Particles adsorbed at various non-aqueous liquid-liquid interfaces.

Particles adsorbed at liquid interfaces are commonly used to stabilise water-oil Pickering emulsions and water-air foams. The fundamental understanding of the physics of particles adsorbed at water-air and water-oil interfaces is improving significantly due to novel techniques that enable the measurement of the contact angle of individual particles at a given interface. The case of non-aqueous interfaces and emulsions is less studied in the literature. Non-aqueous liquid-liquid interfaces in which water is replaced by other polar solvents have properties similar to those of water-oil interfaces. Nanocomposites of non-aqueous immiscible polymer blends containing inorganic particles at the interface are of great interest industrially and consequently more work has been devoted to them. By contrast, the behaviour of particles adsorbed at oil-oil interfaces in which both oils are immiscible and of low dielectric constant (ε<3) is scarcely studied. Hydrophobic particles are required to stabilise these oil-oil emulsions due to their irreversible adsorption, high interfacial activity and elastic shell behaviour.

Interfacial Activity of Gold Nanoparticles Coated with a Polymeric Patchy Shell and the Role of Spreading Agents.

Gold patchy nanoparticles (PPs) were prepared under surfactant-free conditions by functionalization with a binary ligand mixture of polystyrene and poly(ethylene glycol) (PEG) as hydrophobic and hydrophilic ligands, respectively. The interfacial activity of PPs was compared to that of homogeneous hydrophilic nanoparticles (HPs), fully functionalized with PEG, by means of pendant drop tensiometry at water/air and water/decane interfaces. We compared interfacial activities in three different spreading agents: water, water/chloroform, and pure chloroform. We found that the interfacial activity of PPs was close to zero (∼2 mN/m) when the spreading agent was water and increased to ∼14 mN/m when the spreading agent was water/chloroform. When the nanoparticles were deposited with pure chloroform, the interfacial activity reached up to 60 mN/m by compression. In all cases, PPs exhibited higher interfacial activity than HPs, which were not interfacially active, regardless of the spreading agent. The interfacial activity at the water/decane interface was found to be significantly lower than that at the water/air interface because PPs aggregate in decane. Interfacial dilatational rheology showed that PPs form a stronger elastic shell at the pendant drop interface, compared to HPs. The significantly high interfacial activity obtained with PPs in this study highlights the importance of the polymeric patchy shell and the spreading agent.

A simple strategy to improve the interfacial activity of true Janus gold nanoparticles: a shorter hydrophilic capping ligand.

Janus gold nanoparticles (JPs) of ∼4 nm-diameter half functionalized with 1-hexanethiol as a hydrophobic capping ligand exhibit significantly higher interfacial activity, reproducibility and rheological response when the other half is functionalized with 1,2-mercaptopropanediol (JPs-MPD) than with 2-(2-mercaptoethoxy)ethanol (JPs-MEE), both acting as hydrophilic capping ligands. The interfacial pressure measured by pendant drop tensiometry reaches 50 mN m(-1) and 35 mN m(-1) for the JPs-MPD at the water/air and water/decane interface, respectively. At the same area per particle, the JPs-MEE reveal significantly lower interfacial pressure: 15 mN m(-1) and 5 mN m(-1) at the water/air and water/decane interface, respectively. Interfacial dilatational rheology measurements also show an elastic shell behaviour at higher compression states for JPs-MPD while the JPs-MEE present near-zero elasticity. The enhanced interfacial activity of JPs-MPD is explained in terms of chemical and hydration differences between the MPD and MEE ligands, where MPD has a shorter hydrocarbon chain and twice as many hydroxyl terminal groups as MEE.

Testing the mean magnetization approximation, dimensionless and scaling numbers in magnetorheology.

The mean magnetization (MM) approximation is undoubtedly the most widely used approximation in magnetorheology both from theoretical and simulation perspectives. According to this, spherical magnetizable particles under field can be replaced by effective dipole moments m placed at their center with strength m = V(p)⟨M(p)⟩. Here V(p) and ⟨M(p)⟩ are the volume and mean (average) magnetization of the particles, respectively. In spite of being extensively used, there is not a mathematical justification to do so in most cases. In this manuscript, we test this approximation using experiments, theories and simulations, for a wide range of magnetic field strengths and particle loadings, in both conventional magnetorheological fluids (CMRFs) and inverse ferrofluids (IFFs). Results demonstrate that the MM approximation is applicable in IFFs for a very wide range of field strengths (up to external fields of 265 kA m(-1)) and particle loadings (up to 20 vol%). For CMRFs, the MM approximation is only applicable in two particular circumstances; in magnetic saturation or in infinite dilution.

