The effect of metallic cations on the electrophoretic properties of a pretreatedHevea latex

High-ammonia latex concentrate prepared from doubly-centrifuged fieldHevea latex was exhaustively dialysed to remove any residual water-soluble non-rubber constituents. The electrophoretic mobilities of the dialysed latex in the presence of various metallic cations were investigated as a function of electrolyte concentration. The mobility decreased with increasing concentration of the cations Na⁺, Ba²⁺, Mg²⁺ and Ca²⁺ in a manner consistent with the effect of simple electrolyte on compression of the electric double layer. Anomalous behaviour was noted for the divalent ion copper, in that it reversed the charge of the latex particles at a concentration even lower than that of uranyl ions. Multivalent cations (lanthanum, cerium and thorium) had a profound influence on the latex particles where very low charge reversal concentrations were observed. It is believed that strong adsorption of hydrolysed species from the metallic ions was responsible for reversing the charge of the originally negative latex particles. These experiments indicated that the efficiency with which the cations reversed the charge of the latex particle surface was in the order: lanthanum > cerium > copper > thorium > uranyl > calcium > magnesium > barium > sodium. The number of cation binding sites on the latex particle surface and the chemical free energies of cation adsorption were calculated. It was found that the interaction of the latex particle with the hydrolysable metallic cations was much more stronger than that with the simple divalent cations and that this intercation was comparable to that of biological surfaces.     

Effect of pressure on electrophoretic mobility of polystyrene latex particles

A capillary electrophoresis system that can apply arbitrary helium gas pressures at both inlet and outlet reservoirs was constructed. The system was used to investigate the effect of pressure on electrophoretic behavior of polystyrene latex particles. The electrophoretic mobility of latex particles was increased with the application of pressure (< 3.0 kgf/cm2). The shrinkage of particle diameter under pressurization was observed using a microscope, however, the magnitude of shrinkage was not enough to explain the increase in electrophoretic mobility. Therefore, the application of pressure might increase the electric charge of the latex particle. Since methanol inhibited the enhancement in the electrophoretic mobility of the latex particles, water might play an important role in increasing mobility.     

Electric and adsorption properties of pharmaceutical polymers. Part I: Electrokinetics of Aquacoat

The characterization of the electrical surface properties of Aquacoat, a polymer latex of great interest in pharmaceutical sciences, is described. The technique used is electrophoresis. Analysis was carried out of the effect of pH, electrolyte and surfactant concentration on the electrophoretic mobility of the latex particles. Increasing the pH of the dispersion medium provokes a monotonous increase in the value of the negative mobility. The electrolytes LiCl, KCl and NaCl give rise to larger mobilities when their concentration in solution is increased up to ca. 10^–3 M, and a similar behavior is found in the presence of Na₂SO₄. The effect of raising the concentration of CaCl₂ is to decrease the absolute value of the mobility as a consequence of double layer compression. Sodium dodecyl sulphate seems to adsorb on the particle surface increasing its negative charge, but when its concentration is close to 10^–3 M saturation of the surface appears to take place, and an approximately constant mobility is suggested by data, whatever the pH of the medium. Finally, the mobility variations with LaCl₃ concentration indicate adsorption of the La³⁺ cation when it is hydrolyzed (pH5), whereas non-hydrolyzed lanthanum has little effect on the particle charge.     

Effect of particle size and natural organic matter on the migration of nano- and microscale latex particles in saturated porous media

In the interest of fully assessing the potential environmental risks linked to "nanolitter," we need to be able to predict the persistence, toxicity, and mobility of engineered nanomaterials in the natural subsurface environment. To examine the effects of particle size and natural organic matter on nanoparticle mobility, laboratory-scale filtration experiments were performed using different sized model nanomaterials (i.e., latex colloids having diameters of 50, 110, and 1500 nm) in the presence and absence of 5.0 mg/L Suwannee River humic acid (SRHA). At low ionic strengths (1-10 mM KCl), an increase in attachment efficiency (alpha) with increasing particle size was observed. This result contrasts with predictions of particle filtration based on attachment in the primary energy minimum of the particle-grain interaction energy profile evaluated using Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The presence of SRHA generally resulted in a decrease in alpha over the range of experimental conditions investigated. Results of particle transport experiments combined with particle characterization measurements suggest that the decrease in colloid attachment in the presence of SRHA is related to the combined influence of the mechanisms of charge stabilization and steric stabilization.     

