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1.
Langmuir ; 31(45): 12437-46, 2015 Nov 17.
Artículo en Inglés | MEDLINE | ID: mdl-26488560

RESUMEN

Reinforcement of a polymer matrix through the incorporation of nanoparticles (fillers) is a common industrial practice that greatly enhances the mechanical properties of the composite material. The origin of such mechanical reinforcement has been linked to the interaction between the polymer and filler as well as the homogeneous dispersion of the filler within the polymer matrix. In natural rubber (NR) technology, knowledge of the conditions necessary to achieve more efficient NR-filler interactions is improving continuously. This study explores the important physicochemical parameters required to achieve NR-filler interactions under dilute aqueous conditions by varying both the properties of the filler (size, composition, surface activity, concentration) and the aqueous solution (ionic strength, ion valency). By combining fluorescence and electron microscopy methods, we show that NR and silica interact only in the presence of ions and that heteroaggregation is favored more than homoaggregation of silica-silica or NR-NR. The interaction kinetics increases with the ion valence, whereas the morphology of the heteroaggregates depends on the size of silica and the volume percent ratio (dry silica/dry NR). We observe dendritic structures using silica with a diameter (d) of 100 nm at a ∼20-50 vol % ratio, whereas we obtain raspberry-like structures using silica with d = 30 nm particles. We observe that in liquid the interaction is controlled by the hydrophilic bioshell, in contrast to dried conditions, where hydrophobic polymer dominates the interaction of NR with the fillers. A good correlation between the nanoscopic aggregation behavior and the macroscopic aggregation dynamics of the particles was observed. These results provide insight into improving the reinforcement of a polymer matrix using NR-filler films.


Asunto(s)
Nanopartículas/química , Goma/química , Dióxido de Silicio/química , Dureza , Interacciones Hidrofóbicas e Hidrofílicas , Ensayo de Materiales , Nanopartículas/ultraestructura , Concentración Osmolar , Tamaño de la Partícula , Propiedades de Superficie , Agua/química
2.
Sci Rep ; 4: 7389, 2014 Dec 09.
Artículo en Inglés | MEDLINE | ID: mdl-25487130

RESUMEN

Rubber-filler composites are a key component in the manufacture of tyres. The filler provides mechanical reinforcement and additional wear resistance to the rubber, but it in turn introduces non-linear mechanical behaviour to the material which most likely arises from interactions between the filler particles, mediated by the rubber matrix. While various studies have been made on the bulk mechanical properties and of the filler network structure (both imaging and by simulations), there presently does not exist any work directly linking filler particle spacing and mechanical properties. Here we show that using STEM tomography, aided by a machine learning image analysis procedure, to measure silica particle spacings provides a direct link between the inter-particle spacing and the reduction in shear modulus as a function of strain (the Payne effect), measured using dynamic mechanical analysis. Simulations of filler network formation using attractive, repulsive and non-interacting potentials were processed using the same method and compared with the experimental data, with the net result being that an attractive inter-particle potential is the most accurate way of modelling styrene-butadiene rubber-silica composite formation.

3.
Langmuir ; 29(47): 14655-65, 2013 Nov 26.
Artículo en Inglés | MEDLINE | ID: mdl-24152085

RESUMEN

The interfacial structure of natural rubber (NR) colloids is investigated by means of cryogenic transmission electron microscopy (cryo-TEM) and electrokinetics over a broad range of KNO3 electrolyte concentrations (4-300 mM) and pH values (1-8). The asymptotic plateau value reached by NR electrophoretic mobility (µ) in the thin double layer limit supports the presence of a soft (ion- and water-permeable) polyelectrolytic type of layer located at the periphery of the NR particles. This property is confirmed by the analysis of the electron density profile obtained from cryo-TEM that evidences a ∼2-4 nm thick corona surrounding the NR polyisoprene core. The dependence of µ on pH and salt concentration is further marked by a dramatic decrease of the point of zero electrophoretic mobility (PZM) from 3.6 to 0.8 with increasing electrolyte concentration in the range 4-300 mM. Using a recent theory for electrohydrodynamics of soft multilayered particles, this "anomalous" dependence of the PZM on electrolyte concentration is shown to be consistent with a radial organization of anionic and cationic groups across the peripheral NR structure. The NR electrokinetic response in the pH range 1-8 is indeed found to be equivalent to that of particles surrounded by a positively charged ∼3.5 nm thick layer (mean dissociation pK ∼ 4.2) supporting a thin and negatively charged outermost layer (0.6 nm in thickness, pK ∼ 0.7). Altogether, the strong dependence of the PZM on electrolyte concentration suggests that the electrostatic properties of the outer peripheral region of the NR shell are mediated by lipidic residues protruding from a shell containing a significant amount of protein-like charges. This proposed NR shell interfacial structure questions previously reported NR representations according to which the shell consists of either a fully mixed lipid-protein layer, or a layer of phospholipids residing exclusively beneath an outer proteic film.


