the hydrodynamic radius.
We employ a novel Monte Carlo simulation scheme to elucidate the stabilization of neutral colloidal microspheres by means of highly-charged nanoparticles [V. Tohver et al., Proc. Natl. Acad. Sci. U.S.A. 98, 8950 (2001)]. In accordance with the experimental observations, we find that small nanoparticle concentrations induce an effective repulsion that prevents gelation caused by the intrinsic van der Waals attraction between colloids. Higher nanoparticle concentrations induce an attractive potential which is, however, qualitatively different from the regular depletion attraction. We also show h…
Electrolyte theories enable to describe the structural and dynamical properties of simple electrolytes in solution, such as sodium chloride in water. Using these theories for aqueous solutions of charged nanoparticles is a straightforward route to extract their charge and size from experimental data. Nevertheless, for such strongly asymmetric electrolytes, the validity of the underlying approximations have never been properly challenged with exact simulation results. In the present work, well established mesoscopic numerical simulations are used to challenge the ability of advanced electrolyte…
We study charged nanoparticles adsorbed onto surfactant bilayers using small-angle scattering of synchrotron radiation. The in-plane interaction of the particles is well described by a DLVO component (measured independently in solution) and a repulsive dipolar interaction due to the presence of the interface, with an amplitude close to the theoretical prediction. We prove that charged nanoparticles at soft interfaces are well described by the classical model of Poisson-Boltzmann and van der Waals terms; as a corollary, they do not experience the like-charge attraction reported in the literatur…
We present theory and simulations which allow us to quantitatively calculate the amount of surface adsorption excess of charged nanoparticles onto a charged surface. The theory is very accurate for weakly charged nanoparticles and can be used at physiological concentrations of salt. We have also developed an efficient simulation algorithm which can be used for dilute suspensions of nanoparticles of any charge, even at very large salt concentrations. With the help of the new simulation method, we are able to efficiently calculate the adsorption isotherms of highly charged nanoparticles in suspe…
Physical properties of colloidal materials can be modified by addition of nanoparticles. Within a model of like-charged mixtures of particles governed by effective electrostatic interactions, we explore the influence of charged nanoparticles on the structure and thermodynamic phase stability of charge-stabilized colloidal suspensions. Focusing on salt-free mixtures of particles of high size and charge asymmetry, interacting via repulsive Yukawa effective pair potentials, we perform molecular dynamics simulations and compute radial distribution functions and static structure factors. Analysis o…
Ions are critical to the structure and stability of polyelectrolytes such as nucleic acids. In this work, we systematically calculated the potentials of mean force between two like-charged nanoparticles in salt solutions by Monte Carlo simulations. The pseudo-spring method is employed to calculate the potential of mean force and compared systematically with the inversed-Boltzmann method. An effective attraction is predicted between two like-charged nanoparticles in divalent/trivalent salt solution and such attraction becomes weakened at very high salt concentration. Our analysis reveals that f…
The dispersive spreading of microscopic particles in shear flows is influenced both by advection and thermal motion. At the nanoscale, interactions between such particles and their confining boundaries become unavoidable. We address the roles of electrostatic repulsion and absorption on the spatial distribution and dispersion of charged nanoparticles in near-surface shear flows, observed under evanescent illumination. The electrostatic repulsion between particles and the lower charged surface is tuned by varying electrolyte concentrations. Particles leaving the field of vision can be neglected…
The electrostatic interaction between metal spheres is an influential component in the assembly of many nanoscale materials in chemistry. Here we derive a method to calculate the energy and polarizations of metal spheres in arbitrary configurations to an arbitrary multipole order. This helps provide insight into the preferred configurations of charged metal particles and demonstrates the sensitivity of electrostatic interactions to configuration geometry.
