In this paper, we theoretically study the electrostatic interaction between a pair of identical colloids with constant surface potentials sitting in close vicinity of each other at a fluid interface. By employing a simplified yet reasonable model system, the problem is solved within the framework of classical density functional theory and linearized as well as nonlinear Poisson-Boltzmann (PB) theory. Apart from providing a sound theoretical framework generally applicable to any such problem, our novel findings, all of which contradict common beliefs, include the following: first, quantitative as well as qualitative differences between the interactions obtained within the linear and the nonlinear PB theories; second, the importance of the electrostatic interaction between the omnipresent three-phase contact lines in interfacial systems; and third, the occurrence of an attractive electrostatic interaction between a pair of identical metal colloids. The unusual attraction we report on largely stems from an attractive line interaction which although scales linearly with the size of the particle, can compete with the surface interactions and can be strong enough to alter the nature of the total electrostatic interaction. Our results should find applications in metal or metal-coated particle-stabilized emulsions where densely packed particle arrays are not only frequently observed but are sometimes required.
We construct a theoretical model for the dynamics of a microscale colloidal particle, modeled as an interval, moving horizontally on a DNA-coated surface, modelled as a line coated with springs that can stick to the interval. Averaging over the fast DNA dynamics leads to an evolution equation for the particle in isolation, which contains both friction and diffusion. The DNA-induced friction coefficient depends on the physical properties of the DNA, and substituting parameter values typical of a 1$μ$m colloid coated densely with weakly interacting DNA gives a coefficient about 100 times larger …
The possibility of prescribing local interactions between nano- and microscopic components that direct them to assemble in a predictable fashion is a central goal of nanotechnology research. In this article we advance a new paradigm in which self-assembly of DNA-functionalized colloidal particles is programmed using linker oligonucleotides dispersed in solution. We find a phase diagram that is surprisingly rich compared to phase diagrams typical of other DNA-functionalized colloidal particles that interact by direct hybridization, including a re-entrant melting transition upon increasing linke…
Developing construction methods of materials tailored for given applications with absolute control over building block placement poses an immense challenge. DNA-coated colloids offer the possibility of realising programmable self-assembly, which, in principle, can assemble almost any structure in equilibrium, but remains challenging experimentally. Here, we propose an innovative system of linker-mediated mobile DNA-coated colloids (mDNACCs), in which mDNACCs are bridged by the free DNA linkers in solution, whose two single-stranded DNA tails can bind with specific single-stranded DNA receptors…
Colloids coated with single-stranded DNA (ssDNA) can bind selectively to other colloids coated with complementary ssDNA. The fact that DNA-coated colloids (DNACCs) can bind to specific partners opens the prospect of making colloidal `molecules'. However, in order to design DNACC-based molecules, we must be able to control the valency of the colloids, i.e. the number of partners to which a given DNACC can bind. One obvious, but not very simple approach is to decorate the colloidal surface with patches of single-stranded DNA that selectively bind those on other colloids. Here we propose a design…
The physical mechanism of elasticity of liquid surfaces coated with colloidal particles is proposed. It is suggested that particles are separated by water clearings and the capillary interaction between them is negligible. The case is treated when the colloidal layer is deformed normally to its surface. The elasticity arises as an interfacial effect. The effective Young modulus of a surface depends on the interfacial tension, equilibrium contact angle, radius of colloidal particles and their surface density. For the nanometrically scaled particles the line tension becomes essential and has an …
In this thesis, the electrostatic interaction between two chemically identical colloids, both carrying constant surface potential is studied in the limit of short inter-particle separation at the interface of two immiscible fluids. Using an appropriate model system, the problem is solved analytically within the framework of linearized Poisson-Boltzmann theory and classical density functional theory. The governing equation of the electrostatic problem is derived by minimization of the corresponding density functional, which leads to the Debye-Hückel equation. Subsequently, the Debye-Hückel equa…
