A.V. Delgado

Measurement and interpretation of electrokinetic phenomena - (IUPAC technical report)

In this report, the status quo and recent progress in electrokinetics are reviewed. Practical rules are recommended for performing electrokinetic measurements and interpreting their results in terms of well-defined quantities, the most familiar being the z-potential or electrokinetic potential. This potential is a property of charged interfaces, and it should be independent of the technique used for its determination. However, often the z-potential is not the only property electrokinetically characterizing the electrical state of the interfacial region; the excess conductivity of the stagnant layer is an additional parameter. The requirement to obtain the z-potential is that electrokinetic theories be correctly used and applied within their range of validity. Basic theories and their application ranges are discussed. A thorough description of the main electrokinetic methods is given; special attention is paid to their ranges of applicability as well as to the validity of the underlying theoretical models. Electrokinetic consistency tests are proposed in order to assess the validity of the z-potentials obtained. The recommendations given in the report apply mainly to smooth and homogeneous solid particles and plugs in aqueous systems; some attention is paid to nonaqueous media and less ideal surfaces.

Synthesis and characterization of poly(ethyl-2-cyanoacrylate) nanoparticles with a magnetic core

A method is described to prepare composite colloidal nanoparticles, consisting of a magnetic core (magnetite) and a biodegradable polymeric shell (poly(ethyl-2-cyanoacrylate) or PE-2-CA). The method is based on the so-called anionic polymerization procedure, often used in the synthesis of PE-2-CA nanospheres designed for drug delivery. In the present work, the heterogeneous structure of the particles can confer both magnetic-field responsiveness and potential applicability as a drug carrier. In order to investigate to what extent this target is achieved, we compare the structure, chemical composition, and surface properties of the core/shell particles with those of both the nucleus and the coating material. This preliminary study shows that the synthetic new material displays an intermediate behavior between that of magnetite and PE-2-CA spheres. Thus, electrophoresis measurements as a function of pH and as a function of KNO3 concentration, show great similarity between the core/shell and pure polymer nanoparticles. A similar conclusion is reached when a surface thermodynamic study is performed on the three types of particles: the electron-donor component of the surface free energy of the solids is the quantity that appears to be most sensitive to the surface composition. The fact that PE-2-CA is close to being a non-polar material gives rise to a measurable decrease in the electron-donor component of the surface free energy of core/shell particles as compared to magnetite.

Magnetite/poly(alkylcyanoacrylate) (core/shell) nanoparticles as 5-Fluorouracil delivery systems for active targeting.

In this article, a reproducible emulsion polymerization process is described to prepare core/shell colloidal nanospheres, loaded with 5-Fluorouracil, and consisting of a magnetic core (magnetite) and a biodegradable polymeric shell [poly(ethyl-2-cyanoacrylate), poly(butylcyanoacrylate), poly(hexylcyanoacrylate), or poly(octylcyanoacrylate)]. The heterogeneous structure of these carriers can confer them both the possibility of being used as drug delivery systems and the responsiveness to external magnetic fields, allowing an active drug targeting without a concurrent systemic distribution. Zeta potential determinations as a function of ionic strength showed that the surface behaviour of the core/shell particles is similar to that of pure cyanoacrylate particles. The first magnetization curve of both magnetite and magnetite/polymer particles demonstrated that the polymer shell reduces the magnetic responsiveness of the particles, but keeps unchanged their ferrimagnetic character. Two drug loading mechanisms were studied: absorption or entrapment in the polymeric network, and surface adsorption. We found that the acidity of the medium had significant effects on the drug absorption per unit mass of polymer, and needs to be controlled to avoid formation of macroaggregates and to reach significant 5-Fluorouracil absorption. The type of polymer and the drug concentration are also main factors determining the drug incorporation to the core/shell particles. 5-Fluorouracil release evaluations showed a biphasic profile affected by the type of polymeric shell, the type of drug incorporation and the amount of drug loaded.