In nanoparticle haloing, charged nanoparticles have been found to enhance the stability of colloidal suspensions by forming a non-adsorbing layer surrounding neutral colloids which induces an electrostatic repulsion between them. However, there has been some debate that nanoparticles may directly deposit onto the colloidal surfaces and that the stabilization mechanism relies on nanoparticle adsorption. In this study, we have found that these two mechanisms control the stability of colloidal suspensions across a continuum over increasing nanoparticle concentrations. AFM force measurements showe…
The electromagnetic response of a nanoparticle of an ion-doped polymeric elastic insulator, commonly called as an electret, is considered in the continuum model of a uniformly charged elastic sphere. The spectral formulae for the frequency of optically induced spheroidal and torsional shear oscillations driven by bulk force of elastic and dielectric stresses are obtained in analytic form. Particular attention is given to relaxation dielectric mode of the electrostriction response and its stability in the lowest quadrupole mode. The practical usefulness of ultrafine particles of electrets as a …
The Seebeck and Soret coefficients of ionically stabilized suspension of maghemite nanoparticles in dimethyl sulfoxide are experimentally studied as a function of nanoparticle volume fraction. In the presence of a temperature gradient, the charged colloidal nanoparticles experience both thermal drift due to their interactions with the solvent molecules and electric forces proportional to the internal thermoelectric field. The resulting thermodiffusion of nanoparticles is observed through Forced Rayleigh scattering, while the thermoelectric field is accessed through voltage measurements in a th…
We use a coarse-grained molecular dynamics simulation to investigate the interaction between neutral or charged nanoparticles (NPs) and a vesicle consisting of neutral and negatively charged lipids. We focus on the interaction strengths of hydrophilic and hydrophobic attraction and electrostatic interactions between a lipid molecule and an NP. A neutral NP passes through the lipid membrane when the hydrophobic interaction is sufficiently strong. As the valence of the positively charged NP increases, the membrane permeation speed of the NP is increased compared with the neutral NP and charged l…
Ion-mediated interaction is important for the properties of polyelectrolytes such as colloids and nucleic acids. The effective pair interactions between two polyelectrolytes have been investigated extensively, but the many-body effect for multiple polyelectrolytes still remains elusive. In this work, the many-body effect in potential of mean force (PMF) between like-charged nanoparticles in various salt solutions has been comprehensively examined by Monte Carlo simulation and the nonlinear Poisson-Boltzmann theory. Our calculations show that, at high 1:1 salt, the PMF is weakly repulsive and a…
Measurements of the surface diffusivity of colloidal spheres translating along a vapor/liquid inter- face show an unexpected decrease in diffusivity, or increase in surface drag (from the Stokes-Einstein relation) when the particles situate further into the vapor phase. However, direct measurements of the surface drag from the colloid velocity due to an external force find the expected decrease with deeper immersion into the vapor. The paradoxical drag increase observed in diffusion experiments has been attributed to the attachment of the fluid interface to heterogeneities on the colloid surfa…
Hydrodynamic behavior at the vicinity of a confining wall is closely related to the friction properties of the liquid/solid interface. Here we consider, using Molecular Dynamics simulations, the electric contribution to friction for charged surfaces, and the induced modification of the hydrodynamic boundary condition at the confining boundary. The consequences of liquid slippage for electrokinetic phenomena, through the coupling between hydrodynamics and electrostatics within the electric double layer, are explored. Strong amplification of electro-osmotic effects is revealed, and the non-trivi…
In this review, we address the issue of the electrostatic complexation between charged-neutral diblock copolymers and oppositely charged nanocolloids. We show that nanocolloids such as surfactant micelles and iron oxide magnetic nanoparticles share similar properties when mixed with charged-neutral diblocks. Above a critical charge ratio, core-shell hierarchical structures form spontaneously under direct mixing conditions. The core-shell structures are identified by a combination of small-angle scattering techniques and transmission electron microscopy. The formation of multi-level objects is …