Effective electrostatic interactions between colloidal particles, coated with polyelectrolyte brushes and suspended in an electrolyte solvent, are described via linear response theory. The inner cores of the macroions are modeled as hard spheres, the outer brushes as spherical shells of continuously distributed charge, the microions (counterions and salt ions) as point charges, and the solvent as a dielectric continuum. The multi-component mixture of macroions and microions is formally mapped onto an equivalent one-component suspension by integrating out from the partition function the microio…
The self-assembly of DNA-coated colloids into highly-ordered structures offers great promise for advanced optical materials. However, control of disorder, defects, melting, and crystal growth is hindered by the lack of a microscopic understanding of DNA-mediated colloidal interactions. Here we use total internal reflection microscopy to measure in situ the interaction potential between DNA-coated colloids with nanometer resolution and the macroscopic melting behavior. The range and strength of the interaction are measured and linked to key material design parameters, including DNA sequence, po…
Grafting linkers with open ends of complementary single-stranded DNA makes a flexible tool to tune interactions between colloids,which facilitates the design of complex self-assembly structures. Recently, it has been proposed to coat colloids with mobile DNA linkers, which alleviates kinetic barriers without high-density grafting, and also allows the design of valency without patches.However, the self-assembly mechanism of this novel system is poorly understood.Using a combination of theory and simulation, we obtain phase diagrams forthe system in both two and three dimensional spaces, and fin…
We present a quantitative, multi-scale coarse-grained model of DNA coated colloids. The parameters of this model are transferable and are solely based on experimental data. As a test case, we focus on nano-sized colloids carrying single-stranded DNA strands of length comparable to the colloids' size. We show that in this regime, the common theoretical approach of assuming pairwise additivity of the colloidal pair interactions leads to quantitatively and sometimes even qualitatively wrong predictions of the phase behaviour of DNA-grafted colloids. Comparing to experimental data, we find that ou…
The effective electrostatic interaction between a pair of colloids, both of them located close to each other at an electrolyte interface, is studied by employing the full, nonlinear Poisson-Boltzmann (PB) theory within classical density functional theory. Using a simplified yet appropriate model, all contributions to the effective interaction are obtained exactly, albeit numerically. The comparison between our results and those obtained within linearized PB theory reveals that the latter overestimates these contributions significantly at short inter-particle separations. Whereas the surface co…
The electrostatic interaction between colloidal particles trapped at the interface between two immiscible electrolyte solutions is studied in the limit of small inter-particle distances. Within an appropriate model exact analytic expressions for the electrostatic potential as well as for the surface and line interaction energies are obtained. They demonstrate that the widely used superposition approximation, which is commonly applied to large distances between the colloidal particles, fails qualitatively at small distances and is quantitatively unreliable even at large distances. Our results c…
The electrostatic interaction between two non-identical, moderately charged colloids situated in close proximity of each other at a fluid interface is studied. By resorting to a well-justified model system, this problem is analytically solved within the framework of linearized Poisson-Boltzmann (PB) density functional theory (DFT). The resulting interaction comprises a surface and a line part, both of which, as functions of the inter-particle separation, show a rich behavior including monotonic as well as non-monotonic variations. In almost all cases, these variations cannot be captured correc…
Colloidal structure, energy extensivity and Monte Carlo sampling properties of improved short-range interaction models for surfactant-coated magnetic nanoparticles
Self-assembly is traditionally described as the process through which an initially disordered system relaxes towards an equilibrium ordered phase only driven by local interactions between its building blocks. However, This definition is too restrictive. Nature itself provides examples of amorphous, yet functional, materials assembled upon kinetically arresting the pathway towards the ground state. Kinetic self-assembly is intrinsically more flexible and reliable than its equilibrium counterpart, allowing control over the morphology of the final phase by tuning both the interactions and the the…
Charge-stabilized colloidal spheres dispersed in deionized water are supposed to repel each other. Instead, artifact-corrected video microscopy measurements reveal an anomalous long-ranged like-charge attraction in the interparticle pair potential when the spheres are confined to a layer by even a single charged glass surface. These attractions can be masked by electrostatic repulsions at low ionic strengths. Coating the bounding surfaces with a conducting gold layer suppresses the attraction. These observations suggest a possible mechanism for confinement-induced attractions.