Asunto(s)
Técnicas Electroquímicas , Goma/química , Microscopía por Crioelectrón , Cinética , Estructura Molecular , Tamaño de la Partícula , Fosfolípidos/química , Proteínas/química , Propiedades de Superficie
4.
Langmuir ; 25(18): 10873-85, 2009 Sep 15.
Artículo en Inglés | MEDLINE | ID: mdl-19735140

RESUMEN

The stability of native and enzyme-treated human red blood cells of type A (Rh D positive) against agglutination is investigated under conditions where it is mediated by immunoglobuline G (IgG) anti-D antibody binding. The propensity of cells to agglutinate is related to their interphasic (electrokinetic) properties. These properties significantly depend on the concentration of proteolytic papain enzyme and protease-free neuraminidase enzyme that the cells are exposed to. The analysis is based on the interpretation of electrophoretic data of cells by means of the numerical theory for the electrokinetics of soft (bio)particles. A significant reduction of the hydrodynamic permeability of the external soft glycoprotein layer of the cells is reported under the action of papain. This reflects a significant decrease in soft surface layer thickness and a loss in cell surface integrity/rigidity, as confirmed by nanomechanical AFM analysis. Neuraminidase action leads to an important decrease in the interphase charge density by removing sialic acids from the cell soft surface layer. This is accompanied by hydrodynamic softness modulations less significant than those observed for papain-treated cells. On the basis of these electrohydrodynamic characteristics, the overall interaction potential profiles between two native cells and two enzyme-treated cells are derived as a function of the soft surface layer thickness in the Debye-Hückel limit that is valid for cell suspensions under physiological conditions (approximately 0.16 M). The thermodynamic computation of cell suspension stability against IgG-mediated agglutination then reveals that a decrease in the cell surface layer thickness is more favorable than a decrease in interphase charge density for inducing agglutination. This is experimentally confirmed by agglutination data collected for papain- and neuraminidase-treated cells.


Asunto(s)
Sistema del Grupo Sanguíneo ABO , Eritrocitos/inmunología , Eritrocitos/metabolismo , Hemaglutinación/inmunología , Inmunoglobulina G/inmunología , Neuraminidasa/metabolismo , Papaína/metabolismo , Sistema del Grupo Sanguíneo ABO/inmunología , Sistema del Grupo Sanguíneo ABO/metabolismo , Pruebas de Hemaglutinación , Humanos , Modelos Biológicos , Sistema del Grupo Sanguíneo Rh-Hr/inmunología , Electricidad Estática , Termodinámica
5.
FEMS Yeast Res ; 9(3): 391-9, 2009 May.
Artículo en Inglés | MEDLINE | ID: mdl-19416105

RESUMEN

In this study, we investigate the electrohydrodynamic and nanomechanical characteristics of two Saccharomyces cerevisiae yeast strains, a wild-type (WT) strain and a strain overexpressing (OE) Hsp12p, in the presence and absence of hydrophobic Congo red compound. By combining these two advanced biophysical methods, we demonstrate that Hsp12p proteins are mostly located within a thin layer (c. 10 nm thick) positioned at the external side of the cell wall. However, this Hsp12p-enriched layer does not prevent Congo red from entering the cell wall and from interacting with the chitin therein. The entrance of Congo red within the cell wall is reflected in an increase of the turgor pressure for the OE strain and a decrease of that for the WT strain. It is shown that these opposite trends are consistent with significant modulations of the water content within the cell wall from/to the cytoplasm. These are the result of changes in the hydrophobicity/hydrophilicity balance, as governed by the intertwined local concentration variations of Congo red and Hsp12p across the cell wall. In particular, the decrease of the turgor pressure in the case of WT strain upon addition of Congo red is shown to be consistent with an upregulation of Hsp12p in the close vicinity of the plasma membrane.