We consider the translocation of a neutral (uncharged) nanoparticle through a pore in a thin membrane with constant surface charge density. If the concomitant Debye screening layer is sufficiently thin, the resulting forces experienced by the particle on its way through the pore are negligible. But when the Debye length becomes comparable to the pore diameter, the particle encounters a quite significant potential barrier while approaching and entering the pore, and symmetrically upon exiting the pore. The main reason is an increasing pressure which acts on the particle when it intrudes into th…
During the past years we have investigated the complexation between nanocolloids and oppositely charged polymers. The nanocolloids examined were ionic surfactant micelles and inorganic oxide nanoparticles. For the polymers, we used homopolyelectrolytes and block copolymers with linear and comb architectures. In general, the attractive interactions between oppositely charged species are strong and as such, the simple mixing of solutions containing dispersed constituents yield to a precipitation, or to a phase separation. We have developed means to control the electrostatically-driven attraction…
Magnetic composite materials i.e. elastomers, polymer gels, or polymer solutions with embedded magnetic nanoparticles are useful for many technical and bio-medical applications. However, the microscopic details of the coupling mechanisms between the magnetic properties of the particles and the mechanical properties of the (visco)elastic polymer matrix remain unresolved. Here we study the response of a single-domain spherical magnetic nanoparticle that is suspended in a polymer solution to alternating magnetic fields. As interactions we consider only excluded volume interactions with the polyme…
It is shown that low Reynolds number fluid flows can cause suspended particles to respond as though they were in an equilibrium system with an effective potential. This general result follows naturally from the fact that different methods of moving particles in viscous fluids give rise to very different long-range flows. Two examples are discussed: electrophoretic `levitation' of a heavy charged sphere, for which a hydrodynamic `pseudo-potential' can be written in closed form, and quasi-two dimensional crystals of like-charged colloidal spheres which form near charged walls, whose apparent att…
Electrostatic interactions provide a convenient way to modulate interactions between nanoparticles, colloids, and biomolecules because they can be adjusted by the solution pH or salt concentration. While the presence of salt provides an easy method to control the net interparticle interaction, the nonlinearities arising from electrostatic screening make it difficult to quantify the strength of the interaction. In particular, when charged particles assemble into clusters or aggregates, nonlinear effects render the interactions strongly non-pairwise. Here we report Brownian dynamics simulations …
When polyelectrolyte-neutral block copolymers are mixed in solutions to oppositely charged species (e.g. surfactant micelles, macromolecules, proteins etc), there is the formation of stable supermicellar aggregates combining both components. The resulting colloidal complexes exhibit a core-shell structure and the mechanism yielding to their formation is electrostatic self-assembly. In this contribution, we report on the structural properties of supermicellar aggregates made from yttrium-based inorganic nanoparticles (radius 2 nm) and polyelectrolyte-neutral block copolymers in aqueous solution…
We examine the dynamics of silica particles grafted with high molecular weight polystyrene suspended in semidilute solutions of chemically similar linear polymer using x-ray photon correlation spectroscopy. The particle dynamics decouple from the bulk viscosity despite their large hydrodynamic size and instead experience an effective viscosity that depends on the molecular weight of the free polymer chains. Unlike for hard sphere nanoparticles in semidilute polymer solutions, the diffusivities of the polymer-grafted nanoparticles do not collapse onto a master curve as a function of normalized …
In our previous publication (Ref. 1) we have shown that the data for the normalized diffusion coefficient of the polymers, $D_p/D_{p0}$, falls on a master curve when plotted as a function of $h/λ_d$, where $h$ is the mean interparticle distance and $λ_d$ is a dynamic length scale. In the present note we show that also the normalized diffusion coefficient of the nanoparticles, $D_N/D_{N0}$, collapses on a master curve when plotted as a function of $h/R_h$, where $R_h$ is the hydrodynamic radius of the nanoparticles.