Near-IR spectroscopy as a method for studying the formation of calcium naphthenate

A method for studying the precipitation of calcium naphthenate particles by means of near-IR spectroscopy is presented. Naphthenic or fatty acids were dissolved in water at high pH (11.2–11.5). Upon addition of a Ca²⁺ solution the nucleation period and particle growth were monitored. The near-IR spectra experience a baseline elevation owing to the formation and growth of calcium naphthenate particles. The resulting change in optical density over time is discussed on the basis of supersaturation, particle sizes, agglomeration, Ca²⁺-to-carboxylic acid ratio and nucleation process. Solubility products, defined as the ion concentration products where no particle growth was detected, were estimated for the calcium soaps. The method showed some quantitative limitations since the particle sizes changed with supersaturation. Smaller particles will have less influence on the optical density and the larger particle will dominate the resulting scattering contribution. However, it is obvious that the method has qualitative value, for example, to study the efficiency of different calcium naphthenate inhibitors.     

Effect of depletion interactions on transport of colloidal particles in porous media

The influence of depletion interactions on the transport of micrometer-sized, negatively charged polystyrene latex particles through porous media was studied by analysis of particle breakthrough curves as a response to short-pulse particle injections to the inlet of a packed column of glass beads. The column outlet latex particle concentration profiles and the total amount of particles exiting the column were determined as a function of the concentration of small, silica nanoparticles in the solution and the bulk flow rate. Because of similar charges, the silica particles do not adsorb to either the latex particles or glass beads and thus induce an attractive depletion force between the latex particles and glass bead collectors. The total column outlet latex particle amount was calculated by integrating the measured breakthrough concentration curve and compared to the known amount of injected particles at the column inlet. It was found that the particle recovery was a decreasing function of the silica nanoparticle concentration and the carrier fluid residence time, and an increasing function of the velocity in the bed. In addition, removing the silica nanoparticles from the flowing solution caused a second outlet peak to appear, suggesting that some of the polystyrene particles were captured in secondary energy wells. The experimental data were interpreted using the predicted potential energy profile between a single particle and a glass bead, which was assumed to consist of electrostatic, van der Waals, and depletion components. The results indicate that secondary energy wells significantly affect particle transport behavior through porous media.     

The effect of acrylic acid amount on the colloidal properties of polystyrene latex

Poly(styrene-co-acrylic acid) (St/AA) latices were prepared by using a batch soap-free emulsion copolymerisation in non-buffered medium. Polymerisation kinetics, followed by gravimetric method, revealed that increasing AA comonomer concentration was directly proportional to the copolymerisation rate, while adding AA comonomer caused a strong decrease of particle size of final St/AA latex particle without affecting the size distribution. Transmission electron microscopy indicated that the particles were monodispersed and spherical in shape irrespective of AA amount used in the investigated range. The colloidal stability of the latices was increased upon increasing the AA concentration; owing to the electrosteric stabilisation originated from AA-rich layer on the particle surface. In addition, electrophoretic mobility of formed particles versus polymerisation conversion exhibited the constancy of the surface charge density during the polymerisation process and was inferred for discussion of the polymerisation mechanism of this system.     

CALCIUM AS POTENTIAL DETERMINING ION IN AQUEOUS CALCITE SUSPENSIONS

Electrokinetic mobility was measured on calcite particles dispersed in aqueous solutions as a function of pH, ion concentration and type (Na⁺, Ca²⁺, CI^-, S0₄ ^2-). Whatever the pH value, experimental results show a good correlation between electrokinetic potential and Ca²⁺ activity. Considering Ca²⁺ as a potential determining ion and using a simple complexation model at the surface, we show that the displacement of the isoelectric point can be attributed to the relative affinity of CO₃ ^2- and Ca²⁺ for the surface.     

