Biomedical subjects

A Fernández-Nieves

Publications and source records attributed to A Fernández-Nieves.

11 recordsLinked to original sources

PubMed2006

Thermal control over the electrophoresis of soft colloidal particles.

We study the electrophoresis of surface-charged thermosensitive microgel particles based on poly-N-isopropylacrylamide (PNIPAM); these deswell with increasing temperature T. Our results show that the electrophoretic mobility mu is affected by the temperature-induced volume phase transition. It increases with increasing temperature, as a result of the charge density increase induced by particle deswelling. Temperature thus allows control of mu, in contrast to the more conventional charged hard spheres for which mu is T independent. Salt also affects the mu behavior and gives rise to rich phenomenology, sharing common characteristics with charged hard spheres and polyelectrolyte-coated colloids depending on whether the microgels are swollen or deswollen. We interpret the effects of salt concentration n by considering that particle charges are located in an external shell, as confirmed by titrations, and that it is this shell-salt-induced compression that affects the resulting mu behavior.

Journal Article↗

PubMed2005

Ionic correlations in highly charge-asymmetric colloidal liquids.

We use electrophoretic mobility (mu) measurements of charged colloidal particles under the presence of multivalent counterions as a probe of the electrostatic correlations between them; they become important for sufficiently high surface charge densities of the colloid (sigma) and result in a decreasing mu upon increasing sigma. The physics of this decrease is the same as that giving rise to charge inversion. We account qualitatively for the observations by considering recent theoretical arguments that assume the counterions next to the colloid surface as a strongly correlated liquid of properties similar to that of a Wigner crystal.

Journal Article↗

PubMed2005

Electrophoresis of large polyelectrolyte-coated colloidal particles.

We perform electrophoretic mobility mu measurements of spherical colloidal particles coated with a charged polyelectrolyte shell versus 1:1 electrolyte concentration c. Instead of the expected Smoluchowski scaling law mu approximately c(- 1 / 2) for large kappaa, with kappa the inverse of the Debye length, we find that mu scales as mu approximately c(- 1 / 3). We account for this result using a general theory for the electrophoresis of soft particles [H. Ohshima, Adv. Colloid Interface Sci. 62, 189 (1995)] combined with the salt concentration dependence of the shell thickness, as described by Pincus [P. Pincus, Macromolecules 24, 2912 (1991)].

Journal Article↗

PubMed2005

Electrophoresis of ionic microgel particles: from charged hard spheres to polyelectrolyte-like behavior.

We perform electrophoretic mobility measurements of ionic microgel particles in the deswollen and swollen phases. The results show that microgels behave as charged hard spheres in the first case and as free-draining spherical polyelectrolytes in the latter. A unified theory for the electrophoresis of polyelectrolyte-coated particles [H. Ohshima, Adv. Colloid Interface Sci. 62, 189 (1995)] is shown to contain the essential physics for describing the experiments, upon adequate consideration of the particles swelling behavior and network-solvent friction variations.

Journal Article↗

PubMed2004

Electro-optics of bipolar nematic liquid crystal droplets.

We directly visualize the response and relaxation dynamics of bipolar nematic liquid crystal droplets to an applied electric field E. Despite strong planar anchoring, there is no critical field for switching. Instead, upon application of E, the surface region first reorients, followed by movement of the disclinations and the bipolar axis. After removing E, elastic forces restore the drop to its original state. The collective electro-optic properties of ordered hexagonal-close-packed monolayers of drops are probed by diffraction experiments confirming the proposed switching mechanism.

Journal Article↗

PubMed2004

Static light scattering from microgel particles: model of variable dielectric permittivity.

We perform static light scattering experiments on a dilute suspension of microgel particles and model the resultant form factors Pq by assuming an exponentially decaying dielectric permittivity. The result is that Pq is a Lorentzian function of the scattering wavevector q for length scales greater than the particle size; the width approximately corresponding to twice the particle radius. This simple model reasonably accounts for scattered light from both swollen and shrunken microgel phases.

Journal Article↗

PubMed2002

Structural modifications in the swelling of inhomogeneous microgels by light and neutron scattering.

