Conditional equilibrium constants in multicomponent heterogeneous adsorption: The conditional affinity spectrum

The concept of conditional stability constant is extended to the competitive binding of small molecules to heterogeneous surfaces or macromolecules via the introduction of the conditional affinity spectrum (CAS). The CAS describes the distribution of effective binding energies experienced by one complexing agent at a fixed concentration of the rest. We show that, when the multicomponent system can be described in terms of an underlying affinity spectrum [integral equation (IE) approach], the system can always be characterized by means of a CAS. The thermodynamic properties of the CAS and its dependence on the concentration of the rest of components are discussed. In the context of metal/proton competition, analytical expressions for the mean (conditional average affinity) and the variance (conditional heterogeneity) of the CAS as functions of pH are reported and their physical interpretation discussed. Furthermore, we show that the dependence of the CAS variance on pH allows for the analytical determination of the correlation coefficient between the binding energies of the metal and the proton. Nonideal competitive adsorption isotherm and Frumkin isotherms are used to illustrate the results of this work. Finally, the possibility of using CAS when the IE approach does not apply (for instance, when multidentate binding is present) is explored. © 2006 American Institute of Physics.

Affinity distribution functions in multicomponent heterogeneous adsorption. Analytical inversion of isotherms to obtain affinity spectra

An analytical approach for the interpretation of multicomponent heterogeneous adsorption or complexation isotherms in terms of multidimensional affinity spectra is presented. Fourier transform, applied to analyze the corresponding integral equation, leads to an inversion formula which allows the computation of the multicomponent affinity spectrum underlying a given competitive isotherm. Although a different mathematical methodology is used, this procedure can be seen as the extension to multicomponent systems of the classical Sips’s work devoted to monocomponent systems. Furthermore, a methodology which yields analytical expressions for the main statistical properties (mean free energies of binding and covariance matrix) of multidimensional affinity spectra is reported. Thus, the level of binding correlation between the different components can be quantified. It has to be highlighted that the reported methodology does not require the knowledge of the affinity spectrum to calculate the means, variances, and covariance of the binding energies of the different components. Nonideal competitive consistent adsorption isotherm, widely used in metal/proton competitive complexation to environmental macromolecules, and Frumkin competitive isotherms are selected to illustrate the application of the reported results. Explicit analytical expressions for the affinity spectrum as well as for the matrix correlation are obtained for the NICCA case. © 2004 American Institute of Physics.

When Langmuir is too simple: H2 dissociation on Pd(111) at high coverage

Recent experiments of H2 adsorption on Pd(111) [T. Mitsui et al., Nature (London) 422, 705 (2003)] have questioned the classical Langmuir picture of second order adsorption kinetics at high surface coverage requiring pairs of empty sites for the dissociative chemisorption. Experiments find that at least three empty sites are needed. Through density functional theory, we find that H2 dissociation is favored on ensembles of sites that involve a Pd atom with no direct interaction with adsorbed hydrogen. Such active sites are formed by aggregation of at least 3 H-free sites revealing the complex structure of the "active sites."

Estudi dinàmic i manipulació de fluxos en monocapes de Langmuir de molècules fotosensibles

Durant el període de gaudiment de la beca, des del dia 9 de març del 2007 fins el dia 8 de març del 2010, s’han dut a terme diferents tipus d’experiments amb sistemes bidimensionals com són les monocapes de Langmuir. Inicialment es va començar per l’estudi i la caracterització d’aquests sistemes experimentals, tant en repòs com en dinàmic, com és l’estudi de la reposta col•lectiva molecular de dominis d’un azoderivat fotosensible al rotar el pla de polarització mentre es mante sota il•luminació constant i els estudis de sistemes bidimensionals al collapse que es poden relacionar a les propietats viscoplàstiques dels sòlids. Una altra via d’estudi és la reologia d’aquests sistemes bidimensionals quan flueixen a través de canals. Arrel del sistema experimental més simple, una monocapa fluint per un canal, s’ha observat i estudiat l’efecte coll d’ampolla. Un cop assolit i estudiat el sistema més senzill, s’han aplicat tècniques més complexes de fabricació per fotolitografia per fer fluir monocapes de Langmuir per circuits on hi ha un gran contrast de mullat. Un cop aquests circuits es van implementar satisfactòriament en un sistema pel control de fluxos bidimensionals, es posen de manifest les possibles aplicacions futures d’aquests sistemes per l’estudi i el desenvolupament de la microfluídica bidimensional.

Ab initio study of NOx compounds adsorption on SnO2 surface

An ab initio study of the adsorption processes on NOx compounds on (1 1 0) SnO2 surface is presented with the aim of providing theoretical hints for the development of improved NOx gas sensors. From first principles calculations (DFT¿GGA approximation), the most relevant NO and NO2 adsorption processes are analyzed by means of the estimation of their adsorption energies. The resulting values and the developed model are also corroborated with experimental desorption temperatures for NO and NO2, allowing us to explain the temperature-programmed desorption experiments. The interference of the SO2 poisoning agent on the studied processes is discussed and the adsorption site blocking consequences on sensing response are analyzed.