Asunto(s)
Rojo Congo/metabolismo , Regulación Fúngica de la Expresión Génica , Proteínas de Choque Térmico/fisiología , Proteínas de Saccharomyces cerevisiae/fisiología , Saccharomyces cerevisiae/fisiología , Pared Celular/química , Proteínas de Choque Térmico/biosíntesis , Presión Osmótica , Saccharomyces cerevisiae/química , Proteínas de Saccharomyces cerevisiae/biosíntesis , Agua/metabolismo
6.
Artículo en Inglés | MEDLINE | ID: mdl-19167269

RESUMEN

Lengths, strengths and valences of OH bonds in the two aluminium hydroxides gibbsite and bayerite were determined on the basis of vibrational spectral data. The uncoupled OD stretching modes in the range 2400-2800cm(-1) were recorded by means of infrared diffuse reflectance, thereby avoiding effects of surface, vibrational coupling or particle shape. The assignment of the corresponding Raman spectra resulted in the determination of harmonic wavenumbers, force constants and anharmonicity coefficients of bulk OH groups in the two minerals. OH bond lengths deduced from these data varied from 0.964A to 0.975A in gibbsite and 0.962A to 0.973A in bayerite. These lengths appear to correspond to weak H-bonds contrary to previously recognized data from X-ray diffraction and neutron diffraction studies. Finally, bond valences were calculated on the basis of these new bond lengths and discussed as a function of crystallographic structures and the nature of hydrogen bonding in these two structures.


Asunto(s)
Hidróxido de Aluminio/química , Enlace de Hidrógeno , Hidróxidos/química , Minerales/química , Análisis Espectral/métodos , Vibración
7.
PLoS One ; 3(11): e3817, 2008.
Artículo en Inglés | MEDLINE | ID: mdl-19043570

RESUMEN

Analysing the pathogenic mechanisms of a bacterium requires an understanding of the composition of the bacterial cell surface. The bacterial surface provides the first barrier against innate immune mechanisms as well as mediating attachment to cells/surfaces to resist clearance. We utilised a series of Klebsiella pneumoniae mutants in which the two major polysaccharide layers, capsule and lipopolysaccharide (LPS), were absent or truncated, to investigate the ability of these layers to protect against innate immune mechanisms and to associate with eukaryotic cells. The capsule alone was found to be essential for resistance to complement mediated killing while both capsule and LPS were involved in cell-association, albeit through different mechanisms. The capsule impeded cell-association while the LPS saccharides increased cell-association in a non-specific manner. The electrohydrodynamic characteristics of the strains suggested the differing interaction of each bacterial strain with eukaryotic cells could be partly explained by the charge density displayed by the outermost polysaccharide layer. This highlights the importance of considering not only specific adhesin:ligand interactions commonly studied in adherence assays but also the initial non-specific interactions governed largely by the electrostatic interaction forces.


Asunto(s)
Cápsulas Bacterianas/fisiología , Klebsiella pneumoniae/patogenicidad , Polisacáridos Bacterianos/fisiología , Adhesinas Bacterianas , Adhesión Bacteriana , Cápsulas Bacterianas/química , Klebsiella pneumoniae/química , Lipopolisacáridos , Mutación , Electricidad Estática
8.
Water Res ; 42(19): 4751-60, 2008 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-18929388

RESUMEN

Adhesion of the bacteria Campylobacter jejuni and Mycobacterium avium onto polyethylene terephtalate (PET), a polymer widely used within the bottled water industry was measured in two different groundwater solutions. From this, it was found that whilst the percentage cell adhesion for a given strain did not change between groundwater types, substantial variation was obtained between the two bacterial species tested: M. avium (10-30% adhered cells) and C. jejuni (1-2%) and no major variations were measured as a function of groundwater composition for a given strain. To explain this, the interfacial electro-hydrodynamic properties of the bacteria were investigated by microelectrophoresis, with the resultant data analysed on the basis of electrokinetic theory for soft biocolloidal particles. The results obtained showed that M. avium carries a significant volume charge density and that its peripheral layer exhibits limited hydrodynamic flow permeation compared to that of C. jejuni. It was also demonstrated that steric hindrance to flow penetration and the degree of hydrophobicity within/of the outer bacterial interface are larger for M. avium cells. In line with this, the larger amount of M. avium cells deposited onto PET substrates as compared to that of C. jejuni can be explained by hydrophobic attraction and chemical binding between hydrophobic PET and outer soft surface layer of the bacteria. Hydrophobicity of PET was addressed by combining contact angle analyses and force spectroscopy using CH(3)-terminated AFM tip.


