Biomedical subjects

D Bedeaux

Publications and source records attributed to D Bedeaux.

11 recordsLinked to original sources

PubMed2006

Interface film resistivities for heat and mass transfers-integral relations verified by non-equilibrium molecular dynamics.

Integral relations that predict interface film transfer coefficients for evaporation and condensation have recently been derived. According to these relations, all coefficients can be calculated for one-component systems, using the thermal resistivity and the enthalpy profile through the interface. The integral relations were tested in this work using nonequilibrium molecular dynamics simulations for argon-like particles and n-octane molecules. The simulations confirm the integral relations within the accuracy of the calculation for both systems. Evidence is presented for the existence of an excess thermal resistivity on the gas side of the surface, and the fact that this property is decisive for interface heat and mass transfer coefficients. The integral relations were used to predict the mass transfer coefficient for n- octane as a function of surface tension. The findings are important for modeling of one-component phase transitions.

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PubMed2006

Thermodynamics for single-molecule stretching experiments.

We show how to construct nonequilibrium thermodynamics for systems too small to be considered thermodynamically in a traditional sense. Through the use of a nonequilibrium ensemble of many replicas of the system which can be viewed as a large thermodynamic system, we discuss the validity of nonequilibrium thermodynamics relations and analyze the nature of dissipation in small systems through the entropy production rate. We show in particular that the Gibbs equation, when formulated in terms of average values of the extensive quantities, is still valid, whereas the Gibbs-Duhem equation differs from the equation obtained for large systems due to the lack of the thermodynamic limit. Single-molecule stretching experiments are interpreted under the prism of this theory. The potentials of mean force and mean position, now introduced in these experiments in substitution of the thermodynamic potentials, correspond respectively to our Helmholtz and Gibbs energies. These results show that a thermodynamic formalism can indeed be applied at the single-molecule level.

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PubMed2006

Verification of Onsager's reciprocal relations for evaporation and condensation using non-equilibrium molecular dynamics.

Non-equilibrium molecular dynamic (NEMD) simulations have been used to study heat and mass transfer across a vapor-liquid interface for a one-component system using a Lennard-Jones spline potential. It was confirmed that the relation between the surface tension and the surface temperature in the non-equilibrium system was the same as in equilibrium (local equilibrium). Interfacial transfer coefficients were evaluated for the surface, which expressed the heat and mass fluxes in temperature and chemical potential differences across the interfacial region (film). In this analysis it was assumed that the Onsager reciprocal relations were valid. In this paper we extend the number of simulations such that we can calculate all four interface film transfer coefficients along the whole liquid-vapor coexistence curve. We do this analysis both for the case where we use the measurable heat flux on the vapor side and for the case where we use the measurable heat flux on the liquid side. The most important result we found is that the coupling coefficients within the accuracy of the calculation are equal. This is the first verification of the validity of the Onsager relations for transport through a surface using molecular dynamics. The interfacial film transfer coefficients are found to be a function of the surface temperature alone. New expressions are given for the kinetic theory values of these coefficients which only depend on the surface temperature. The NEMD values were found to be in good agreement with these expressions.

Journal Article↗

PubMed2005

Electrically induced anisotropy in a colloidal dispersion of nanospheres as measured by electric birefringence.

Electrically induced birefringence experiments were performed on dispersions consisting of sulfate latex nanospheres of two different sizes and charges dispersed in an electrolyte solution, at various ionic strengths. The induced birefringence was found to have an important contribution increasing as a quadratic power law of the volume fraction of the spheres. This shows that interparticle interactions play a role in the observed birefringence. The data were analyzed, using a theory from Hafkenscheid and Vlieger [Physica 75 (1974) 57], in terms of the changes of the interparticle separations in the directions parallel and perpendicular to the applied electric field.

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PubMed2005

Active transport: a kinetic description based on thermodynamic grounds.

We show that active transport processes in biological systems can be understood through a local equilibrium description formulated at the mesoscale, the scale to describe stochastic process. This new approach uses the method established by nonequilibrium thermodynamics to account for the irreversible processes occurring at this scale and provides nonlinear kinetic equations for the rates in terms of the driving forces. The results show that the application domain of nonequilibrium thermodynamics method to biological systems goes beyond the linear domain. A model for transport of Ca2+ by the Ca2+-ATPases, nonlinear way. Our results unify thermodynamic and kinetic descriptions, thereby opening new perspectives in the study of different transport phenomena in biological systems.

Animals↗

PubMed2004

Nonequilibrium thermodynamic description of the three-phase contact line.