Adsorption potentials for nonplanar geometries

We present a method to compute, assuming a continuous distribution of sources, the elementary potential created by a differential element of volume of matter, whose integral generates a known adsorption field V(z) for a planar surface. We show that this elementary potential is univocally determined by the original field and can be used to generate adsorption potentials for other nontrivial geometries. We illustrate the method for the Chizmeshya-Cole-Zaremba physisorption potential and discuss several examples and applications.

Probing elastic anisotropy from defect dynamics in Langmuir monolayers

We study the dynamics of annihilation of point defects in Langmuir monolayers. The absence of hydrodynamic effects allows us to quantitatively relate the asymmetry in defect mobility to the elastic anisotropy of the material, which in turn can be varied through the control of the surface pressure applied to the monolayer. Using the proposed theoretical analysis, we are able to obtain rather elusive equilibrium properties out of relatively simple dynamical measurements. In particular, we measure the elastic constants and their pressure dependence.

Adsorption of colloidal particles in the presence of external fields

We present a new class of sequential adsorption models in which the adsorbing particles reach the surface following an inclined direction (shadow models). Capillary electrophoresis, adsorption in the presence of a shear, and adsorption on an inclined substrate are physical manifestations of these models. Numerical simulations are carried out to show how the new adsorption mechanisms are responsible for the formation of more ordered adsorbed layers and have important implications in the kinetics, in particular, modifying the jamming limit.

Adsorption kinetics in the presence of external fields

In this article we present a detailed analysis of the kinetics of a class of sequential adsorption models that take into account the effect of externally applied fields (as an electric field, or a shear rate) on the adsorption. The excluded volume interactions related to the finite size of the adsorbing particles are modified by the external fields. As a result, new adsorption mechanisms appear with respect to the ones used to describe the kinetics in a quiescent fluid. In particular, if the adsorbing particles are allowed to roll over preadsorbed ones, adsorption becomes non local even in the simplest geometry. An exact analytic theory cannot be developed, but we introduce a self-consistent theory that turns out to agree with the simulation results over all the range of the parameters.

Adsorption kinetics in the presence of external fields

In this article we present a detailed analysis of the kinetics of a class of sequential adsorption models that take into account the effect of externally applied fields (as an electric field, or a shear rate) on the adsorption. The excluded volume interactions related to the finite size of the adsorbing particles are modified by the external fields. As a result, new adsorption mechanisms appear with respect to the ones used to describe the kinetics in a quiescent fluid. In particular, if the adsorbing particles are allowed to roll over preadsorbed ones, adsorption becomes non local even in the simplest geometry. An exact analytic theory cannot be developed, but we introduce a self-consistent theory that turns out to agree with the simulation results over all the range of the parameters.

Understanding and modulating the competitive surface-adsorption of proteins through coarse-grained molecular dynamics simulations

It is now well accepted that cellular responses to materials in a biological medium reflect greatly the adsorbed biomolecular layer, rather than the material itself. Here, we study by molecular dynamics simulations the competitive protein adsorption on a surface (Vroman effect), i.e. the non-monotonic behavior of the amount of protein adsorbed on a surface in contact with plasma as functions of contact time and plasma concentration. We find a complex behavior, with regimes during which small and large proteins are not necessarily competing between them, but are both competing with others in solution ("cooperative" adsorption). We show how the Vroman effect can be understood, controlled and inverted.

Nonequilibrium orientational patterns in two-component Langmuir monolayers

A model of a phase-separating two-component Langmuir monolayer in the presence of a photoinduced reaction interconverting two components is formulated. An interplay between phase separation, orientational ordering, and reaction is found to lead to a variety of nonequilibrium self-organized patterns, both stationary and traveling. Examples of the patterns, observed in numerical simulations, include flowing droplets, traveling stripes, wave sources, and vortex defects.

Probing elastic anisotropy from defect dynamics in Langmuir monolayers

We study the dynamics of annihilation of point defects in Langmuir monolayers. The absence of hydrodynamic effects allows us to quantitatively relate the asymmetry in defect mobility to the elastic anisotropy of the material, which in turn can be varied through the control of the surface pressure applied to the monolayer. Using the proposed theoretical analysis, we are able to obtain rather elusive equilibrium properties out of relatively simple dynamical measurements. In particular, we measure the elastic constants and their pressure dependence.

Alignment of hexatic langmuir monolayers under shear

We have studied the structural changes that fatty acid monolayers in the Ov phase undergo when a simple shear flow is imposed. A strong coupling is revealed by the changes in domain structure that are observable using Brewster angle microscopy, suggesting the possibility of shear alignment. The dependence of the alignment on the molecular polar tilt proves that the mechanism is different than in nematic liquid crystals. We argue that the degenerate lattice symmetry lines of the underlying pseudohexagonal lattice align in the flow direction, and we explain the observed alignment angle using geometrical arguments.