The physical behaviour of anisotropic charged colloids is determined by their material dielectric anisotropy, affecting colloidal self-assembly, biological function and even out-of-equilibrium behaviour. However, little is known about anisotropic electrostatic screening, which underlies all electrostatic effective interactions in such soft or biological materials. In this work, we demonstrate anisotropic electrostatic screening for charged colloidal particles in a nematic electrolyte. We show that material anisotropy behaves markedly different from particle anisotropy: The electrostatic potent…
We show that describing the screened electrostatic interactions in a periodic stack of rigid parallel identical charged plate-like colloids within a local density functional theory approach, generically leads to a swelling behaviour. Within the same framework, we find that the effective potential between a pair of such plates immersed in an electrolyte is repulsive at all distances. This general result is in contradiction with a theory put forward by Sogami, Shinohara and Smalley, that we criticize and thoroughly reconsider to show how the two approaches can be reconciled.
Within the framework of a Modified Poisson-Boltzmann theory accounting for steric effects of microions, we prove analytically that the effective pair interactions between like-charge colloids immersed in a confined electrolyte are repulsive. Our approach encompasses and extends previously known results to the case of complete confinement, and further incorporates the finite size of the microions which is absent in the standard Poisson-Boltzmann theory.
Interparticle interactions and bulk properties of colloidal suspensions can be substantially modified by addition of nanoparticles. Extreme asymmetries in size and charge between colloidal particles and nanoparticles present severe computational challenges to molecular-scale modeling of such complex systems. We present a statistical mechanical theory of effective electrostatic interactions that can greatly ease large-scale modeling of charged colloid-nanoparticle mixtures. By applying a sequential coarse-graining procedure, we show that a multicomponent mixture of charged colloids, nanoparticl…
Electrostatic repulsions can drive crystallization in many-particle systems. For charged colloidal systems, the phase boundaries as well as crystal structure are highly tunable by experimental parameters such as salt concentration and pH. By using projections of the colloid-ion mixture to a system of (soft) repulsive spheres and the one-component plasma (OCP), we study the hitherto unexplained experimentally observed reentrant melting of electrostatically repelling colloids upon increasing the colloid density. Our study shows that the surface chemistry should involve a competition between adso…
Colloidal particles partially coated with platinum and dispersed in H2O2 solution are often used as model self-propelled colloids. Most current data suggest that neutral self-diffusiophoresis propels these particles. However, several studies have shown strong ionic effects in this and related systems, such as a reduction of propulsion speed by salt. We investigate these ionic effects in Pt-coated polystyrene colloids, and find here that the direction of propulsion can be reversed by addition of an ionic surfactant, and that although adding pH neutral salts reduces the propulsion speed, adding …
In a recent study [Phys. Rev. E 60, 6530 (1999)], Trizac and Raimbault showed that the effective pair interaction between like charged colloids immersed in a cylindrically confined electrolyte remains repulsive even when the size of the micro-ions or the finite longitudinal extension of the confining cylinder are taken into account. Contrary to their claim, we argue that the case of finite longitudinal confinement doesn't always generate repulsive interactions and to illustrate this point we also provide a simple example.
By exploiting the exquisite selectivity of DNA hybridization, DNA-Coated Colloids (DNACCs) can be made to self-assemble in a wide variety of structures. The beauty of this system stems largely from its exceptional versatility and from the fact that a proper choice of the grafted DNA sequences yields fine control over the colloidal interactions. Theory and simulations have an important role to play in the optimal design of self- assembling DNACCs. At present, the powerful model-based design tools are not widely used, because the theoretical literature is fragmented and the connection between di…
We present a comment to a recent paper by Dominguez et. al. They claimed that the electrostatic interaction between charged colloids trapped at an interface formed by a dielectric and a screening phase is always isotropic to order $d^-3$. Base on this result, they claimed that in-plane dipolar attraction of order $d^-3$ between colloids cannot exist, in contrast to previous proposals. We point out that their analysis is not completed and anisotropic (dipolar) interaction between colloids can exist up to order $d^-3$.
The general form of the electrostatic potential around an arbitrarily charged colloid at an interface between a dielectric and a screening phase (such as air and water, respectively) is analyzed in terms of a multipole expansion. The leading term is isotropic in the interfacial plane and varies with $d^{-3}$ where $d$ is the in--plane distance from the colloid. The electrostatic interaction potential between two arbitrarily charged colloids is likewise isotropic and $\propto d^{-3}$, corresponding to the dipole--dipole interaction first found for point charges at water interfaces. Anisotropic …
Electrostatic forces between small groups of colloidal particles are measured using blinking optical tweezers. When the electrostatic screening length is significantly larger than the particle radius, forces are found to be non-pairwise additive. Both pair and multi-particle forces are well described by the linearized Poisson-Boltzmann equation with constant potential boundary conditions. These findings may play an important role in understanding the structure and stability of a wide variety of systems, from micron-sized particles in oil to aqueous nanocolloids.