The influence of hydrodynamic interactions on lane formation of oppositely charged driven colloidal suspensions is investigated using Brownian dynamics computer simulations performed on the Rotne-Prager level of the mobility tensor. Two cases are considered, namely sedimentation and electrophoresis. In the latter case the Oseen contribution to the mobility tensor is screened due to the opposite motion of counterions. The simulation results are compared to that resulting from simple Brownian dynamics where hydrodynamic interactions are neglected. For sedimentation, we find that hydrodynamic int…
Mesoscale simulations of diffusion and sedimentation in shape-anisotropic nanoparticle suspensions
Johannes Gutenberg University Mainz（美因茨约翰内斯·古腾堡大学）；Auburn University（奥本大学）；Leibniz-Institut für Polymerforschung Dresden e.V.（德累斯顿莱布尼茨聚合物研究所）；Technische Universität Dresden（德累斯顿工业大学）
We investigate the dynamics of nanoparticles in semidilute polymer solutions when the nanoparticles are comparably sized to the polymer coils using explicit- and implicit-solvent simulation methods. The nanoparticle dynamics are subdiffusive on short time scales before transitioning to diffusive motion on long time scales. The long-time diffusivities scale according to theoretical predictions based on full dynamic coupling to the polymer segmental relaxations. In agreement with our recent experiments, however, we observe that the nanoparticle subdiffusive exponents are significantly larger tha…
Dynamic processes in dispersions of charged spherical particles are of importance both in fundamental science, and in technical and bio-medical applications. There exists a large variety of charged-particles systems, ranging from nanometer-sized electrolyte ions to micron-sized charge-stabilized colloids. We review recent advances in theoretical methods for the calculation of linear transport coefficients in concentrated particulate systems, with the focus on hydrodynamic interactions and electrokinetic effects. Considered transport properties are the dispersion viscosity, self- and collective…
We calculate the force between two spherical metal nanoparticles of charge Q 1 and Q 2 in a dilute 1:1 electrolyte solution. Numerically solving the non-linear Poisson-Boltzmann equation, we find that metal nanoparticles with the same sign of charge can attract one another. This is fundamentally different from what is found for like-charged, non-polarizable, colloidal particles, the two body interaction potential for which is always repulsive inside a dilute 1:1 electrolyte. Furthermore, existence of like-charge attraction between spherical metal nanoparticles is even more surprising in view o…
We report on the formation and the structural properties of supermicellar aggregates also called electrostatic complexes, made from mineral nanoparticles and polyelectrolyte-neutral block copolymers in aqueous solutions. The mineral particles put under scrutiny are ultra-fine and positively charged yttrium hydroxyacetate nanoparticles. Combining light, neutron and x-ray scattering experiments, we have characterized the sizes and the aggregation numbers of the organic-inorganic complexes. We have found that the hybrid aggregates have typical sizes in the range 100 nm and exhibit a remarkable co…
Based on extensive Monte Carlo simulations and analytical considerations we study the electrostatically driven adsorption of flexible polyelectrolyte chains onto charged Janus nanospheres. These net-neutral colloids are composed of two equally but oppositely charged hemispheres. The critical binding conditions for polyelectrolyte chains are analysed as function of the radius of the Janus particle and its surface charge density, as well as the salt concentration in the ambient solution. Specifically for the adsorption of finite-length polyelectrolyte chains onto Janus nanoparticles, we demonstr…
The manipulation of micro- and nano-objects is of great technological significance to construct new materials, manipulate tiny amounts of liquids in fluidic systems, or detect minute concentrations of analytes. It is commonly approached by the generation of potential energy landscapes, for example, with optical fields. Here we show that strong hydrodynamic boundary flows enable the trapping and manipulation of nano-objects near surfaces. These thermo-osmotic flows are induced by modulating the van der Waals interaction at a solid-liquid interface with optically induced temperature fields. We u…