Surface activity of Janus particles adsorbed at fluid-fluid interfaces: Theoretical and experimental aspects.

Since de Gennes coined in 1992 the term Janus particle (JP), there has been a continued effort to develop this field. The purpose of this review is to present the most relevant theoretical and experimental results obtained so far on the surface activity of amphiphilic JPs at fluid interfaces. The surface activity of JPs at fluid-fluid interfaces can be experimentally determined using two different methods: the classical Langmuir balance or the pendant drop tensiometry. The second method requires much less amount of sample than the first one, but it has also some experimental limitations. In all cases collected here the JPs exhibited a higher surface or interfacial activity than the corresponding homogeneous particles. This reveals the significant advantage of JPs for the stabilization of emulsions and foams.

Interfacial Activity and Contact Angle of Homogeneous, Functionalized, and Janus Nanoparticles at the Water/Decane Interface.

Surface heterogeneity affects the behavior of nanoparticles at liquid interfaces. To gain a deeper understanding on the details of these phenomena, we have measured the interfacial activity and contact angle at water/decane interfaces for three different types of nanoparticles: homogeneous poly(methyl methacrylate) (PMMA), silica functionalized with a capping ligand containing a methacrylate terminal group, and Ag-based Janus colloids with two capping ligands of different hydrophobicity. The interfacial activity was analyzed by pendant drop tensiometry, and the contact angle was measured directly by freeze-fracture shadow-casting cryo-scanning electron microscopy. The silver Janus nanoparticles presented the highest interfacial activity, compared to the silica nanoparticles and the homogeneous PMMA nanoparticles. Additionally, increasing the bulk concentration of the PMMA and silica nanoparticles up to 100-fold compared to the Janus nanoparticles led to silica particles forming fractal-like structures at the interface, contrary to the PMMA particles that did not show any spontaneous adsorption.

Specific ion effects on the electrokinetic properties of iron oxide nanoparticles: experiments and simulations.

We report experimental and simulation studies on ion specificity in aqueous colloidal suspensions of positively charged, bare magnetite nanoparticles. Magnetite has the largest saturation magnetization among iron oxides and relatively low toxicity, which explain why it has been used in multiple biomedical applications. Bare magnetite is hydrophilic and the sign of the surface charge can be changed by adjusting the pH, its isoelectric point being in the vicinity of pH = 7. Electrophoretic mobility of our nanoparticles in the presence of increasing concentrations of different anions showed that anions regarded as kosmotropic are more efficient in decreasing, and even reversing, the mobility of the particles. If the anions were ordered according to the extent to which they reduced the particle mobility, a classical Hofmeister series was obtained with the exception of thiocyanate, whose position was altered. Monte Carlo simulations were used to predict the diffuse potential of magnetite in the presence of the same anions. The simulations took into account the ion volume, and the electrostatic and dispersion forces among the ions and between the ions and the solid surface. Even though no fitting parameters were introduced and all input data were estimated using Lifshitz theory of van der Waals forces or obtained from the literature, the predicted diffusion potentials of different anions followed the same order as the mobility curves. The results suggest that ionic polarizabilities and ion sizes are to a great extent responsible for the specific ion effects on the electrokinetic potential of iron oxide particles.

Comparison of the interfacial activity between homogeneous and Janus gold nanoparticles by pendant drop tensiometry.

The interfacial activity of 3.5 nm homogeneous (HPs) and amphiphilic Janus gold nanoparticles (JPs) was characterized by pendant drop tensiometry for water/air and water/decane interfaces. This technique requires a smaller quantity of nanoparticles than the traditional Langmuir balance technique. The direct deposition at the interface of the nanoparticles dispersed in a spreading solvent also requires smaller quantities of sample than does adsorption from the bulk. From the growing and shrinking of the pendant drops, the interfacial activity of the nanoparticles can be evaluated and compared within a wide range of area per particle. In this work, the JPs exhibited a higher interfacial activity than did the HPs in all cases. A hard disk model fits the piecewise compression isotherm of the HPs, yet this model underestimates the interactions between the JPs adsorbed at the interface.