Small-angle neutron scattering and dynamic light scattering have been used to study the thermodynamics of swelling and the associated structure modifications of highly cross-linked temperature-sensitive poly (N-isopropylacrylamide) [poly(NIPAM)] microgels in D2O. A particle core-shell model is proposed, with the core containing most of the cross-linker molecules. The Flory-Rehner theory, with the inclusion of a concentration dependent Flory solvency parameter, successfully describes the experimental swelling, despite the inhomogeneous character of the particles. Interestingly, the shell evolution with temperature controls the whole particle swelling, exerting an external pressure over the core, which in turn influences its size during the swelling process. Scaling laws for the correlation lengths were found with respect to temperature and polymer concentration. Finally, it has been encountered that for the collapsed microgel states, the particle surface seems to have a fractal character.

Journal Article↗

PubMed2002

Thermodynamics of ionic microgels.

We present a theory of dilute aqueous suspensions of microgel particles. It is found that as the number of charged monomers in the polymer network composing mesoscopic gel increases, the particles undergo a swelling transition. Depending on the hydrophobicity of the polymer, this transition can be either continuous or discontinuous. Furthermore, similar to charge stabilized colloidal particles, we find that the electrophoretic mobility of the microgel is controlled by an effective charge. Unlike the colloids, however, for which the effective charge grows asymptotically with the logarithm of the bare charge, the effective charge of an ionic microgel scales as Z(eff) approximately Z0.5. The findings are in good agreement with the experimental measurements.

Journal Article↗

PubMed2001

Structure formation from mesoscopic soft particles.

In this work, the aggregation of mesoscopic gel particles (soft colloids) has been experimentally investigated. The interaction between particles was controlled through the addition of salt, above the critical coagulation concentration, resulting in aggregation with finite bond energies. Attention has been paid to the structure of the clusters formed in the process as well as to the aggregation kinetics. The results indicate that the clusters are fractal and the kinetics of aggregation can be described through the dynamic scaling solution of the Smoluchowski equation. As the energy minimum increases in depth the resultant clusters pass from a very compact structure to typical diffusion-limited cluster aggregation (DLCA) fractal dimension values. In addition, the kinetics of growth change from those observed in reaction controlled aggregation to DLCA. These results can be explained within the framework of a reversible growth model, arising from the fact that aggregation takes place in an energy minimum of restricted depth. Moreover, they show that structure and kinetics decouple for such a soft sphere system, in contrast to what is encountered for DLCA and reaction-limited processes. Finally, an unexpected return to a reaction controlled aggregation kinetics was observed for sufficiently deep energy minima, which could be due to the polymerlike particularities of the soft particles considered in this work.

Journal Article↗

PubMed2001

Nonlinear effects in the stability of highly charged colloidal suspensions.

We investigate the nonlinear effects related to the formation of particle-counterion clusters in highly charged asymmetric colloidal suspensions. The ocurrence of such clustering is experimentally probed by studying the stability of the colloidal system. The results demonstrate that a renormalized charge is needed in order to explain the observed critical coagulation concentrations. This renormalization is predicted by an extension of the Debye-Hückel-Bjerrum liquid state theory [A. Diehl, M. C. Barbosa, and Y. Levin, Europhys. Lett. 53, 86 (2001)]. Therefore, counterion condensation seems to become apparent in particle aggregation processes through control of the repulsive barrier that keeps the system stable. As a consequence of the agreement, new insights into the microscopic state of highly charged complex fluids follow.

Journal Article↗

PubMed2001

Particle-counterion clustering in highly charge-asymmetric complex fluids.

The formation of particle-counterion clusters through electrostatic interaction is studied in this work for a highly charge asymmetric colloidal suspension. The occurrence of such clustering is probed by the particle electrophoretic mobility, i.e., with the aid of a transport property. The results show that the effective charge manifesting under the presence of an external electric field is the renormalized charge predicted by an extension of the Debye-Hückel-Bjerrum theory to the fluid state of highly charged colloids.

Biophysics↗