Fulvic acids concentration and pH influence on the stability of hematite nanoparticles in aquatic systems

In aquatic systems, fulvic acids (FAs) are expected to play key roles on the stability and aggregation behavior of manufactured nanoparticles (NPs). The exact conditions under which aggregation or dispersion occurs will depend on the nanoparticle surface charge properties, FAs concentration as well as solution conditions, such as pH and ionic strength. The systematic calculation of stability (aggregation versus disaggregation) diagrams is therefore a key aspect in the prediction of the environmental fate and behavior of manufactured nanoparticles in aquatic systems. In this study, the responses to changes in pH and FAs concentrations on the resulting surface charge of purified iron oxide nanoparticles (53nm nominal diameter) is investigated. By adjusting the pH, different nanoparticle surface charge electrostatic regions are found, corresponding to positively, neutral, and negatively charged nanoparticle solutions. For each situation, the adsorption of negatively charged FAs at variable concentrations is considered by analyzing surface charge modifications and calculating experimental kinetics aggregation rates. Results show that, under the conditions used, and range of FAs environmental relevant conditions, the nanoparticle aggregation process is promoted only when the nanoparticle positive surface charge (solution pH less than the charge neutralization point) is compensated by the adsorption of FAs. In all the other cases, FAs adsorption and increase of FAs concentration are expected to promote not only the NPs stabilization but also the disaggregation of NPs aggregates. In addition, our study suggest that very low concentrations of FAs >0.1mg/l are sufficient to rapidly stabilize iron hydroxide NPs solutions at concentration <5mg/

Salt concentration influence on the efficiency of two cationic polymeric flocculants

The influence of the increase of the solution ionic strength on the flocculation of charged latex particles in the presence of cationic polymers is reported. Empirical flocculation rate constants are experimentally determined using particle counting and for two cationic polymers, one linear and the second with two branches. Comparisons are made with a solution containing monovalent salt only at different ionic concentrations in the absence of polymers. In all cases, polymer-induced flocculation is significantly more efficient than charge screening effects using salt only. Analysis of zeta potential measurements indicates that the charge neutralization and surface charge variations dictate the stability of the latex suspensions. Moreover, the addition of a small amount of salt in the polymer-particle mixtures results in a dramatic decrease of the polymer efficiency which is more pronounced for the linear polymeric flocculant. By increasing further the ionic strength, the rates of polymer flocculation are found to increase again but remain smaller than in the absence of sal

Simulations and scattering functions of polyelectrolyte-macroion complexes

Using Monte Carlo simulations of complex formation between a polyelectrolyte chain and an oppositely charged macroion, we calculated the scattering function of the polyelectrolyte chain. We investigated the case of the isolated polyelectrolyte chain and studied the effect and influence of key parameters such as the ionic concentration of the solution, polyelectrolyte length and intrinsic rigidity on the scattering function. Then, we focused on the polyelectrolyte-macroion complex by calculating the structure factor S(q) of the adsorbed polyelectrolyte chain. Typical conformations ranging from coils, extended chains to solenoids are revealed and the corresponding S(q) analysed. The effects of ionic concentration, chain length and intrinsic rigidity and relative size ratio between the polyelectrolyte and the macroion are investigated. Important effects on the structure factor of the adsorbed polyelectrolyte are observed when the macroion is partially or totally wrapped by the polyelectrolyte. Distance correlations between the polyelectrolyte monomer positions at the surface of the macroion induce the formation of peaks in the fractal regime of S(q). For semiflexible chains, when solenoid conformations are observed, the position of the peaks in the fractal regime corresponds directly to the separation distance between the turns. The formation of a protruding tail in solution is also observed through the formation in the fractal regime of a linear domai

The many facets of polyelectrolytes and oppositely charged macroions complex formation

A review. Various models of the complex formation between polyelectrolyte chains and oppositely charged macroions are reviewed. In recent years, a great deal of knowledge of the multitude of possible polyelectrolyte conformations at the macroion surface has been accumulated, which consequently has led to increasing interest in using such complexes in the design of nanomaterials. This review focuses on key studies relating to the effects of various physico-chem. parameters on complex formation and areas for future research are identified

Towards a better understanding on agglomeration mechanisms and thermodynamic properties of TiO2 nanoparticles interacting with natural organic matter