Spin-coating technique is very fast, cheap, reproducible, simple and needs less material to fabricate films of particulate systems/colloids. Their thickness and uniformity may be controlled by means of external fields. We apply magnetic fields during the spin-coating of a moderately concentrated superparamagnetic colloid (made of silica coated magnetite particles). We study the influence of different magnetic field configurations (homogeneous and inhomogeneous) on the resulting spin-coated deposits and compare experimental results under various conditions. Superparamagnetic colloids behave as,…
In his Comment (cond-mat/0104060) to [Phys. Rev. E 60, 6530 (1999)], Mateescu shows that while the effective interactions remain repulsive when the specific size of the micro-ions is taken into account via a Modified Poisson-Boltzmann equation, a similar conclusion cannot be reached for the situation of complete lateral confinement. This point is correct but has already been considered in a more general study [Phys. Rev. E 62, R1465 (2000), where repulsion is generically obtained]; moreover, we argue that it illustrates the irrelevancy of the notion of pair potential in completely confined con…
Self-assembly of nanoparticles can enable composites with pre-designed properties but remains challenged by reproducing structural diversity of atomic and molecular crystals. We combine anisotropic elastic and weakly screened electrostatic interactions to guide both orientational and triclinic positional self-ordering of inorganic nanocrystals in a nematic fluid host. The lattice periodicity of these low-symmetry colloidal crystals is more than an order of magnitude larger than the nanoparticle size. Orientations of nanocrystals, as well as crystallographic axes of ensuing triclinic colloidal …
We study the effective electrostatic interactions between a pair of charged colloidal particles without salt ions while the system is confined in two dimensions. In particular we use a simplified model to elucidate the effects of rotational fluctuations in counterion distribution. The results exhibit effective colloidal attractions under appropriate conditions. Meanwhile, long-range repulsions persist over most of our studied cases. The repulsive forces arise from the fact that in two dimensions the charged colloids cannot be perfectly screened by counterions, as the residual quadrupole moment…
DNA-coated colloids can self-assemble into an incredible diversity of crystal structures, but applications of this technology are limited by poor understanding and control over the dynamical crystallization pathways. To address this challenge, we use microfluidics to quantify the self-assembly dynamics of DNA-programmed colloidal crystals, from thermally-activated nucleation through reaction-limited and diffusion-limited phases of crystal growth. Our detailed measurements of the temperature and concentration dependence of the kinetics at all stages along the crystallization pathway provide a s…
We study macroion correlation effects on the thermodynamics of highly charged colloidal suspensions using a mean-field theory and primitive model computer simulations. We suggest a simple way to include the macroion correlations into the mean-field theory as an extension of the renormalized jellium model of Trizac and Levin [Phys. Rev. E {\bf 69}, 031403 (2004)]. The effective screening parameters extracted from our mean-field approach are then used in a one-component model with macroions interacting via Yukawa-like potential to predict macroion distributions. We find that inclusion of macroio…
While the important role of electrostatic interactions in aqueous colloidal suspensions is widely known and reasonably well-understood, the relevance of charge in nonpolar suspensions remains mysterious. We demonstrate that particles can have surprisingly strong electrostatic interactions in low dielectric constant environments when ions are solubilized by reverse micelles. A simple thermodynamic model, relating the structure of the micelles to the equilibrium ionic strength, is in good agreement with both conductivity and interaction measurements. Since dissociated ions are solubilized by rev…
We report a study of reversible adsorption of DNA-coated colloids on complementary functionalized oil droplets. We show that it is possible to control the surface coverage of oil droplets by colloidal particles, by exploiting the fact that during slow adsorption, compositional arrest takes place well before structural arrest occurs. As a consequence, we can prepare colloid-coated oil droplets with a `frozen' degree of loading, but with fully ergodic colloidal dynamics on the droplets. We illustrate the equilibrium nature of the adsorbed colloidal phase by exploring the quasi two-dimensional (2…
