Thermoresponsive microgels at the air-water interface: the impact of the swelling state on interfacial conformation.

Poly(N-vinylcaprolactam) (PVCL) is a new temperature-responsive type of polymer microgel with improved biocompatibility as compared to more commonly used poly(N-isopropylacrylamide) (PNIPAM). Both polymers swell at low temperatures and collapse at high ones, showing a volume phase transition temperature (VPTT) around the physiological temperature. Exploring the interfacial characteristics of thermoresponsive microgels is important due to their potential application in emulsion based systems with tailored stabilities and controlled degradation profiles. In this work, we study the properties of charged PVCL particles at the air-water interface by a combination of adsorption, dilatational rheology and Langmuir monolayers. Although PVCL particles adsorb spontaneously at the air-water interface in both, swollen and collapsed conformations, the interfacial properties show significant differences depending on the swelling state. In particular, the total amount of adsorbed microgels and the rigidity of the monolayer increase as the temperature increases above the VPTT, which is connected to the more compact morphology of the microgels in this regime. Dilatational rheology data show the formation of a very loose adsorbed layer with low cohesivity. In addition, collapsed microgels yield a continuous increase of the surface pressure, whereas swollen microgels show a phase transition at intermediate compressions caused by the deformation of the loose external polymer shell of the particles. We also provide a qualitative interpretation for the surface pressure behavior in terms of microgel-microgel effective pair potentials, and correlate our experimental findings to recent rescaling models that take into account the importance of the internal polymer degrees of freedom in the rearrangement of the conformation of the microgel particles at the interface.

Effect of surface charge on colloidal charge reversal.

The objective of this research work is to understand the effect of the surface charge density on the charge reversal phenomenon. To this end, we use experimental results and computer simulations. In particular, we measure the electrophoretic mobility of latex particles (macroions) in the presence of a multivalent electrolyte. We have focused on the electrolyte concentration range at which a reversal in the electrophoretic mobility is expected to happen. In particular, the role of the surface charge on the charge reversal process is looked into from several latexes with the same functional group but different surface charge densities. Although the mechanism responsible for the colloidal charge reversal is still a controversial issue, it is proved that ionic correlations are behind the appearance of such phenomenon (especially near the macroion surface). This conclusion can be inferred from a great variety of theoretical models. According to them, one of the factors that determine the charge reversal is the surface charge density of the macroions. However, this feature has been rarely analyzed in experiments. Our results appear therefore as a demanded survey to test the validity of the theoretical predictions. Moreover, we have also performed Monte Carlo simulations that take the ion size into account. The correlation found between experiments and simulations is fairly good. The combination of these techniques provides new insight into the colloidal charge reversal phenomena showing the effect of surface charge.

Additional considerations about the role of ion size in charge reversal.

The effect of the ion size on the charge reversal process is studied via canonical Monte Carlo simulation. To this end, a primitive model of electrolyte is used to analyze the electric double layer formed by an asymmetric electrolyte in the presence of a charged planar wall. Different values of ion diameters and surface charge densities are used so as to determine the conditions at which the charge reversal first occurs. For each case, the apparent surface charge density is calculated as a function of the distance from the charged wall for the different electrolyte concentrations in order to establish the minimal salt concentration required for the charge reversal. We will refer to this electrolyte concentration as the reversal concentration and will show how it depends on the surface charge density and on the ion size. From the apparent surface charge density profiles, the distance from the wall at which the charge reversal arises as well as its intensity can be also inferred.

Electric double layers with electrolyte mixtures: integral equations theories and simulations.

A study of a planar electric double layer (EDL) in the presence of mixtures of electrolyte is presented. In particular, results from the Hyper-Netted-Chain/Mean-Spherical-Approximation (HNC/MSA) theory are compared with Monte Carlo (MC) simulations. In this way, the charge inversion induced by mixtures of multivalent and monovalent counterions is probed. Since overcharging phenomena in nature emerge under such conditions, the role of ion-ion correlations in the EDL appears as a crucial point in this kind of study. Unlike previous related works, a realistic hydrated ion size is used in the HNC/MSA calculations and simulations. In this way, a qualitative agreement between the results obtained from the theory and MC simulations is found. However, some discrepancies arise when the charge inversion is expected to be more noticeable, namely at high surface charges and/or elevated concentrations of multivalent electrolytes. Such differences are explained in terms of an overestimation of the charge inversion by the integral equation (IE) formalism.

Simulation of electric double layers undergoing charge inversion: mixtures of mono- and multivalent ions.

In this paper, the electric double layer (EDL) of a charged plane in the presence of mixtures of 1:1 and 3:1 electrolytes has been investigated through Monte Carlo (MC) simulations using a nonrestrictive primitive model of EDL. In particular, the charge inversion in colloids (attributable to an accumulation of counterions on the surface) can be better understood by means of the simulations performed here. Moreover, two mechanisms proposed for charge inversion are probed: The formation of a strongly correlated layer (SCL) of multivalent counterions and excluded volume effects (to which we will also refer as ion size correlations). Our results are in agreement with the behavior found experimentally for some model colloids with increasing the concentration of monovalent salt in the presence of trivalent ions, which clearly supports the relevance of ion size correlations. In contrast, certain disagreement with predictions of SCL theories is reported.

Simulation of electric double layers with multivalent counterions: ion size effect.

In this paper, the structure of the electric double layer in the presence of (mostly) multivalent counterions is investigated through Monte Carlo simulations. Unlike previous similar studies addressing this matter, the difference of this study lies in the use of realistic hydrated ion sizes. Additionally, two different methods for calculating energies in the Metropolis algorithm are applied. The obtained results show that the conclusions of preceding papers must be revised. In particular, our simulations suggest the existence of certain ion layering effects at high surface charge densities, which are not accounted for by integral equation theories in the case of divalent counterions. These layering effects could justify why the overcharging phenomena due to ion size correlations are hardly observable in real colloids with divalent counterions. The existence of charge inversion due to ion size correlations (and without requiring specific counterion adsorption) is probed for trivalent counterions. Moreover, the hypernetted-chain/mean-spherical-approximation is tested under conditions not studied yet.

Amino, chloromethyl and acetal-functionalized latex particles for immunoassays: a comparative study.

Latex particles with different functionalized surface groups (amino, acetal and chloromethyl) for the covalent linking of protein molecules were synthesized and characterized. Immunopurified anti-ferritin antibodies were then covalently coupled with a mean efficiency rate (protein covalently bound to latex particles with respect to the total amount of protein added) of 60%. The reagents developed were applied to the measurement of serum ferritin concentration in a turbidimetric procedure, showing a good measuring range and a lowest detection limit of 3.5 ng/ml in the case of the amino-modified particles. These immunological reagents were compared with a commercial nephelometric method, showing a good linear correlation in all cases but no transferability in the acetal and chloromethyl latex with additional carboxyl groups, probably due to interference with other serum components. The differences among latex found in this study indicate that it would be necessary to optimize the assay conditions for each type of particle, in order to achieve a maximum immunoreactivity.