Biomedical subjects

Jacques Buffle

Publications and source records attributed to Jacques Buffle.

At least 19 recordsLinked to original sources

PubMed2006

Effects of surface site distribution and dielectric discontinuity on the charging behavior of nanoparticles: a grand canonical Monte Carlo study.

The surface site distribution and the dielectric discontinuity effects on the charging process of a spherical nanoparticle (NP) have been investigated. It is well known that electrostatic repulsion between charges on neighbouring sites tends to decrease the effective charge of a NP. The situation is more complicated close to a dielectric breakdown, since here a charged site is not only interacting with its neighbours but also with its own image charge and the image charges of all its neighbours. Coexistence of opposite charges, titration sites positions, and pH dependence are systematically studied using a grand canonical Monte Carlo method. A Tanford and Kirkwood approach has been applied to describe the interaction potentials between explicit discrete ampholytic charging sites. Homogeneous, heterogeneous and patch site distributions were considered to reproduce the titration site distribution at the solid/solution interface of natural NPs. Results show that the charging process is controlled by the balance between Coulomb interactions and the reaction field through the solid-liquid interface. They also show that the site distribution plays a crucial role in the charging process. In patch distributions, charges accumulate at the perimeter of each patch due to finite size effects. When homogeneous and heterogeneous distributions are compared, three different charging regimes are obtained. In homogeneous and heterogeneous (with quite low polydispersity indexes) distributions, the effects of the NP dielectric constant on Coulomb interactions are counterbalanced by the reaction field and in this case, the dielectric breakdown has no significant effect on the charging process. This is not the case in patch distributions, where the dielectric breakdown plays a crucial role in the charging process.

Hydrogen-Ion Concentration↗

PubMed2006

Combining small angle neutron scattering (SANS) and fluorescence correlation spectroscopy (FCS) measurements to relate diffusion in agarose gels to structure.

Small angle neutron scattering (SANS) and fluorescence correlation spectroscopy (FCS) measurements were carried out on agarose hydrogels to link their microscopic structure to the diffusivity of solutes at different scales. SANS allowed for the determination of the distribution of void volumes within the gels. They were shown to be compatible with a random network of cylindrical fibers as described by the Ogston model. FCS measured solute diffusivity in spaces similar in size to the void volumes, and thus, the results reflected the gel heterogeneity. Solute diffusivity was predicted by modeling the gel as microscopic geometrical cells. Variations in the diffusivity of solutes of different sizes could be predicted from the structural parameters of the gel using theory, taking into account obstruction by cylindrical cells and solute hydrodynamics. Prediction of the FCS autocorrelation functions for solutes from a cell model demonstrated a lack of sensitivity of this technique for multicomponent analysis.

Biophysics↗

PubMed2006

Roles of metal ion complexation and membrane permeability in the metal flux through lipophilic membranes. Labile complexes at permeation liquid membranes.

The various physicochemical factors that influence the flux of carrier-transported metal ions through permeation liquid membranes (PLM) are studied systematically. Understanding PLM behavior is important (i) to optimize the application of PLM as metal speciation sensors in environmental media and (ii) because PLM may serve as bioanalogical devices that help to elucidate the environmental physicochemical processes occurring at the surface of biological membranes. Diffusion of free and complexed metal ions in solution, as well as diffusion of the metal carrier complex in the membrane, is considered. The respective roles of diffusion layer thickness, ligand concentration, complex stability, carrier concentration, and membrane thickness are studied experimentally in detail and compared with theory, using various labile complexes, namely, Pb(II)-diglycolate, Cu(II)-diglycolate, and Cu(II)-N-(2-carboxyphenyl)glycine. Conditions where either membrane diffusion or solution diffusion is rate limiting are clearly discriminated. It is shown in particular, that, by tuning the carrier concentration or membrane thickness, either the free metal ion concentration or the total labile metal species are measured. PLM can thus be used to determine whether models based on the free ion activity in solution (such as BLM or FIAM models) are applicable to metal uptake by microorganisms in a real natural medium.

Journal Article↗

PubMed2006

Two grid refinement methods in the lattice Boltzmann framework for reaction-diffusion processes in complex systems.

This paper studies the optimisation of a numerical model and a computer code to solve numerically reaction-diffusion processes in environmental or biological systems with complicated geometries and mixtures of reactions including time and spatial scales extending over several order of magnitude. In particular, we consider different grid refinement techniques in the framework of a lattice Boltzmann solver for reaction-diffusion systems. Two new grid refinement methods are proposed, which are both quantitatively good. The first method is based on the matching of the concentration profiles and fluxes across two adjacent sub-domains, while the second method is based on nested subgrids. The focus of our study is the trade off between accuracy and CPU time. We show how the different parameters of the method, such as the refinement factors, the location of the boundary between different grids or coupling methods at the interface affect the quality of the numerical solution and the efficiency of the method.