Particle morphology of self-hydrolyzed acrylate polymer colloids: A 13C NMR and DSC study

Methyl acrylate polymer colloids can be hydrolyzed self-catalytically by bound strong acid surface groups derived from the polymerization initiator. The kinetics of hydrolysis were earlier shown to be apparently pseudo-zeroth-order for any given latex, and first order with respect to surface strong acid concentration. A surface reaction zone model was proposed to explain the kinetics. This model leads to the prediction that the polymer particles will possess a core-shell morphology after some hydrolysis has occurred. This study employs ¹³C NMR spectroscopy to investigate the particle morphology in the wet latex, a new application for this method. The temperature dependence of the ¹³C NMR integrated intensities at various levels of hydrolysis provides strong evidence that the particles do possess core-shell morphology, and that the shell is composed of PAA/PMA copolymer. This shell is swollen and plasticized by water, resulting in greatly enhanced segmental mobility of the polymer chains as evidenced by marked narrowing of the NMR lines. Thermal measurements alone cannot distinguish particle morphology because PMA appears to be somewhat compatible with its partially hydrolyzed analog at the temperatures of measurement.     

Modeling of metal-humate complexation based on the mean molecular weight and charge of humic substances: Application to Eu(III) humate complexes using ion exchange

A general model, the so called Mean Molecular Weight Model (MMWM), of complexation of metal cations (Me^z+) with macromolecular polyanions of humic acid (HA^p-) is proposed. The model is based on the results of previous studies of the electrophoretic mobility of humate complexes and assumes that the complexation proceeds by consecutive neutralization of the dissociated carboxyl groups of the central polyanion HA^p- with Me^z+ cations. It reflects the macromolecular character of humic acid, applies molar concentrations of reacting components with equations for stability constants and incorporates also the mean charge of humic macromolecules. The model has been verified with experimental data obtained in the study of complexation of Eu(III) with Aldrich humic acid using ion exchange (Amberlite IR-120), over a broad range of [Eu] to [HA] ratio, at pH 4 and 7.     

Polymer mediated peptide immobilization onto amino-containing N-isopropylacrylamide-styrene core-shell particles

Monodisperse cationic core-shell latex particles have been prepared using a shot polymerization process, with N-(3-aminopropyl)-methacrylamide-hydrochloride (APMH) as the functional monomer. The final latexes were characterized with respect to final polymerization conversion, water soluble polymer formation, particle size and size distribution, surface charge density and electrokinetic properties. Then the covalent grafting of maleic anhydride-alt-methyl vinyl ether (MAMVE) copolymer onto aminated latex particles was investigated. The most efficient conditions to obtain derivatised particles with no alteration of the colloidal stability were to control both polymer amount/latex particles concentration ratio and the mixing method of the two species. The charge inversion of the hydrolysed MAMVE functionalized particles was demonstrated by measuring the electrophoretic mobility as a function of pH. Finally, the covalent binding approach was implemented with peptide-MAMVE conjugates, confirming the great potential of this promising methodology for the preparation of reactive latex particles bearing peptides.     

Effect of electrolyte type on the electrokinetic behavior of sulfonated polystyrene model colloids

Sulfonated polystyrene latex particles were prepared by a two-stage shot-growth emulsion polymerization process in the absence of emulsifier. Sodium styrene sulfonate (NaSS) was used as an ionic co-monomer to produce a series of latex particles with the same particle size but with different surface charge densities. The electrophoretic mobility of this functionalized model colloid was studied in the presence of various types of inorganic electrolytes. The _e curves of these latexes exhibit a pronounced maximum at high electrolyte concentrations: 5·10^–2 M for 11 electrolytes and 10^–2 M for 21 and 12 electrolytes. When a 31 electrolyte (LaCl₃) was used, the electrophoretic mobility changed to positive values at high concentration due to the specific adsorption of lanthanum species. The experimental results for the electrokinetic characterization of these sulfonated polystyrene model colloids suggest that the surface of the particles is covered by a layer of oligomers or polymer chains which shift the shear plane toward the bulk solution, increasing the anomalous surface conductance of the polystyrene microsphere-electrolyte solution interface.     