Asunto(s)
Adhesión Bacteriana , Campylobacter jejuni/fisiología , Mycobacterium avium/fisiología , Tereftalatos Polietilenos/química , Abastecimiento de Agua , Ensayo de Cambio de Movilidad Electroforética , Microscopía de Fuerza Atómica
9.
J Colloid Interface Sci ; 327(2): 472-6, 2008 Nov 15.
Artículo en Inglés | MEDLINE | ID: mdl-18799165

RESUMEN

We report a study of the acid-base properties of Na-montmorillonite suspensions at temperatures from 25 degrees C to 80 degrees C, by continuous and batch potentiometric methods, combined with analysis of the dissolved and readsorbed species. The batch titration curves reveal that the dissolution processes of Na-montmorillonite and silica-rich secondary phases are increasingly predominant, respectively at acid and basic pH, and according to the temperature. The continuous titration curves are less affected by these side reactions. In the absence of a common intersection point, the thermodynamic analysis of the curves was based on the shift of the PZNPC with the ionic strength. This shift was not significantly altered by the temperature, by comparison with the dissociation product of water in the same conditions. Therefore we concluded that protonation-deprotonation of the dissociable sites at the edges of the clay platelets is not significantly temperature dependent.

10.
Langmuir ; 24(19): 10988-95, 2008 Oct 07.
Artículo en Inglés | MEDLINE | ID: mdl-18512877

RESUMEN

The interactions of bacteria with their environment are governed by a complex interplay between biological and physicochemical phenomena. The main challenge is the joint determination of the intertwined interfacial characteristics of bacteria such as mechanical and hydrodynamic softness, interfacial heterogeneity, and electrostatic properties. In this study, we have combined electrokinetics and force spectroscopy to unravel this intricate coupling for two types of Shewanella bacterial strains that vary according to the nature of their outer, permeable, charged gel-like layers. The theoretical interpretation of the bacterial electrokinetic response allows for the estimation of the hydrodynamic permeability, degree of interfacial heterogeneity, and volume charge density for the soft layer that constitutes the outer permeable part of the bacteria. Additionally, the electrostatic interaction forces between an AFM probe and the bacteria were calculated on the basis of their interfacial properties obtained from advanced soft particle electrokinetic analysis. For both bacterial strains, excellent agreement between experimental and theoretical force curves is obtained, which highlights the necessity to account for the interfacial heterogeneity of the bioparticle to interpret AFM and electrokinetic data consistently. From the force profiles, we also derived the relevant mechanical parameters in relation to the turgor pressure within the cell and the nature of the bacterial outer surface layer. These results corroborate the heterogeneous representation of the bacterial interface and show that the decrease in the turgor pressure of the cell with increasing ionic strength is more pronounced for bacteria with a thin surface gel-like layer.


Asunto(s)
Shewanella putrefaciens , Agua/química , Medios de Cultivo , Cinética , Microscopía de Fuerza Atómica , Shewanella putrefaciens/ultraestructura , Electricidad Estática
11.
Water Res ; 42(10-11): 2769-77, 2008 May.
Artículo en Inglés | MEDLINE | ID: mdl-18329685