Dynamic characterization of extremely bidisperse magnetorheological fluids

In this work, we investigate the stability and redispersibility of magnetorheological fluids (MRFs). These are disperse systems where the solid is constituted by ferro- or ferri-magnetic microparticles. Upon the application of external magnetic field, they experience rapid and reversible increases in yield stress and viscosity. The problem considered here is first of all the determination of their stability against sedimentation, an essential issue in their practical application. Although this problem is typically faced through the addition of thixotropic agents to the liquid medium, in this work, we propose the investigation of the effect of magnetic nanoparticles addition, so that the dispersion medium is in reality a ferrofluid. It is found that a volume fraction of nanoparticles not higher than 3% is enough to provide a long-lasting stabilization to MRFs containing above 30% iron microparticles. In the, in fact unavoidable, event of settling, the important point is the ease of redispersion of the sediment. This is indirectly evaluated in the present investigation by measuring the penetration force in the suspension, using a standard hardness needle. Again, it is found that the nanoparticles addition produces soft sediments by avoiding short-range attractions between the large iron particles. Finally, the performance of the designed MRFs is evaluated by obtaining their steady-state rheograms for different volume fractions of magnetite and different magnetic field strengths. The yield stress is found to be strongly field-dependent, and it can achieve the high values expected in standard magnetorheological fluids but with improved stability and redispersibility.

Dielectric response of concentrated colloidal suspensions

The determination of the low-frequency (typically 0–1 MHz) dielectric dispersion of colloidal suspensions may become an electrokinetic tool of wider use if the accuracy of experimental data can be improved and if trustable theories, available for a wide range of situations, are made available. In the present work, we focus on the latter aspect: Since the dielectric constant of the suspensions is in fact a collective property, its determination could be most useful in concentrated suspensions. This is our aim in this paper. Using the classical electrokinetic equations and a cell model accounting for particle–particle interactions, we present calculations of the dielectric spectra of concentrated (volume fractions up to 50%) suspensions of spheres. Most of our results cannot be thought of as any sort of extrapolation of those corresponding to dilute suspensions (the reverse is true), and in fact the notion of a dilute colloidal system is itself not free of uncertainties, as no “critical volume fraction” can...

AC Electrokinetics of Concentrated Suspensions of Soft Particles

In this work, we show how the cell model traditionally used for the evaluation of the electrokinetic properties of concentrated suspensions can be modified to include the case of soft particles, that is, particles consisting of a rigid core and a polyelectrolyte membrane. The Navier-Stokes and Poissons equations have been modified to account for the presence of extra friction and a volume-distributed charge in the membrane. In addition to the boundary conditions on the particle and the cell boundary, it is necessary to define conditions on the polymer-electrolyte solution interface. The frequency dependence of the dynamic mobility and electric permittivity of suspensions of soft particles with arbitrary solids concentration is computed. It is shown that the dynamic mobility of these systems is larger than that corresponding to hard particles with the same charge. For the permittivity, the same trends are observed: the R-relaxation amplitude increases upon coating. It is found that friction plays an important role in determining the mobility, while the permittivity is more affected by the concentration of solids. The model also predicts that the charges on the core and in the membrane are very important parameters, although their effects differ on the mobility and the permittivity. While the former depends mainly on the membrane charge, the latter is responsive to both charges at comparable extents.

Electrophoretic characterization of gold nanoparticles functionalized with human serum albumin (HSA) and creatine

The synthesis of composite nanoparticles consisting of a gold core coated with a human serum albumin (HSA)/creatine layer is described, and their possible application as novel drug carriers for brain delivery is discussed. In this paper, the effect of the concentration of creatine and HSA in the different formulations is studied by electrophoretic mobility measurements as a function of pH and ionic strength. Due to the permeable character of the coatings surrounding the gold cores, an appropriate analysis of their electrophoretic mobility must be addressed. Recent developments of electrokinetic theories for particles covered by soft surface layers have rendered possible the evaluation of the softness degree from raw electrophoretic mobility data. In the present contribution, the data are quantitatively analyzed on the basis of three theoretical models of the electrokinetics of soft particles. As a result, information is obtained on both the surface potential and the charge density of the surrounding layer. The three models used reproduce properly the experimental behavior, although Duval and Ohshimas calculations appear to yield a more accurate fit of the data. It is shown that the albumin/nanogold particles absorb large amounts of creatine. In addition, the low surface charge and the albumin layer are expected to make it possible to deliver the particles through the blood-brain barrier.