Calcium-induced aggregation of bovine caseins: effect of phosphate and citrate

The formation of colloidal particles by Ca²⁺ precipitation of whole caseinates in the presence of phosphate (Pi), citrate (Cit), or both of the anions in concentrations found to be effective in previous works was followed comparing the colloidal particle size and the ionic and proteic composition of the precipitates obtained. Ca²⁺ was incorporated to the precipitate and colloidal particles in a different way than Pi, differences which were related to the presence of Pi and/or Cit in the media. A sequential salting-out process due to progressive Ca²⁺ binding to at least two kinds of sites was observed. The precipitation curves were fitted, and the affinity constants and binding site numbers were calculated with a modification of the Farrell’s equation based on the concept of Wyman’s linked functions. Precipitates obtained at low total Ca²⁺ concentrations in different conditions varied their casein composition. Colloidal particles appeared at the beginning of the second salting-out step, in different amount, and in average size according to the presence or absence of Pi and/or Cit in the media. Consideration of these differences showed that Cit favored the formation of bigger colloidal particles, acting especially in the first steps of the casein aggregation and conditioning the mechanism of this process.     

U(VI) mono-hydroxo humate complexation

The complexation of the uranyl ion with humic acid is investigated. The humic acid ligand concentration is described as the concentration of reactive humic acid molecules based on the number of humic acid molecules, taking protonation of functional groups into account. Excess amounts of U(VI) are used and the concentration of the humic acid complex is determined by the solubility enhancement over the solid phase. pH is varied between 7.5 to 7.9 in 0.1M NaClO₄ under normal atmosphere and room temperature. The solubility of U(VI) in absence of humic acid is determined over amorphous solid phase between pH 4.45 and 8.62. With humic acid, only a limited range of data can be used for the determination of the complexation constant because of flocculation or sorption of the humic acid upon progressive complexation. Analysis of the complex formation dependency with pH shows that the dominant uranyl species in the concerned pH range are UO₂(OH)⁺ and (UO₂)₃(OH)₅ ⁺. The complexation constant is evaluated for the humate interaction with the to UO₂(OH)⁺ ion. The stability constant is found to be logβ = 6.94±0.3 l/mol. The humate complexation constant of the uranyl mono-hydroxo species thus is significantly higher than that of the nonhydrolyzed uranyl ion (6.2 l/mol). Published data on the Cm³⁺, CmOH²⁺ and Cm(OH)₂ ⁺ humate complexation are reevaluated by the present approach. The higher stability of the hydrolysis complex is also found for Cm(III) humate complexation.     

[14C]-Cellulase-humic complexes that are stable in soil

[¹⁴C]-Cellulase was extracted from the culture medium ofTrichoderma viride and an attempt made to complex it with humic acid by adsorption. The result showed that the humic acid extracted from soil does not form a stable complex with [¹⁴C]-cellulase. In contrast, the flocculation of humic acid by 0.025M Ca²⁺ in the presence of the cellulase resulted in the formation of stable humic-cellulase complexes. DEAE cellulose chromatography of cellulase-humic complex revealed that cellulase could not be separated from the humic acid. Enzyme activity was only eluted along with humic acid upon increasing gradient concentration from 1.0 to 1.5M NaCl. Furthermore, in order to test its stability, the enzyme-humic complex was incorporated into fresh soil for 90 d. During this period the enzyme-humic complex remained stable. The cellulase-humic complex was then extracted from soil. Fractionation of the extract on DEAE cellulose and G100 sephadex revealed that cellulase activity could not be separated from humic acid and was again eluted in the form of enzyme-humic complex. This confirmed the stability of cellulase-humic complex in soil.     

Adsorption of U(VI) on montmorillonite pillared with hydroxy-aluminum

Hydroxy-aluminum pillared Na-montmorillonite(OH–Al-MT) was prepared for studying sorption of U(VI) in the existence of soluble calcium (Ca²⁺), carbonate ion (CO₃^2?) and humic acid. Various characterizations confirm that hydroxy-aluminum was successfully pillared into Na-montmorillonite (Na-MT). The effects of pH, concentration of Ca²⁺ and CO₃^2? as well as HA on the sorption capacity of Na-MT and OH–Al-MT for U(VI) has been investigated by batch experiments. Additionally, the kinetics, isotherms and thermodynamics of adsorption of U(VI) were discussed in detailed. The study indicates that OH–Al-MT can be a potentially promising low-cost adsorbent for removal of U(VI) in wastewaters.     