RESUMEN

We report an experimental investigation of the electrokinetic properties and size variations of four F-specific bacteriophages of the types MS2, GA, Qbeta and SP (21-30 nm in diameter) over a broad range of pH values (1.5-7.5) and NaNO3 electrolyte concentrations (1-100 mM). The results obtained by dynamic light scattering show that the aggregation of SP and GA particles takes place over the whole range of pH and ionic strength conditions examined. For MS2 phages, the aggregation of MS2 particles is not observed for pH higher than the isoelectric point (pI) and large ionic strengths for which interparticular repulsive electrostatic interactions are however expected to be sufficiently screened. Aggregation of the MS2 phages, dispersed in 1 and 100 mM electrolyte concentration, occurs at pH 4, which basically corresponds to the pI as determined by electrophoresis measurements. The Qbeta particles suspended in solutions of low electrolyte concentrations aggregate at low pH values (pI approximately 3) and, unlike MS2, at large ionic strengths over the whole range of pH conditions considered in this study. These elements allow the determination of the hydrophobic sequence for the four phages SP approximately GA>Qbeta>MS2. Close inspection of the electrokinetic results reveals small to significant variations of the pI values-depending on the phage considered-with respect to the concentration of indifferent NaNO3 electrolyte. This indicates that features other than chemical and electrostatic in nature play a key role in determining the pI and more generally the electrophoretic mobility mu of viral particles. A qualitative interpretation is given and is based on the consideration of inner electro-osmotic flow within the isolated or aggregated particles. The impact of the flow properties within the particles is further in agreement with recent theoretical formalism developed for the electrokinetics of soft multiplayer particles, the phages analyzed here being some illustrative examples. The determination and qualitative interpretation of the surface properties of the viral particles as reported in the current study are commented within the context of water treatment especially concerning viral removal by membrane filtration processes.


Asunto(s)
Filtración/métodos , Membranas Artificiales , Fagos ARN/química , Difusión/efectos de los fármacos , Electrólitos/farmacología , Electroforesis , Punto Isoeléctrico , Fagos ARN/efectos de los fármacos , Propiedades de Superficie/efectos de los fármacos , Virión/química
12.
Biophys J ; 94(8): 3293-312, 2008 Apr 15.
Artículo en Inglés | MEDLINE | ID: mdl-18192368

RESUMEN

We report a theoretical investigation of the electrohydrodynamic properties of spherical soft particles composed of permeable concentric layers that differ in thickness, soft material density, chemical composition, and flow penetration degree. Starting from a recent numerical scheme developed for the computation of the direct-current electrophoretic mobility (mu) of diffuse soft bioparticles, the dependence of mu on the electrolyte concentration and solution pH is evaluated taking the known three-layered structure of bacteriophage MS2 as a supporting model system (bulk RNA, RNA-protein bound layer, and coat protein). The electrokinetic results are discussed for various layer thicknesses, hydrodynamic flow penetration degrees, and chemical compositions, and are discussed on the basis of the equilibrium electrostatic potential and hydrodynamic flow field profiles that develop within and around the structured particle. This study allows for identifying the cases where the electrophoretic mobility is a function of the inner structural and chemical specificity of the particle and not only of its outer surface properties. Along these lines, we demonstrate the general inapplicability of the notions of zeta potential (zeta) and surface charge for quantitatively interpreting electrokinetic data collected for such systems. We further shed some light on the physical meaning of the isoelectric point. In particular, numerical and analytical simulations performed on structured soft layers in indifferent electrolytic solution demonstrate that the isoelectric point is a complex ionic strength-dependent signature of the flow permeation properties and of the chemical and structural details of the particle. Finally, the electrophoretic mobilities of the MS2 virus measured at various ionic strength levels and pH values are interpreted on the basis of the theoretical formalism aforementioned. It is shown that the electrokinetic features of MS2 are to a large extent determined not only by the external proteic capsid but also by the chemical composition and hydrodynamic flow permeation of/within the inner RNA-protein bound layer and bulk RNA part of the bacteriophage. The impact of virus aggregation, as revealed by decreasing diffusion coefficients for decreasing pH values, is also discussed.


Asunto(s)
Electroforesis/métodos , Levivirus/química , Levivirus/ultraestructura , Modelos Químicos , Modelos Moleculares , Anisotropía , Simulación por Computador , Elasticidad , Dureza , Levivirus/aislamiento & purificación , Modelos Biológicos , Conformación Molecular , Tamaño de la Partícula
13.
Colloids Surf B Biointerfaces ; 62(2): 206-13, 2008 Apr 01.
Artículo en Inglés | MEDLINE | ID: mdl-18023156