In order to give a solid foundation of the description of the motion of the three-phase contact line, we develop the nonequilibrium thermodynamic description of the contact line. It is postulated that during its motion the contact line is featured as a separate thermodynamic system. Conservation laws are given for the excess densities of the components, the momentum and the energy along the line. The Gibbs law is formulated for the contact line and using this law the excess entropy production density along the line is constructed. This identifies the conjugate thermodynamic forces and fluxes for the contact line. Linear laws relating these quantities can then be given. The special case considered by Shikmurzaev, who gave the first satisfactory description of the motion of the contact line, is considered in more detail. A new boundary condition is found, which was not used by Shikhmurzaev. The need for such an additional boundary condition for this case was discussed in recent work by Billingham.

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PubMed2002

The interpretation of dielectric spectroscopy measurements on silica and hematite sols.

Experimental data on the dielectric response of silica and hematite sols from the literature are interpreted using an analytical theory developed previously (Chassagne, C., Bedeaux, D., and Koper, G. J. M., J. Phys. Chem B105, 11,743 (2001), and Physica A, to be published). The theory is found to correctly predict both the relaxation frequency and the dielectric permittivity enhancement at low frequencies with only one free parameter. This parameter can be the zeta potential or the Stern layer conductance, in the case that the zeta potential is fixed to agree with the electrophoretic mobility measurements.

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PubMed2000

Osmotic Compressibility of Poly(propylene imine) Dendrimers in Deuterated Methanol.

The inverse osmotic compressibility of the poly(propylene imine) dendrimers in deuterated methanol has been measured as a function of concentration with small-angle neutron scattering. The experimental results reveal three different regimes. First, there is a dilute regime going up to a maximum in the inverse osmotic compressibility. This region can be subdivided into a very dilute region, where the behavior is hard-sphere-like, and a denser region, where the solvation layers overlap. The maximum, occurring around volume fraction 0.30 for each generation, is found to be the concentration where the distance between the centers of two dendrimers is twice their radius of gyration. It designates the crossover to the second regime of a semidilute phase with shrinking dendrimers. Interpenetration of the dendrimers does not seem to take place. Finally, for the higher generations, at high concentrations, the dendrimers are collapsed and the inverse osmotic compressibility starts to increase again. As dendrimers are regularly and very highly branched molecules, they can be considered as ultimately hyperbranched polymers. For both types, the experimental inverse osmotic compressibility shows similar features. The dendrimers seem to be more compact, however. Copyright 2000 Academic Press.

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PubMed2000

Nonequilibrium Molecular Dynamics Simulations of Steady-State Heat and Mass Transport in Condensation.

We present evidence for the hypothesis of local equilibrium for a liquid-vapor interface in a one-component fluid, using molecular dynamics simulations. Lennard-Jones/spline particles are studied in a two-phase system that is out of global equilibrium. Equilibrium simulations are first used to establish the equation of state for the vapor and interface. A procedure is developed to define the boundaries of the interface. Finally it is shown that the equation of state for the interface applies also when there is heat and mass transport through the interface. The temperature gradient in the vapor was 10(8) K/m in these studies. Copyright 2000 Academic Press.

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PubMed1997

A molecular theory for nonohmicity of the ion leak across the lipid-bilayer membrane.

The current-voltage relationship of ion leak (i.e., ion transport involving neither special channels nor carriers) across the lipid-bilayer membrane has been observed to be log-linear above the ohmic regime. The coefficient of the linear term has been found to be universal for membranes and penetrants examined. This universality has been explained in terms of diffusion in an external field, where the ion position is described as a Markovian process. Such a diffusion picture can be questioned, however. It is also probable that a leaking ion gets over the potential barrier before experiencing sufficient random collision in the membrane, considering that each ion is surrounded with long lipid molecules aligned almost unidirectionally. As an alternative, we discuss this ion leak in terms of velocity distribution of the ions entering the membrane and density fluctuation of the lipids. We conclude that we can explain the universality without resorting to the diffusion picture.

Biophysical Phenomena↗

PubMed1991

When and why is the random force in Brownian motion a Gaussian process.

It is shown that the assumptions of causality and time-reversal invariance severely restrict the possibility to describe the fluctuations of a variable in a non-linear Markovian system using a Langevin equation. In fact a theorem is proven which implies that with the aforementioned assumptions a Langevin force which is independent of the state of the system is necessarily Gaussian and white. The theorem furthermore implies that such a description is only possible if the socalled "systematic force" is proportional to the derivative of the logarithm of the equilibrium distribution of the variable. Our analysis is given for a system with one variable which may be either even or odd under time reversal.

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