When a micron-sized magnetizable particle is introduced into a suspension of nanosized magnetic particles, the nanoparticles accumulate around the microparticle and form thick anisotropic clouds extended in the direction of the applied magnetic field. This phenomenon promotes colloidal stabilization of bimodal magnetic suspensions and allows efficient magnetic separation of nanoparticles used in bioanalysis and water purification. In the present work, size and shape of nanoparticle clouds under the simultaneous action of an external uniform magnetic field and the flow have been studied in deta…
A static light scattering (SLS) study of bovine serum albumin (BSA) mixtures with two anionic graft copolymers of poly (sodium acrylate-co-sodium 2-acrylamido-2-methyl-1-propanesulphonate)-graft-poly (N, N-dimethylacrylamide), with a high composition in poly (N, N-dimethylacrylamide) (PDMAM) side chains, revealed the formation of oppositely charged complexes, at pH lower than 4.9, the isoelectric point of BSA. The core-corona nanoparticles formed at pH = 3.00, were characterized. Their molecular weight and radius of gyration were determined by SLS, while their hydrodynamic radius was determine…
Single-chain nanoparticles (SCNPs) are a new class of macromolecular objects, synthesized through purely intramolecular cross-linking of single polymer chains. We use a multi-scale hydrodynamics simulation approach to study, for the first time, SCNPs under shear flow. We investigate the case of irreversible SCNPs (permanent cross-links) in dilute solution. SCNPs emerge as a novel class of macromolecular objects with response to shear distinct from other systems such as linear chains, star polymers, rings or dendrimers. This is evidenced by the observed set of scaling exponents for the shear ra…
Charge Regulation Effect on Nanoparticles Interaction Mediated by Polyelectrolyte
Indian Institute of Technology Jodhpur（印度焦浦尔理工学院）；University of Chinese Academy of Sciences（中国科学院大学）；Institute of Physics, Chinese Academy of Sciences（中国科学院物理研究所）；University of Ljubljana（卢布尔雅那大学）
Single-chain nanoparticles (SCNPs) are ultrasoft objects obtained through purely intramolecular cross-linking of single polymer chains. By means of computer simulations with implemented hydrodynamic interactions, we investigate for the first time the effect of the shear flow on the structural and dynamic properties of SCNPs in semidilute solutions. We characterize the dependence of several conformational and dynamic observables on the shear rate and the concentration, obtaining a set of power-law scaling laws. The concentration has a very different effect on the shear rate dependence of the fo…
Star polymers with magnetically functionalized end groups are presented as a novel polymeric system whose morphology, self-aggregation, and orientation can easily be tuned by exposing these macromolecules simultaneously to an external magnetic field and to shear forces. Our investigations are based on a specialized simulation technique which faithfully takes into account the hydrodynamic interactions of the surrounding, Newtonian solvent. We find that the combination of magnetic field (including both strength and direction) and shear rate controls the mean number of magnetic clusters, which in…
We report the co-assembly and adsorption properties of coacervate complexes made from polyelectrolyte-neutral block copolymers and oppositely charged nanocolloids. The nanocolloids put under scrutiny were ionic surfactant micelles and highly charged 7 nm cerium oxide (CeO2) nanoparticles. Static and dynamic light scattering was used to investigate the microstructure and stability of the organic and hybrid complexes. The microstructure of the CeO2-based complexes was resolved using cryogenic transmission electronic microscopy (Cryo-TEM), and it revealed that the cores were clusters made from de…
Nanofluids; dispersions of nanometer-sized particles in a liquid medium; have been proposed for a wide variety of thermal management applications. It is known that a solid-like nanolayer of liquid of typical thickness 0.5-1 nm surrounding the colloidal nanoparticles can act as a thermal bridge between the nanoparticle and the bulk liquid. Yet, its effect on the nanofluid viscosity has not been elucidated so far. In this article, we compute the local viscosity of the nanolayer using equilibrium molecular dynamics based on the Green-Kubo formula. We first assess the validity of the method to pre…