RESUMEN

Force spectroscopy using the atomic force microscope (AFM) is a powerful technique for measuring physical properties and interaction forces at microbial cell surfaces. Typically for such a study, the point at which a force measurement will be made is located by first imaging the cell using AFM in contact mode. In this study, we image the bacterial cell Shewanella putrefaciens for subsequent force measurements using AFM in force-volume mode and compare this to contact-mode images. It is known that contact-mode imaging does not accurately locate the apical surface and periphery of the cell since, in contact mode, a component of the applied load laterally deforms the cell during the raster scan. Here, we illustrate that contact-mode imaging does not accurately locate the apical surface and periphery of the cell since, in contact mode, a component of the applied load laterally deforms the cell during the raster scan. This is an artifact due to the deformability and high degree of curvature of bacterial cells. We further show that force-volume mode imaging avoids the artifacts associated with contact-mode imaging due to surface deformation since it involves the measurement of a grid of individual force profiles. The topographic image is subsequently reconstructed from the zero-force height (the contact distance between the AFM tip and the surface) at each point on the cell surface. We also show how force-volume measurements yield applied load versus indentation data from which mechanical properties of the cell such as Young's modulus, cell turgor pressure and elastic and plastic energies can be extracted.


Asunto(s)
Bacterias/química , Algoritmos , Artefactos , Bacterias/ultraestructura , Fenómenos Químicos , Química Física , Electrólitos , Técnicas In Vitro , Microscopía de Fuerza Atómica , Shewanella putrefaciens/química , Shewanella putrefaciens/ultraestructura , Soluciones
14.
Colloids Surf B Biointerfaces ; 54(1): 10-9, 2007 Jan 15.
Artículo en Inglés | MEDLINE | ID: mdl-17067786

RESUMEN

In recent years, the physical properties and interaction forces of microbial cell surfaces have been extensively studied using atomic force microscopy (AFM). A variety of AFM force spectroscopy approaches have been developed for investigating native cell surfaces with piconewton (nanonewton) sensitivity and nanometer lateral resolution, providing novel information on the nanomechanical properties of cell walls, on surface forces such as van der Waals and electrostatic forces, solvation and steric/bridging forces, and on the forces and localization of molecular recognition events. The intention of this article is to survey these different applications and to discuss related methodologies (how to prepare tips and samples, how to record and interpret force curves).


Asunto(s)
Microscopía de Fuerza Atómica/instrumentación , Microscopía de Fuerza Atómica/métodos , Nanoestructuras/ultraestructura , Animales , Adhesión Bacteriana , Saccharomyces cerevisiae/ultraestructura , Shewanella putrefaciens/ultraestructura , Propiedades de Superficie
15.
Biochim Biophys Acta ; 1774(1): 131-7, 2007 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-17161030

RESUMEN

The yeast S. cerevisiae cell wall comprising a 10 nm thick layer of polysaccharides, predominantly beta(1,3)-glucan and proteins, is the interface between the cell and the neighbouring environment. As such it is not a static entity but rather one that is dynamically remodelled in response to changes in the environmental conditions. We have recently proposed from studies using yeast cells lacking the gene encoding Hsp12p (Deltahsp12 yeast) and from incorporation of Hsp12p into agarose, used as a model system for the beta-glucan layer of the cell wall, that the hydrophilic stress response cell wall protein Hsp12p acts as a cell wall plasticizer. In this report we have used force spectroscopy to confirm that Deltahsp12 yeast are indeed less flexible than the wild type strain. The spring constant of the cell wall of Deltahsp12 yeast, kcw was determined to be 72+/-3 mN m-1 as compared to 17+/-5 mN m-1 obtained for the wild type strain. A similar result was found on the basis of a quantitative analysis of the electrophoretic mobilities measured for the two yeast strains. Those indicated that the hydrodynamic permeability quantified through the softness parameter of the external layer of Deltahsp12 cells was smaller than the one of wild type cells. We proposed from surface infrared spectroscopy measurements that yeast compensate for the lack of Hsp12p by reducing the carbohydrate/proteins ratio of the cell wall or increasing the cell wall chitin content.


Asunto(s)
Pared Celular/fisiología , Proteínas de Choque Térmico/fisiología , Proteínas de Saccharomyces cerevisiae/fisiología , Saccharomyces cerevisiae/ultraestructura , Pared Celular/ultraestructura , Elasticidad , Microscopía de Fuerza Atómica , Saccharomyces cerevisiae/fisiología , Espectrofotometría Infrarroja
16.
Colloids Surf B Biointerfaces ; 52(2): 108-16, 2006 Oct 01.
Artículo en Inglés | MEDLINE | ID: mdl-17120322