Small-amplitude oscillatory shear magnetorheology of inverse ferrofluids.

A comprehensive investigation is performed on highly monodisperse silica-based inverse ferrofluids under small-amplitude oscillatory shear in the presence of external magnetic fields up to 1 T. The effect of particle volume fraction and continuous medium Newtonian viscosity is thoroughly investigated. Experimental results for storage modulus are used to validate existing micromechanical magnetorheological models assuming different particle-level field-induced structures.

Study on the correlation between lateral diffusion effect and effective charge in neutral liposomes.

An experimental investigation is described on the variables that affect the lateral diffusion coefficient (D(lat)) of dimyristoylphosphatidylcholine, a zwitterionic phospholipid, and the effective charge (Z(ef)) on liposomes. The lateral diffusion coefficient was obtained from the dielectric relaxation time of the zwitterionic phospholipids in the bilayer, and the effective charge on the external monolayer was estimated from microelectrophoretic mobility measurements by means of the Henry and Coulomb equations. The measurements were performed at different pH values and salt (KBr) concentrations as well as in two physical states of the phospholipid: the liquid-crystalline phase and gel phase. The Z(ef) and D(lat) values in the gel phase are always lower than those in the fluid phase. A very small change of pH (approximately 0.5 pH units) caused a pronounced variation of the effective charge and the lateral diffusion coefficient. Both variations are correlated, which demonstrates that the adsorption of the ions that determine the electrokinetic potential also controls the lateral diffusion of dipolar phospholipids in the bilayer and the effective charge on the external surface of the liposomes.

Physical properties of elongated magnetic particles: magnetization and friction coefficient anisotropies.

Anisotropy counts: A brief review of the main physical properties of elongated magnetic particles (EMPs) is presented. The most important characteristic of an EMP is the additional contribution of shape anisotropy to the total anisotropy energy of the particle, when compared to spherical magnetic particles. The electron micrograph shows Ni-ferrite microrods fabricated by the authors.We present an overview of the main physical properties of elongated magnetic particles (EMPs), including some of their more relevant properties in suspension. When compared to a spherical magnetic particle, the most important characteristic of an EMP is an additional contribution of shape anisotropy to the total anisotropy energy of the particle. Increasing aspect ratios also lead to an increase in both the critical single-domain size of a magnetic particle and its resistance to thermally activated spontaneous reversal of the magnetization. For single-domain EMPs, magnetization reversal occurs primarily by one of two modes, coherent rotation or curling, the latter being facilitated by larger aspect ratios. When EMPs are used to prepare colloidal suspensions, other physical properties come into play, such as their anisotropic friction coefficient and the consequent enhanced torque they experience in a shear flow, their tendency to align in the direction of an external field, to form less dense sediments and to entangle into more intricate aggregates. From a more practical point of view, EMPs are discussed in connection with two interesting types of magnetic colloids: magnetorheological fluids and suspensions for magnetic hyperthermia. Advances reported in the literature regarding the use of EMPs in these two systems are included. In the final section, we present a summary of the most relevant methods documented in the literature for the fabrication of EMPs, together with a list of the most common ferromagnetic materials that have been synthesized in the form of EMPs.

Preparation and characterization of extruded magnetoliposomes.

Phospholipid vesicles encapsulating magnetic nanoparticles (here after called magnetoliposomes) have been prepared for targeting a drug to a specific organ using a magnetic force, as well as for local hyperthermia therapy. Magnetoliposomes are also an ideal platform for use as contrast agents. We describe the preparation and characterization of liposomes containing magnetite, a ferrimagnetic material. These liposomes were obtained by extrusion. To prevent the aggregation of particles, the magnetite was treated--prior to encapsulation--with a surfactant, resulting in a stable ferrofluid suspension. Once the ferrofluid had been obtained, it was used to hydrate the phospholipid layers. Magnetoliposomes had a diameter of around 200 nm, the same pore size as the membranes used for the extrusion. The encapsulation efficiency was dependent on the initial amount of ferrofluid present at the encapsulation stage, and in the worst case was 19%. This value corresponded to 82.06 mmol of magnetite per mole of phospholipid. Although we have used a determined membrane pore to obtain the magnetoliposomes, the method described here allows to prepare magnetoliposomes of different sizes as well as of different magnetite content.