Numerical solutions of the standard electrokinetic model provide a basis for interpreting a variety of electrokinetic phenomena involving `bare' colloids. However, the model rests on the classical notion of a shear or slipping plane, whose location is unknown when surfaces are coated with permeable polymer. Consequently, an electrokinetic model for `soft', `hairy' or `fuzzy' colloids has been developed, but until recently solutions were available only for several restricted cases, most notably for particles with thin, uniform layers, and without polarization and relaxation. Here we present num…
In its original formulation, the seminal Deryaguin-Landau-Verwey-Overbeek (DLVO) theory of colloidal stability seemed like a simple but realistic description of the world of colloid interactions in electrolyte solutions. It is based on a straightforward superposition of the mean-field Poisson-Boltzmann (PB) electrostatics with the electrodynamic van der Waals (vdW) interactions driven by thermal and quantum fluctuations. However, subsequent developments continued to reveal a much richer and deeper structure of fundamental interactions on the nano- and micro-scale: the granularity and structure…
We have measured equilibrium sedimentation profiles in a colloidal model system with confocal microscopy. By tuning the interactions, we have determined the gravitational length in the limit of hard-sphere-like interactions, and using the same particles, tested a recent theory [R.van Roij, J. Phys. Cond. Mat. 15, S3569, (2003)], which predicts a significantly extended sedimentation profile in the case of charged colloids with long-ranged repulsions, due to a spontaneously formed macroscopic electric field. For the hard-sphere-like system we find that the gravitational length matches that expec…
The equilibrium phase behavior of a binary mixture of charged colloids and neutral, non-adsorbing polymers is studied within free-volume theory. A model mixture of charged hard-sphere macroions and ideal, coarse-grained, effective-sphere polymers is mapped first onto a binary hard-sphere mixture with non-additive diameters and then onto an effective Asakura-Oosawa model [S. Asakura and F. Oosawa, J. Chem. Phys. 22, 1255 (1954)]. The effective model is defined by a single dimensionless parameter -- the ratio of the polymer diameter to the effective colloid diameter. For high salt-to-counterion …
We investigate spherical macroions in the strong Coulomb coupling regime within the primitive model in salt-free environment. We first show that the ground state of an isolated colloid is naturally overcharged by simple electrostatic arguments illustrated by the Gillespie rule. We furthermore demonstrate that in the strong Coulomb coupling this mechanism leads to ionized states and thus to long range attractions between like-charged spheres. We use molecular dynamics simulations to study in detail the counterion distribution for one and two highly charged colloids for the ground state as well …
A nonlinear response theory is developed and applied to electrostatic interactions between spherical macroions, screened by surrounding microions, in charge-stabilized colloidal suspensions. The theory describes leading-order nonlinear response of the microions (counterions, salt ions) to the electrostatic potential of the macroions and predicts microion-induced effective many-body interactions between macroions. A linear response approximation [Phys. Rev. E 62, 3855 (2000)] yields an effective pair potential of screened-Coulomb (Yukawa) form, as well as a one-body volume energy, which contrib…
We present a theory of effective electrostatic interactions in polydisperse suspensions of charged macroions, generalizing to mixtures a theory previously developed for monodisperse suspensions. Combining linear response theory with a random phase approximation for microion correlations, we coarse-grain the microion degrees of freedom to derive general expressions for effective macroion-macroion pair potentials and a one-body volume energy. For model mixtures of charged hard-sphere colloids, we give explicit analytical expressions. The resulting effective pair potentials have the same general …
We perform computational investigations of electrolyte-mediated interactions of charged colloidal particles confined within nanochannels. We investigate the role of discrete ion effects, valence, and electrolyte strength on colloid-wall interactions. We find for some of the multivalent charge regimes that the like-charged colloids and walls can have attractive interactions. We study in detail these interactions and the free energy profile for the colloid-wall separation. We find there are energy barriers and energy minima giving preferred colloid locations in the channel near the center and at…
Within a general framework we study the effective, deformation-induced interaction between two colloids trapped at a fluid interface. As an application, we consider the interface deformation owing to the electrostatic field of charged colloids. The effective interaction is attractive and overcomes the direct electrostatic repulsion at large separations if the system is not mechanically isolated. Otherwise, a net attraction seems possible only for large enough colloidal charges.