Development of iron/ethylcellulose (core/shell) nanoparticles loaded with diclofenac sodium for arthritis treatment

Diclofenac sodium is a non-steroidal anti-inflammatory drug of choice to treat arthritis because of its potential anti-inflammatory and analgesic activity. Because of its shorter biological half-life, it is needed to be given frequently and at high doses to elicit the required therapeutic activity, simultaneously leading to severe side effects. We hypothesized that the efficient delivery of diclofenac sodium to inflammation using a magnetic colloid could reduce the dose required to bring out sufficient therapeutic response. Hence, we have developed a diclofenac sodium-loaded magnetic nanomedicine, consisting of a magnetic core (iron) and a biocompatible polymeric shell (ethylcellulose) for parenteral administration. These core/shell nanoparticles were synthesized by an emulsion solvent evaporation process. Two drug loading methods were analyzed: the first one being drug addition prior to the emulsion solvent evaporation process (leading to drug entrapment into the polymeric network), and the second method based on diclofenac sodium surface adsorption onto the preformed nanoparticles. Compared to drug adsorption, the entrapment of this active agent into the polymeric matrix yielded a higher drug loading and a slower drug release profile. Such nanocomposites possessed very important characteristics such as unusually high drug loading, enhanced magnetic susceptibility and prolonged drug release, indicating their potential use as nanocarriers for efficient delivery of diclofenac sodium to inflammation sites.

The effect of the concentration of dispersed particles on the mechanisms of low-frequency dielectric dispersion (LFDD) in colloidal suspensions

Abstract There are two mechanisms which are currently used to explain the low-frequency (kHz range) dispersion of the dielectric permittivity of suspensions in electrolyte solutions (LFDD). The first, the surface diffusion mechanism (SDM), associates the LFDD with the diffusion of bound ions along the particle surface caused by the applied electric field. The second, the volume diffusion mechanism (VDM), follows from the generalization for alternating fields of the classical theory of the relaxation effect in electrophoresis and associates the LFDD with the diffusion of free ions in the diffuse double layer. It has been found that VDM is much more strongly dependent on particle concentration than SDM, opening new possibilities for the investigation of each of these two mechanisms separately. The reason is that when the concentration of particles in suspension increases, the characteristic length for the propagation of volume diffusion processes decreases together with the decrease of the free electrolyte volume, whereas the characteristic length for the surface diffusion remains constant. Correspondingly, when particle concentration is raised, the relaxation time of the VDM effect must decrease, whereas it must remain constant for the SDM mechanism. Thus, by varying the concentration of particles in suspension, one can separate the dispersion curves of SDM and VDM. A simple model is elaborated which can be useful to predict the volume fraction dependence of the parameters of LFDD; in particular, its amplitude and critical frequency. The results are compared with experimental data obtained with polymer latex dispersions of volume fractions ranging from 3 to 16%. It is found that the dielectric behaviour (the volume fraction dependence of both the amplitude and critical frequency of LFDD) of the dispersions is reasonably well explained with our model, thus demonstrating that VDM prevails in the systems studied. Experimental data previously found by other authors are also discussed in the light of the model presented.

Study of carbonyl iron/poly(butylcyanoacrylate) (core/shell) particles as anticancer drug delivery systems Loading and release properties.

The aim of this study is to develop a detailed investigation of the capabilities of carbonyl iron/poly(butylcyanoacrylate) (core/shell) particles for the loading and release of 5-Fluorouracil and Ftorafur. The anionic polymerization procedure, used to obtain poly(alkylcyanoacrylate) nanoparticles for drug delivery, was followed in the synthesis of the composite particles, except that the polymerization medium was a carbonyl iron suspension. The influence of the two mechanisms of drug incorporation (entrapment in the polymeric network and surface adsorption) on the drug loading and release profiles were investigated by means of spectrophotometric and electrophoretic measurements. The optimum loading conditions were ascertained and used to perform drug release evaluations. Among the factors affecting drug loading, both pH and drug concentration were found to be the main determining ones. For both drugs, the release profile was found to be biphasic, since the drug adsorbed on the surface was released rather rapidly (close to 100% in 1h), whereas the drug incorporated in the polymer matrix required between 10 and 20h to be fully released. The kinetics of the drug release from the core/shell particles was mainly controlled by the pH of the release medium, the type of drug incorporation, and the amount of drug loaded.