Evidence of direct crystal growth and presence of hollow microspheres in magnetite particles prepared by oxidation of Fe(OH)2.

We provide new information relevant to the crystallinity and growth mechanism of magnetite particles that were fabricated following the method of Sugimoto and Matijevic [J. Colloid Interface Sci. 74 (1980) 227]. These authors observed that in a small excess of Fe(2+), particles grew by aggregation and recrystallization of smaller units, so that until now the resulting particles were thought to be polycrystalline. With the help of transmission electron microscopy (TEM) and selected area electron diffraction (SAED), we also detected the presence of monocrystalline particles, which are strong evidence of the occurrence of direct crystal growth. This growth mechanism seems to coexist with that of the aggregation of primary units proposed by Sugimoto and Matijevic. Careful examination of electron microscopy micrographs also revealed the presence of many hollow polycrystalline microspheres.

Influence of a magnetic field on the formation of magnetite particles via two precipitation methods.

An experimental investigation is described on the effects of the presence of a magnetic field during the fabrication of magnetite particles. We considered two well-known synthesis methods: that of Massart [IEEE Trans. Magn. 1981, 17, 1247-1248] for the synthesis of nanometer-sized, monodomain particles; and that of Sugimoto and Matijevic [J. Colloid Interface Sci. 1980, 74, 227-243.] for the fabrication of micrometer-sized multidomain spherical particles. The latter method was studied with two systems of different ionic compositions that lead to two different mechanisms of growth: either growth by aggregation and recrystallization of primary particles or direct crystal growth. When growth was dominated by aggregation of primary units, the magnetic field had a dramatic effect on the morphology, inducing the formation of rodlike particles. Growth dynamics of that system were studied for particles obtained in the presence as well as in the absence of the magnetic field. Particles were also characterized by powder magnetometry, electrophoresis, X-ray diffraction, and optical absorbance techniques. Interestingly, growth dynamics of the rods cross section were comparable to those of the diameter of the spheres. With the exception of the morphology, no other significant difference was found between the rodlike particles and the spheres.

Testing one component plasma models on colloidal overcharging phenomena.

In this paper, the mechanisms of overcharging of a colloidal macroion in the presence of multivalent counterions are investigated by means of Monte Carlo simulations. This computational technique appears as a powerful tool for probing the validity of semianalytical models developed for this issue. In particular, the simulations performed are compared with the predictions of two different models based on the one component plasma (OCP) theory. Therein, the multivalent ionic atmosphere confined at the macroion surface is approximated by a two-dimensional Wigner crystal. These kinds of models are largely used in the literature since (in some cases) they present quite simple equations to describe the electric double layer (EDL) of macroions with different geometries in the presence of much smaller (but still multivalent) ions. In this sense, charge inversion phenomena of membranes, polyelectrolytes, DNA molecules, etc., are straightforwardly predicted in terms of these expressions. Unfortunately, comparisons between these predictions and experimental results are scarce, mostly due to the difficulty to reproduce the experimental conditions in the laboratory. Accordingly, the goal of the present paper is to simulate EDLs under real conditions (in which overcharging phenomena are expected to happen) and use the results obtained in this way for comparing with those obtained from OCP models.

Self-assembly in two-dimensions of colloidal particles at liquid mixtures.

The aim of this work is to simulate the formation of colloidal rings, circular clusters, and voids induced by oily lenses at the air-water interface. The presence of two liquids with different surface tension leads to the formation of a nonhomogeneous interface. In this case, the total interaction potential is assumed to be composed of only two terms; the first one is due to the (repulsive) pairwise dipolar force between partly immersed charged microspheres, whereas the second depends on the position of the particle at the interface and is connected to the interfacial stress caused by the difference of surface tension between both liquids. This simple potential is able to reproduce the experimental rings, circular clusters and voids found by different authors.