Journal Article↗

PubMed2006

Quasi-reversible faradaic depolarization processes in the electrokinetics of the metal/solution interface.

Bipolar faradaic depolarization of the metal/solution interface is quantitatively analyzed for the case where the solution is subject to lateral flow and contains a quasi-reversible redox couple. Transversal convective diffusion of the electroactive species and a position-dependent degree of reversibility of the interfacial electron-transfer (e.t.) reaction are among the primary features that govern depolarization. The spatial distributions of species concentrations and electric potential are numerically simulated. The system is characterized by nonlinear coupling between the transport (diffusion and flow) and the electric potential distribution under conditions of finite local currents. The resulting picture is that the reversibility of the e.t. reaction varies with position on the surface, with the highest reversibility downstream. This, in itself, generally leads to strongly asymmetric profiles of the faradaic current density along the surface. The impact on the electrokinetic properties of the interface is huge. For example, the steady-state streaming potential is depressed by the contribution from the bipolar faradaic process to the back current to an extent that varies from insignificant to complete, depending on the e.t. rate constant and concentrations of the electroactive species.

Journal Article↗

PubMed2006

Comparison of analytical techniques for dynamic trace metal speciation in natural freshwaters.

Several techniques for speciation analysis of Cu, Zn, Cd, Pb, and Ni are used in freshwater systems and compared with respect to their performance and to the metal species detected. The analytical techniques comprise the following: (i) diffusion gradients in thin-film gels (DGT); (ii) gel integrated microelectrodes combined to voltammetric in situ profiling system (GIME-VIP); (iii) stripping chronopotentiometry (SCP); (iv) flow-through and hollow fiber permeation liquid membranes (FTPLM and HFPLM); (v) Donnan membrane technique (DMT); (vi) competitive ligand-exchange/stripping voltammetry (CLE-SV). All methods could be used both under hardwater and under softwater conditions, although in some cases problems with detection limits were encountered at the low total concentrations. The detected Cu, Cd, and Pb concentrations decreased in the order DGT > or = GIME-VIP > or = FTPLM > or = HFPLM approximately = DMT (>CLE-SV for Cd), detected Zn decreased as DGT > or = GIME-VIP and Ni as DGT > DMT, in agreement with the known dynamic features of these techniques. Techniques involving in situ measurements (GIME-VIP) or in situ exposure (DGT, DMT, and HFPLM) appear to be appropriate in avoiding artifacts which may occur during sampling and sample handling.

Artifacts↗

PubMed2006

Model predictions of metal speciation in freshwaters compared to measurements by in situ techniques.

Measurements of trace metal species in situ in a softwater river, a hardwater lake, and a hardwater stream were compared to the equilibrium distribution of species calculated using two models, WHAM 6, incorporating humic ion binding model VI and visual MINTEQ incorporating NICA-Donnan. Diffusive gradients in thin films (DGT) and voltammetry at a gel integrated microelectrode (GIME) were used to estimate dynamic species that are both labile and mobile. The Donnan membrane technique (DMT) and hollow fiber permeation liquid membrane (HFPLM) were used to measure free ion activities. Predictions of dominant metal species using the two models agreed reasonably well, even when colloidal oxide components were considered. Concentrations derived using GIME were generally lower than those from DGT, consistent with calculations of the lability criteria that take into account the smaller time window available forthe fluxto GIME. Model predictions of free ion activities generally did not agree with measurements, highlighting the need for further work and difficulties in obtaining appropriate input data.

Benzopyrans↗

PubMed2006

Electrohydrodynamic properties of succinoglycan as probed by fluorescence correlation spectroscopy, potentiometric titration and capillary electrophoresis.

The electrostatic, hydrodynamic and conformational properties of aqueous solutions of succinoglycan have been analyzed by fluorescence correlation spectroscopy (FCS), proton titration, and capillary electrophoresis (CE) over a large range of pH values and electrolyte (NaCl) concentrations. Using the theoretical formalism developed previously for the electrokinetic properties of soft, permeable particles, a quantitative analysis for the electro-hydrodynamics of succinoglycan is performed by taking into account, in a self-consistent manner, the measured values of the diffusion coefficients, electric charge densities, and electrophoretic mobilities. For that purpose, two limiting conformations for the polysaccharide in solution are tested, i.e. succinoglycan behaves as (i) a spherical, random coil polymer or (ii) a rodlike particle with charged lateral chains. The results show that satisfactory modeling of the titration data for ionic strengths larger than 50 mM can be accomplished using both geometries over the entire range of pH values. Electrophoretic mobilities measured for sufficiently large pH values (pH > 5-6) are in line with predictions based on either model. The best manner to discriminate between these two conceptual models is briefly discussed. For low pH values (pH < 5), both models indicate aggregation, resulting in an increase of the hydrodynamic permeability and a decrease of the diffusion coefficient.