RESUMEN

The bacterial surface properties of gram-negative Shewanella putrefaciens were characterized by microbial adhesion to hydrocarbons (MATH), adhesion to polystyrene dishes, and electrophoresis at different values of pH and ionic strength. The bacterial adhesion to these two apolar substrates shows significant variations according to pH and ionic strength. Such behavior could be partly explained by electrostatic repulsions between bacteria and the solid or liquid interface. However, a similar trend was also observed at rather high ionic strength where electrostatic interactions are supposed to be screened. The nanomechanical properties at pH 4 and 10 and at high ionic strength were investigated by using atomic force microscopy (AFM). The indentation curves revealed the presence of a polymeric external layer that swells and softens up with increasing pH. This suggests a concomitant increase of the water permeability and so did of the hydrophilicity of the bacterial surface. Such evolution of the bacterial envelope in response to changes in pH brings new insight to the pH dependence in the bacterial adhesion tests. It especially demonstrates the necessity to consider the hydrophobic/hydrophilic surface properties of bacteria as not univocal for the various experimental conditions investigated.


Asunto(s)
Shewanella putrefaciens/metabolismo , Adhesión Bacteriana , Fenómenos Biomecánicos , Fenómenos Biofísicos , Biofisica , Membrana Celular/química , Membrana Celular/metabolismo , Membrana Celular/ultraestructura , Electroforesis , Hidrocarburos , Concentración de Iones de Hidrógeno , Microscopía de Fuerza Atómica , Microscopía Electrónica , Nanotecnología , Concentración Osmolar , Poliestirenos , Shewanella putrefaciens/química , Shewanella putrefaciens/ultraestructura , Electricidad Estática , Propiedades de Superficie , Termodinámica
17.
Langmuir ; 22(20): 8366-73, 2006 Sep 26.
Artículo en Inglés | MEDLINE | ID: mdl-16981750

RESUMEN

Well-adherent sol-gel-derived silica films functionalized with amine or thiol groups have been electrogenerated on gold electrodes and both the deposition process and the film properties have been studied by various physicochemical techniques. Electrodeposition was achieved by combining the formation of a self-assembled "nanoglue" on the electrode surface, the sol-gel process, and the electrochemical manipulation of pH to catalyze polycondensation of the precursors. Gold electrodes pretreated with mercaptopropyltrimethoxysilane (MPTMS) were immersed in sol solutions containing the selected precursors (tetraethoxysilane, TEOS, in mixture with (3-aminopropyl)triethoxysilane, APTES, or MPTMS) where they underwent a cathodic electrolysis to generate the hydroxyl ions that are necessary to catalyze the formation of the organosilica films on the electrode surface. Special attention was given to analyze the effects of deposition time and applied potential and to compare APTES and MPTMS films. Characterization was made using quartz crystal microbalance, scanning electron microscopy, cyclic voltammetry, and atomic force microscopy (including in situ monitoring). The electrodeposition process was found to occur at two growing rates: a first slow stage giving rise to rather homogeneous, yet rough, films with thickness in the sub-mum range (increasing continuously when increasing the deposition time), which was followed by a faster gelification step resulting in much thicker (>1 microm) and rougher macroporous deposits. These two successive situations were observed independently on the applied potential except that more cathodic values led to narrower sub-microm ranges (as expected from the larger amounts of the electrogenerated hydroxyl catalyst). Thiol-functionalized silica films were deposited more rapidly than the amine ones and, for both of them, permeability to redox probe was found to decrease when increasing the film thickness because of higher resistance to mass transport.