On the effect of Ca2+ and La3+ on the colloidal stability of liposomes.

This work deals with the effect of Ca2+ and La3+ on the colloidal stability of phosphatidylcholine (PC) liposomes in aqueous media. As physical techniques, nephelometry, photon correlation spectroscopy, electrophoretic mobility, and surface tension were used. The theoretical predictions of the colloidal stability of liposomes were followed using the Derjaguin-Landau-Verwey-Overbeek theory. Changes in the size of liposomes and high polydispersity values were observed as La3+ concentration increases, suggesting that this cation induces the aggregation of liposomes. However, changes in polydispersity were not observed with Ca2+, suggesting a coalescence mechanism or fusion of liposomes. The stability factor (W), calculated from the nephelometry measurements indicated that aggregation/fusion occurs at a critical concentration (c.c.) of 0.3 and 0.7 M for La3+ and Ca2+, respectively. To gain a better insight into the interaction mechanism between the liposomes and the studied ions, the interaction between PC monolayers and Ca2+ and La3+ was studied. Changes in the surface area per lipid molecule (A0) in the monolayer at the c.c. values were found for both ions, with a more pronounced effect in the case of Ca2+. This corresponds with a larger reduction of the steric repulsive interaction between the headgroups at the phospholipid membrane (pi(head)). The experimental result validates the hypothesis made on the liposome fusion in the presence of Ca2+ and liposome aggregation in the presence of La3+. These aggregation mechanisms have also been confirmed by transmission electron microscopy.

Overcharging in colloids: beyond the Poisson-Boltzmann approach.

A broad range of manufactured products and biological fluids are colliods. The ability to understand and control the processes (of scientific, technological and industrial interest) in which such colloids are involved relies upon a precise knowledge of the electrical double layer. The traditional approach to describing this ion cloud around colloidal particles has been the Gouy-Chapman model developed on the basis of the Poisson-Boltzmann equation. Since the early 1980s, however, more sophisticated theoretical treatments have revealed both quantitative and qualitative deficiencies in the Poisson-Boltzmann theory, particularly at high ionic strengths and/or high surface charge densities. This review deals with these novel approaches, which are mostly computer simulations and approximate integral equation theories based on the so-called primitive model. Special attention is paid to phenomena that cannot be accounted for by the classic theory as a result of neglecting ion size correlations, such as overcharging, namely, the counterion concentration in the immediate neighborhood of the surface is so large that the particle surface is overcompensated. Other illustrative examples are the nonmonotonic behavior of the electrostatic potential and attractive interactions between equally charged surfaces. These predictions are certainly remarkable and, on paper, they can have an effect on experimentally measurable quantities (for instance, electrophoretic mobility). Even so, these new approaches have scarcely been applied in practice. Thus a critical survey on the relevance of ion size correlation in real systems is also included. Overcharging of macroions can also be brought about by adsorption of oppositely charged polyelectrolytes. Noteworthy examples and theoretical approaches for them are also briefly reviewed.

Electrokinetic parameters of colloidal model systems: analysis and comparison between dilute and concentrated dispersions.

In the last decades, the interest of many scientists has been focused on the atypical electrokinetic behavior of charged colloidal systems since several studies have shown, in most cases; it is not so ideal as expected. Particularly, two interesting phenomena have not been clearly explained yet. First, the zeta potential magnitude does not decrease monotonically with increasing ionic strength, as expected according to the Gouy-Chapmann model predicts. Second, the zeta potential obtained from different techniques shows discrepancies. More specifically, the zeta potential obtained from streaming potential is lower (in absolute value) than that measured through electrophoretic mobility. However, a recent work has pointed out that these discrepancies seem to disappear if certain conditions (related with the surface charge density) are satisfied. This work also revealed that unexpected results are found when the electric conductivity was used. Spherical polystyrene particles of appropriate particle size and charge density are employed as polymeric colloidal model in the present work. Common and adequate models are used to make clear and easy our theoretical analysis and its interpretation. To test the surface conductance and ionic mobility effects at the solid-liquid interface, both water medium and alcohol-water mixtures are used.