Electrophoretic mobility of latex particles: effect of particle size and surface structure

The influence of particle size on the electrophoretic mobility of negatively charged latex particles was examined by a comparison between theory and experiment. Theoretical values for the dependence of the mobility on electrolyte concentration were calculated by a modified White–O’Brian model (Hidalgo-Alvarez et al., Adv. Coll. Interf. Sci. 67 (1996) 1) which enables the consistent calculation of the zeta (ζ) potential. For three polystyrene latexes of different size but similar surface charge density the measured mobilities increased with increasing radius for the electrolyte range under consideration. The theoretical calcalations resulted in a qualitatively correct prediction of the experimental data. The experimental comparison of the mobilities of hydrophobic and hydrophilic particles of similar size and surface charge density lead to the conclusion that hydrophilic surfaces lower the electrophoretic mobility. The same theoretical model was able to describe correctly this observed behavior by assuming a greater distance of the plane of shear. The effect of a spatial distribution of the charges was examined by characterizing an electrosterically stabilized latex. Contrary to all standard latices with surface charges this latex didn't show any mobility maximum as a function of electrolyte concentration.     

Highly selective transport of silver ion through a supported liquid membrane using calix[4]pyrroles as suitable ion carriers

Facilitated transport of silver ion across a supported liquid membrane (SLM) by calix[4]pyrroles, as selective ion carriers, dissolved in kerosene has been investigated. The influences of fundamental parameters affecting the transport of silver ion including ion carrier concentration in the membrane phase, thiosulfate concentration in strip phase, picric acid concentration in the feed phase, stirring speed of aqueous phases, type of membrane solvent and time of transport have been studied. In the presence of thiosulfate as a suitable metal ion acceptor in the strip phase and picrate ion as ion pairing agent in the source phase, transport of silver occurs almost quantitatively after 75 min. The selectivity and efficiency of silver transport from aqueous solution containing Cu²⁺, Mg²⁺, Ni²⁺, Ca²⁺, Zn²⁺, Pb²⁺, Co²⁺, Al³⁺, Hg²⁺, Cd²⁺, Fe³⁺, Fe²⁺ and Cr³⁺ were investigated.     

Surface study on the rubber particles in pretreated Hevea latex system

Summary From centrifuged high-ammonia latex concentrate, a fraction which contains rubber particles of a narrow particle size distribution in a serum phase freed from any water-soluble non-rubber constituents was obtained. The electrophoretic mobility of the dialysed latex particles has been studied as a function of dry rubber content, surface pH and concentration of sodium chloride. The rubber particles were shown to have an amphoteric nature with an isoelectric point at pH 3.8. The electrokinetic study showed that the net negative charge on the rubber particle surface is derived from the carboxyl groups of the adsorbed proteins and the adsorbed long-chain fatty acids. This is in agreement with the infrared data of the rubber film. The surface charge density of the rubber particle at pH > 6 was found to be 1.43 ,µC cm^–2. The stability of the latex is briefly discussed in terms of its surface charge and compared with that of synthetic latices.

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Zusammenfassung Durch Zentrifugieren von stark ammoniakhaltigen Latex-Konzentraten wurde eine Fraktion erhalten, welche Gummiteilchen mit einer engen Teilchengrößenverteilung in einem Serum enthielt, welches frei von wasserlöslichen Nichtgummibestandteilen war. Die elektrophoretische Beweglichkeit der dialysierten Latexteilchen wurde als Funktion des Gummigehaltes, des Oberflächen-pH-Wertes und der Natriumchloridkonzentration gemessen. Die Gummiteilchen verhalten sich amphoter mit einem isoelektrischen Punkt bei pH 3,8. Die Oberflächenladung rührt von Carboxylgruppen adsorbierter Proteine und adsorbierter langkettiger Fettsäuren her. Die Oberflächenladungsdichte bei pH > 6 wurde zu 1,43 ,µC cm^–2 bestimmt. Die Stabilität wird im Zusammenhang mit der Ladungsdichte diskutiert und mit der von synthetischen Latices verglichen.

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With 7 figures and 1 table