Colloids dispersed in a non-polar solvent become charged when reverse micelles are added. We study the charge of individual sterically-stabilized poly(methyl methacrylate) spheres dispersed in micellar solutions of the surfactants sodium bis(2-ethyl 1-hexyl) sulfosuccinate [AOT], zirconyl 2-ethyl hexanoate [Zr(Oct)$_{2}$], and a copolymer of poly(12-hydroxystearic acid)--poly(methyl methacrylate) [PHSA-PMMA]. Although the sign of the particle charge is positive for Zr(Oct)$_{2}$, negative for AOT, and essentially neutral for PHSA-PMMA the different micellar systems display a number of common f…
Electrostatic-Elastic Softening and Ultraviolet Instability Driven by Non-DLVO Interactions in Charged Colloidal Crystals
Wenzhou Institute, University of Chinese Academy of Sciences（温州研究院，中国科学院大学）；Institute of Theoretical Physics, Chinese Academy of Sciences（中国科学院理论物理研究所）
We report extensive numerical simulations of a simple model for charged colloidal particles in suspension with small non-adsorbing polymers. The chosen effective one-component interaction potential is composed of a short-range attractive part complemented by a Yukawa repulsive tail. We focus on the case where the screening length is comparable to the particle radius. Under these conditions, at low temperature, particles locally cluster into quasi one-dimensional aggregates which, via a branching mechanism, form a macroscopic percolating gel structure. We discuss gel formation and contrast it w…
In this dissertation we analyzed the double-layer force interaction between two dielectric charged colloidal spheres of different radii immersed in a solution of ions in water and in thermal equilibrium. In the limit of low electrostatic potential the interaction is governed by the Linearized Poisson-Boltzmann Equation (LPBE). We obtained an analytical solution from the LPBE for the electrostatic interaction via multipole expansion, considering a uniform and fixed surface charge density on the spheres. A code in the Mathematica platform was developed, allowing us to calculate the force between…
We compute the electrostatic potential at the surface, or zeta potential $ζ$, of a charged particle embedded in a colloidal suspension using a hybrid mesoscopic model. We show that for weakly perturbing electric fields, the value of $ζ$ obtained at steady state during electrophoresis is statistically indistinguishable from $ζ$ in thermodynamic equilibrium. We quantify the effect of counterions concentration on $ζ$. We also evaluate the relevance of the lattice resolution for the calculation of $ζ$ and discuss how to identify the effective electrostatic radius.
We study the Brownian motion of a charged colloid, confined between two charged walls, for small separation between the colloid and the walls. The system is embedded in an ionic solution. The combined effect of electrostatic repulsion and reduced diffusion due to hydrodynamic forces results in a specific motion in the direction perpendicular to the confining walls. The apparent diffusion coefficient at short times as well as the diffusion characteristic time are shown to follow a sigmoid curve as function of a dimensionless parameter. This parameter depends on the electrostatic properties and …
The new free energy functional that describes general elastic interaction between colloidal particles and nematic liquid crystal has been proposed. It generalizes results of the paper \cite{lupe} on the case of arbitrary orientation of colloidal particles and is valid for arbitrary surface anchoring strength. Formal analogies and differences between electric particles and colloidal particles in LC are found. It is first time shown that spur of the quadrupole moment tensor is different from zero $Sp\hat{Q}_μ\neq 0$ in the case of axial symmetry breaking of the director field around colloidal pa…
Microorganisms are able to overcome the thermal randomness of their surroundings by harvesting energy to navigate in viscous fluid environments. In a similar manner, synthetic colloidal microswimmers are capable of mimicking complex biolocomotion by means of simple self-propulsion mechanisms. Although experimentally the speed of active particles can be controlled by e.g. self-generated chemical and thermal gradients, an in-situ change of swimming direction remains a challenge. In this work, we study self-propulsion of half-coated spherical colloids in critical binary mixtures and show that the…
We study analytically the structural properties of a system with a short-range attraction and a competing long-range screened repulsion. This model contains the essential features of the effective interaction potential among charged colloids in polymeric solutions and provides novel insights on the equilibrium phase diagram of these systems. Within the self-consistent Hartree approximation and by using a replica approach, we show that varying the parameters of the repulsive potential and the temperature yields a phase coexistence, a lamellar and a glassy phase. Our results strongly suggest tha…