18.
J Colloid Interface Sci ; 300(2): 616-25, 2006 Aug 15.
Artículo en Inglés | MEDLINE | ID: mdl-16777124

RESUMEN

The present work addresses the protolytic charge of montmorillonite, which occurs on the broken-bond sites at the particle edges. The purpose is to overcome the general difficulty arising in potentiometric titration due to coupled side reactions, which severely impede the titrant budget (partial dissolution of the clay and of secondary phases, hydrolysis and readsorption of dissolved species, cation exchange). Batch potentiometric titrations were carried out on the montmorillonite fractions extracted from two bentonites (MX80 and SWy2) to quantify their protolytic charge. The effects of equilibration time (24 h and 7 days), pH from 4 to 10, and ionic strength (0.1 and 0.01 mol L(-1)) were extensively studied for the MX80 sample. Quantification of dissolution was achieved by analysis of the equilibrium solutions for dissolved species and by La(3+) exchange of the readsorbed species. The results clearly show that secondary phases such as iron- or silica-rich minerals contribute to the dissolved species, according to the nature of the raw bentonite. Furthermore, readsorption affects significant amounts of dissolved species. The overconsumption of proton/hydroxide due to dissolution, readsorption, and hydrolysis of dissolved species was evaluated using a self-consistent thermodynamic calculation. The ability of such calculation to correct the raw titration curves in order to extract the titrable surface charge of montmorillonite was evaluated by comparison with the continuous titration procedure. Especially in the alkaline domain, correcting the raw batch titration curves for the measured side reactions failed to reproduce the continuous titration curves. These observations demonstrate the limitations of the batch titration method and the superiority of fast, continuous methods for quantifying the dissociable surface charge of clays.


Asunto(s)
Silicatos de Aluminio , Bentonita/química , Sodio/química , Adsorción , Calibración , Fenómenos Químicos , Química Física , Arcilla , Electrólitos , Concentración de Iones de Hidrógeno , Hidrólisis , Hidróxidos/química , Iones , Potenciometría , Protones , Soluciones , Difracción de Rayos X
19.
Biophys J ; 90(7): 2612-21, 2006 Apr 01.
Artículo en Inglés | MEDLINE | ID: mdl-16415062

RESUMEN

Long-range electrostatic forces substantially influence bacterial interactions and bacterial adhesion during the preliminary steps of biofilm formation. The strength of these forces depends strongly on the structure of the bacterium surfaces investigated. The latter may be addressed from appropriate analysis of electrophoretic mobility measurements. Due to the permeable character of the bacterium wall and/or surrounding polymer layer, bacteria may be regarded as paradigms of soft bioparticles. The electrophoretic motion of such particles in a direct-current electric field differs considerably from that of their rigid counterparts in the sense that electroosmotic flow takes place around and within the soft surface layer. Recent developments of electrokinetic theories for soft particles now render possible the evaluation of the softness degree (or equivalently the hydrodynamic permeability) from the raw electrokinetic data. In this article, the electrophoretic mobilities of three Shewanella strains (MR-4, CN32, and BrY) presenting various and well-characterized phenotypes of polymer fringe are reported over a wide range of pH and ionic strength conditions. The data are quantitatively analyzed on the basis of a rigorous numerical evaluation of the governing electrostatic and hydrodynamic equations for soft particles. It is clearly shown how the peculiar surface structures of the bacteria investigated are reflected in their electrohydrodynamic properties.


Asunto(s)
Electroforesis/métodos , Shewanella/metabolismo , Adhesión Bacteriana , Fenómenos Fisiológicos Bacterianos , Electrólitos , Campos Electromagnéticos , Electrofisiología , Concentración de Iones de Hidrógeno , Iones , Cinética , Modelos Químicos , Modelos Estadísticos , Concentración Osmolar , Permeabilidad , Polímeros/química , Electricidad Estática , Propiedades de Superficie , Agua
20.
J Colloid Interface Sci ; 296(2): 614-23, 2006 Apr 15.
Artículo en Inglés | MEDLINE | ID: mdl-16236304

RESUMEN

The distribution of edge and basal surface areas of phyllosilicate particles is an essential parameter for understanding the interaction mechanisms at solid/gas or solid/liquid interfaces. Among the techniques proposed to determine the geometrical heterogeneities of flat solids, low-pressure argon adsorption and AFM analysis are the most promising to derive the weight-averaged values of specific surface areas. A series of publications have recently been dedicated to the combination of both methods showing the correlation between the two approaches. As obtaining a large set of high-resolution AFM images is time-consuming, it is necessary to test the ability of AFM routine analysis to derive surface areas and aspect ratio systematically and statistically, with all possible experimental and instrumental artefacts. In the present study, the expected agreement was found between AFM and argon adsorption determination for total, basal, and edge-specific surface areas of nonswelling clay minerals, except for one kaolinite, which is very heterogeneous in size. In addition, it was observed that for a given sample, individual particles present similar shapes, whatever their size, making it possible to derive a statistical relationship between AFM basal and total surface areas. On the basis of the obtained results, recommendations are given to derive accurate edge, basal, and total specific surface areas of phyllosilicates by combining conventional gas adsorption (nitrogen BET) and routine AFM techniques.

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