Interaction between engineered nanoparticles and natural organic matter is investigated by measuring the exchanged heat during binding process with isothermal titration calorimetry. TiO2 anatase nanoparticles and alginate are used as engineered nanoparticles and natural organic matter to get an insight into the thermodynamic association properties and mechanisms of adsorption and agglomeration. Changes of enthalpy, entropy and total free energy, reaction stoichiometry and affinity binding constant are determined or calculated at a pH value where the TiO2 nanoparticles surface charge is positive and the alginate exhibits a negative structural charge. Our results indicate that strong TiO2-alginate interactions are essentially entropy driven and enthalpically favorable with exothermic binding reactions. The reaction stoichiometry and entropy gain are also found dependent on the mixing order. Finally correlation is established between the binding enthalpy, the reaction stoichiometry and the zeta potential values determined by electrophoretic mobility measurements. From these results two types of agglomeration mechanisms are proposed depending on the mixing order. Addition of alginate in TiO2 dispersions is found to form agglomerates due to polymer bridging whereas addition of TiO2 in alginate promotes a more individually coating of the nanoparticles.Comment: 30 pages, 6 figures, 11 figures in S

Dielectric discontinuity effects on the adsorption of a linear polyelectrolyte at the surface of a neutral nanoparticle

The formation of complexes between nanoparticles and polyelectrolytes is a key process for the control of the reactivity of manufd. nanoparticles and rational design of core shell nanostructures. In this work, we investigate the influence of the nanoparticle dielec. const. on the adsorption of a linear charged polymer (polyelectrolyte) at the surface of a neutral nanoparticle. The polyelectrolyte linear charge d., as well as the image charges in the nanoparticle due to the dielec. discontinuity, is taken into account. Monte Carlo simulations are used to predict the adsorption/desorption limits and system properties. Effects of the nanoparticle size and polyelectrolyte length are also investigated. The polyelectrolyte is found adsorbed on the nanoparticle when the dielec. const. of the nanoparticle is greater than the dielec. const. of the medium. Attractive interactions induced by the presence of opposite sign image charges are found strong enough to adsorb the polyelectrolyte showing that the reaction field contribution has to be considered. The affinity between the polyelectrolyte and the nanoparticle is found to increase in magnitude by increasing the nanoparticle size and dielec. const. The reaction field magnitude is also found to depend in a nonlinear way from the polyelectrolyte length

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 dielec. discontinuity effects on the charging process of a spherical nanoparticle (NP) have been investigated. It is well known that electrostatic repulsion between charges on neighboring sites tends to decrease the effective charge of a NP. The situation is more complicated close to a dielec. breakdown, since here a charged site is not only interacting with its neighbors but also with its own image charge and the image charges of all its neighbors. Coexistence of opposite charges, titrn. 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 titrn. site distribution at the solid/soln. 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-liq. 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 dielec. const. on Coulomb interactions are counterbalanced by the reaction field and in this case, the dielec. breakdown has no significant effect on the charging process. This is not the case in patch distributions, where the dielec. breakdown plays a crucial role in the charging process

Design and characterization of protein-quercetin bioactive nanoparticles

<p>Abstract</p> <p>Background</p> <p>The synthesis of bioactive nanoparticles with precise molecular level control is a major challenge in bionanotechnology. Understanding the nature of the interactions between the active components and transport biomaterials is thus essential for the rational formulation of bio-nanocarriers. The current study presents a single molecule of bovine serum albumin (BSA), lysozyme (Lys), or myoglobin (Mb) used to load hydrophobic drugs such as quercetin (Q) and other flavonoids.</p> <p>Results</p> <p>Induced by dimethyl sulfoxide (DMSO), BSA, Lys, and Mb formed spherical nanocarriers with sizes less than 70 nm. After loading Q, the size was further reduced by 30%. The adsorption of Q on protein is mainly hydrophobic, and is related to the synergy of Trp residues with the molecular environment of the proteins. Seven Q molecules could be entrapped by one Lys molecule, 9 by one Mb, and 11 by one BSA. The controlled releasing measurements indicate that these bioactive nanoparticles have long-term antioxidant protection effects on the activity of Q in both acidic and neutral conditions. The antioxidant activity evaluation indicates that the activity of Q is not hindered by the formation of protein nanoparticles. Other flavonoids, such as kaempferol and rutin, were also investigated.</p> <p>Conclusions</p> <p>BSA exhibits the most remarkable abilities of loading, controlled release, and antioxidant protection of active drugs, indicating that such type of bionanoparticles is very promising in the field of bionanotechnology.</p