Biocompatible Materials↗

PubMed2005

Dynamic speciation analysis and bioavailability of metals in aquatic systems.

Dynamic metal speciation analysis in aquatic ecosystems is emerging as a powerful basis for development of predictions of bioavailability and reliable risk assessment strategies. A given speciation sensor is characterized by an effective time scale or kinetic window that defines the measurable metal species via their labilities. Here we review the current state of the art for the theory and application of dynamic speciation sensors. We show that a common dynamic interpretation framework, based on rigorous flux expressions incorporating the relevant diffusion and reaction steps, is applicable for a suite of sensors that span a range of time scales. Interpolation from a kinetic spectrum of speciation data is proposed as a practical strategy for addressing questions of bioavailability. Case studies illustrate the practical significance of knowledge on the dynamic features of metal complex species in relation to biouptake, and highlight the limitations of equilibrium-based models.

Bacteria↗

PubMed2005

Humic substances are soft and permeable: evidence from their electrophoretic mobilities.

Due to the complexity of the humic substances (HS), mathematical models have often been employed to understand their roles in the environment. Since no consensus exists with respect to the structure and conformation of the HS, models have alternatively given them properties corresponding to impermeable hard spheres or fully permeable polyelectrolytes. In this study, the hydrodynamic permeability of standard HS (Suwannee River fulvic, humic, and peat humic acids) are evaluated as a function of pH and ionic strength. A detailed theoretical model is used to determine the softness parameter (lambda0), which characterizes the degree of flow penetration into the HS on the basis of measured values of electrophoretic mobilities, diffusion coefficients, and electric charge densities. Their motion in an electric field is evaluated by a rigorous numerical evaluation of the governing electrokinetic equations for soft particles. The hydrodynamic impact of the polyelectrolyte chains is accounted for by a distribution of Stokes resistance centers and partial dissociation of the hydrodynamically immobile ionogenic groups distributed throughout the polyelectrolyte. The results demonstrate thatthe studied HS are small (radius ca. 1 nm), highly charged (500-650 C g(-1) when all sites are dissociated), and very permeable (typical flow penetration length of 25-50% of the radius, depending on pH). The HS also coagulate slightly when lowering the pH of the solution. Modeling of the HS as hard spheres with a charge and slip plane located at the surface is thus physically inappropriate, as are a number of analytical theories for soft particles that hold for low to moderate electrostatic potentials and large colloids. The shortcomings of these simpler approaches, when interpreting the electrophoretic mobilities of HS, are highlighted by comparison with rigorous theoretical predictions.

Colloids↗

PubMed2005

LBGK method coupled to time splitting technique for solving reaction-diffusion processes in complex systems.

A new approach to numerically solve a reaction-diffusion system is given, specifically developed for complex systems including many reacting/diffusing species with broad ranges of rate constants and diffusion coefficients, as well as complicated geometry of reacting interfaces. The approach combines a Lattice Boltzmann (LB) method with a splitting time technique. In the present work, the proposed approach is tested by focusing on the typical reaction process between a metal ion M and a ligand L, to form a complex ML with M being consumed at an electrode. The aim of the paper is to systematically study the convergence conditions of the associated numerical scheme. We find that the combination of LB with the time splitting method allows us to solve the problem for any value of association and dissociation rate constant of the reaction process. Also, the method can be extended to a mixture of ligands. We stress two main points: (1) the LB approach is particularly convenient for the flux computation of M and (2) the splitting time procedure is very well suited for reaction processes involving association-dissociation rate constants varying on many orders of magnitude.

Chemical Industry↗

PubMed2004

The interaction of azacrown ether with fatty acid in nonpolar solvents and at the organic-aqueous interface.

In the paper, we show that lipophilic azacrown ether (22DD) in solvents of low to intermediate polarity forms the complexes with fatty acids, like lauric or palmitic acid. Due to the weak acid-base properties of the azacrown ether-fatty acid system, no proton transfer between the two molecules was observed, as shown by IR and 1H NMR studies. The Job plot exhibits double maximum, suggesting the coexistence of two 22DD-fatty acid complexes, of 1:1 and 1:2 stoichiometry, respectively. Their stability constants were calculated by taking into account the dimerization of fatty acid in toluene. The diffusion coefficients for the free molecules and their complexes were measured with diffusion-ordered spectroscopy (DOSY) NMR in order to prove the close spatial proximity of the molecules. Interfacial tension measurements at the water-toluene interface showed that due to the presence of two decyl chains, 22DD adsorbs at the interface much stronger than dodecanoic (lauric) acid does. The shape of the adsorption isotherm for the mixture of 22DD and lauric acid suggests that the two molecules also interact at the interface in a similar manner as in the bulk of low to intermediate polarity solvents. As a result of the affinity of the fatty acid to strongly surface-active azacrown ether, the interface might be enriched with fatty acid molecules, which without 22DD shows little adsorption at the liquid-liquid interface.

Adsorption↗

PubMed2004

Permeation liquid membrane as a tool for monitoring bioavailable Pb in natural waters.

In order to predict metal bioavailability by microorganisms in natural waters, analytical speciation techniques such as the permeation liquid membrane (PLM) are required. A planar sheet PLM has been characterized by measuring Pb fluxes in the absence and presence of tiron and nitrilotriacetic, iminodiacetic, malonic, citric, polyacrylic and fulvic (Suwannee River fulvic, SRFA) acids. Important parameters such as the diffusion coefficient in the membrane phase and the effective distribution coefficient between the solution and membrane were evaluated in order to determine limiting conditions for the overall transport flux through the membrane. Subsequently, the PLM was tested for its ability to predict bioavailability by the freshwater alga, Chlorella kesslerii by comparing Pb PLM fluxes (JPLM) to Pb biouptake fluxes (Jint) in the absence and presence of the synthetic ligands and SRFA. The capability of the PLM to mimic transport across biological membranes was demonstrated, in particular, from the similarity between the accumulated (PLM, algal) Pb vs. time plots under the different conditions. Under membrane transport limiting conditions, fluxes across both the PLM and biological membranes were proportional to the free metal ion and directly correlated to each other in the zone below saturation of the biological metal uptake sites. The correlation between the different fluxes may be used to predict Pb uptake by C. kesslerii in the presence of the synthetic ligands. However, in the presence of SRFA, the observed Jint was much higher than predicted by results obtained either in the absence or presence of the synthetic ligands.

Acids↗

PubMed2004

Permeation liquid membrane for trace metal speciation in natural waters. Transport of liposoluble Cu(II) complexes.

In this paper, the transport of Cu(II) in the presence of lipophilic Cu(II) organic complexes through permeation liquid membranes (PLMs) have been investigated. In natural waters, small organic compounds, which form liposoluble neutral complexes with Cu(II), are potentially toxic and bioavailable. Hence, to understand the role of liposoluble Cu(II) complexes in natural waters, four organic ligands: phthalic acid, bipyridyl, pyrocatechol and hydroxyquinoline, which form uncharged or lipophilic Cu(II) complexes, were tested. The results showed that the transport of lipophilic Cu(II) complexes through PLM depends on the lipophilicity of the complex. Applications of PLMs in natural waters are presented.

Copper↗

PubMed2004

Size effects on diffusion processes within agarose gels.

To investigate diffusion processes in agarose gel, nanoparticles with sizes in the range between 1 and 140 nm have been tested by means of fluorescence correlation spectroscopy. Understanding the diffusion properties in agarose gels is interesting, because such gels are good models for microbial biofilms and cells cytoplasm. The fluorescence correlation spectroscopy technique is very useful for such investigations due to its high sensitivity and selectivity, its excellent spatial resolution compared to the pore size of the gel, and its ability to probe a wide range of sizes of diffusing nanoparticles. The largest hydrodynamic radius (R(c)) of trapped particles that displayed local mobility was estimated to be 70 nm for a 1.5% agarose gel. The results showed that diffusion of particles in agarose gel is anomalous, with a diverging fractal dimension of diffusion when the large particles become entrapped in the pores of the gel. The latter situation occurs when the reduced size (R(A)/R(c)) of the diffusing particle, A, is >0.4. Variations of the fractal exponent of diffusion (d(w)) with the reduced particle size were in agreement with three-dimensional Monte Carlo simulations in porous media. Nonetheless, a systematic offset of d(w) was observed in real systems and was attributed to weak nonelastic interactions between the diffusing particles and polymer fibers, which was not considered in the Monte Carlo simulations.

Biophysics↗

PubMed2003

Flocculation of hematite particles by a comparatively large rigid polysaccharide: schizophyllan.

We studied the flocculation kinetics and structure of hematite aggregates induced by a large rigid extracellular polysaccharide, schizophyllan. Transmission electron microscopy (TEM), atomic force microscopy (AFM), photon correlation spectroscopy (PCS), and static light scattering (SLS) were used to characterize hematite particles, schizophyllan chains, and their flocs, to follow the time evolution of floc sizes, and to determine floc fractal dimensions. A maximum flocculation rate was found at a certain schizophyllan/hematite ratio. The maximum rate was considerably smaller than the rate of diffusion-limited aggregation (DLA) of hematite particles induced by simple electrolytes. To interpret the experimental results and to reveal various factors affecting the optimal dosage, Monte Carlo simulations were performed on the flocculation of small colloidal particles by relatively long, monodisperse linear polymers. The existence of the maximum flocculation rate was confirmed by computer simulation. However, a higher optimal dosage of schizophyllan was obtained in the experiments. The difference in the optimal dosage can be attributed mostly to the higher adsorption affinity of the hematite on schizophyllan aggregates present in the initial solution and the presence of a large fraction of free polymer chains which do not participate in the flocculation process. Both experiments and computer simulations demonstrated the fractal nature of the schizophyllan-hematite flocs. The fractal dimensions of the flocs at the optimal dosage were determined. A higher fractal dimension was obtained from experiments than from computer simulations, suggesting a reconstruction of the floc structure. Finally, a two-stage flocculation mechanism for hematite particles in the presence of a relatively long schizophyllan polymer was proposed. In the first flocculation stage, the hematite particles are preferentially adsorbed onto the schizophyllan aggregates in solution. The second stage consists of the association of these reactive entities with each other and also with naked chains to form fractal flocs by a bridging mechanism, where the hematite particles play the role of ligands.

Chromatography, Gel↗

PubMed2003

Theoretical and analytical characterization of a flow-through permeation liquid membrane with controlled flux for metal speciation measurements.

Speciation measurements with the permeation liquid membrane (PLM) technology require necessarily a good control of the flux of the analyte. In this perspective, a PLM-based multichannel flow-through cell has been designed. The first objective of this study has been to adapt the classical Levich model commonly used for electrochemical flow devices to the characteristic geometry of the PLM cell. In the latter case and contrary to the Levich model, the effects of the channel lateral walls on the flux of active species through the membrane have to be taken into account. The problem was solved by considering the existence of two parabolic Poiseuille profiles perpendicular to each other and developing along the fluid motion. The theoretical results obtained match satisfactorily with experimental data. The analytical study of this PLM system has been performed with copper(II) ions as test species and has shown that the preconcentration factor is (1) linear at least for preconcentration times of < or = 120 min, (2) reproducible on the same membrane as well as on different membranes, and (3) independent of the initial test metal ion concentration in the sample solution. The capabilities of this cell to determine metal speciation by considering lability of complexes and the flux of metal at variable flow rates of the test solution is also discussed by means of Cu(II)/sulfosalicylic complexes.

Journal Article↗

PubMed2002

Application of fluorescence correlation spectroscopy: a study of flocculation of rigid rod-like biopolymer (schizophyllan) and colloidal particles.

The flocculation between the rod-like biopolymer Schizophyllan and two types of colloidal particles (latex with diameter 40 nm and alumina with diameter 60 nm) has been investigated by means of fluorescence correlation spectroscopy (FCS). The concentration ratio of Schizophyllan/particle q was varied in the range 0.1 approximately 20. Under conditions of pH about 5.7, 1 mmol.L(-1) NaCl, and room temperature (22+/-0.5 degrees C), the particles are strongly charged (alumina particles positively charged, latex negatively), while Schizophyllan is neutral. We observed that Schizophyllan chains flocculate with both types of particles, which suggests that the charge neutralization does not play a decisive role in these interactions. The ratio of fluorescence intensity of one floc over that of one particle, Q(f)/Q(p), and the corresponding hydrodynamic radius (r(h)) of the flocs have been measured. For a Schizophyllan-latex system, Q(f)/Q(p) reached a maximum value of 5 for q=3 indicating that the flocs contained five particles on average. The corresponding value of r(h) was r(h)=455 nm. The flocculation kinetic of latex particles with Schizophyllan was too fast to be measurable by FCS. For the Schizophyllan-alumina system, Q(f)/Q(p) was stable at about 1 in the whole studied range of q but r(h) increased with q suggesting that many Schizophyllan chains are adsorbed on individual particles. The flocculation kinetic of this system was studied by FCS and the obtained results were compatible with those of photon correlation spectroscopy.

Aluminum Oxide↗