Oppositely Charged Nanoparticles Research Articles

Colloidal Clusters and Networks Formed by Oppositely Charged Nanoparticles with Varying Stiffnesses.

Colloidal clusters and gels are ubiquitous in science and technology. Particle softness has a strong effect on interparticle interactions; however, our understanding of the role of this factor in the formation of colloidal clusters and gels is only beginning to evolve. Here, we report the results of experimental and simulation studies of the impact of particle softness on the assembly of clusters and networks from mixtures of oppositely charged polymer nanoparticles (NPs). Experiments were performed below or above the polymer glass transition temperature, at which the interaction potential and adhesive forces between the NPs were significantly varied. Hard NPs assembled in fractal clusters that subsequently organized in a kinetically arrested colloidal gel, while soft NPs formed dense precipitating aggregates, due to the NP deformation and the decreased interparticle distance. Importantly, interactions of hard and soft NPs led to the formation of discrete precipitating NP aggregates at a relatively low volume fraction of soft NPs. A phenomenological model was developed for interactions of oppositely charged NPs with varying softnesses. The experimental results were in agreement with molecular dynamics simulations based on the model. This work provides insight on interparticle interactions before, during, and after the formation of hard-hard, hard-soft, and soft-soft contacts and has impact for numerous applications of reversible colloidal gels, including their use as inks for additive manufacturing.

Single-step generation of double emulsions in aqueous two-phase systems

This communication presents a simple yet straightforward method for preparing water-in-water-in-water particle-stabilized double emulsions, also known as Pickering double emulsions. The approach involves using oppositely charged nanoparticles (OCNPs) in two distinct fluid phases, promoting self-assembly and the formation of aggregates with varying sizes and compositions. By enhancing the interfacial area through the adsorption of aggregates at the interface, this method increases the Gibbs detachment energy of particles between the two aqueous phases, forming stable double emulsions. Furthermore, we investigated the impact of the molecular weight of polyethylene oxide and dextran in the respective fluid phases and the mass ratio (M) of the OCNPs on double emulsion formation. The results demonstrate that the molecular weight of the polymers used in the aqueous phase is a critical parameter influencing the structural formation of the emulsion and the generation of double emulsions. Consequently, double emulsions are formed when equal molecular weight polymer mixtures are employed at an appropriate M, with the dispersed phase placed in the highly viscous continuous phase. The proposed method offers a one-step synthesis process, enabling easy preparation, and exhibits excellent stability for at least 30 days. This study represents the first reported approach for the one-step synthesis of multiple emulsions in an aqueous two-phase system utilizing a Pickering emulsion template.

Droplet-Bijel-Droplet Transition in Aqueous Two-Phase Systems Stabilized by Oppositely Charged Nanoparticles: A Simple Pathway to Fabricate Bijels.

We demonstrate a novel yet straightforward methodology of stabilizing aqueous two-phase systems (ATPS) using oppositely charged nanoparticles (OCNPs). We employ commercial-grade, Ludox, OCNPs to induce self-assembly. This self-assembly route promotes the stronger adsorption of nanoparticles at the water-water interface by triggering the formation of 2D and 3D aggregates of varying sizes and shapes. The interplay of this size and shape promotes stability due to increased Gibbs detachment energy and modulates the resulting cluster adsorption at the interface, thereby the structural state of emulsions. We demonstrate the influence of polymers' and particles' composition on the structural transformation from droplet-bijel-droplet using a phase diagram. For the first time, such a structural transition and the single pathway are reported within the domain of ATPS to produce stable bijels or colloidal capsules. It is asserted that the essential condition of three-phase contact angle (θ) = 90° to favor the formation of bijels can be established by selecting a suitable experimental condition using a phase diagram without employing any complicated surface modification procedures reported in the literature. Further, the mechanistic route favoring the formation of bijels and emulsion droplets at different experimental regimes is presented based on the empirical study using turbidity and zeta potential measurements. These studies reveal that the formation of bijels will be most favored when the parameter M (ratio of weight fraction of positively charged nanoparticles to negatively charged nanoparticles) is chosen between 0.7 and 4. It is intriguing to note the fact that, while the droplets stabilized by OCNPs have shown good resilience under high centrifugal action, the bijels produced in this way continued to remain stable for a long time, offering a facile route to prepare the bijels with a hierarchical bicontinuous network structure.

NanoTiO2@DNA complex: a novel eco, durable, fire retardant design strategy for cotton textiles

A strategy for the design of cotton flame retardant coatings is described, exploiting the natural intumescent formulation of nucleic acids, the intrinsic thermal inertia of TiO2 ceramic phase and the strong affinity that TiO2 nanoparticles shows for amphiphilic biomolecules (e.g. proteins, nucleic acids) and hydrophilic substrates. Two different self-assembled TiO2@DNA systems are obtained by mixing two opposite charged TiO2 nanoparticles suspensions with DNA solution. The colloidal behavior of separate and mixed phases was investigated, as well as the morphological, chemical structure and thermal properties of resulting coatings, in order to make some hypothesis on the observed synergic effects. Scanning electron microscopy (SEM) and Attenuated Total Reflectance (ATR) spectroscopy demonstrated the homogeneous distribution of nano-TiO2@DNA based coatings on the treated fabrics. The washing fastness tests evidenced the highly improved performance of hybrid coatings if compared with DNA alone. The flammability and cone calorimetry test results confirmed this positive synergy that resulted quite effective in slowing down (or even blocking) the propagation of a flame within the treated substrates and in improving the resistance of the fabrics to the applied heat flux, these latter leaving increased residues at the end of the test.

Existence of a Precipitation Threshold in the Electrostatic Precipitation of Oppositely Charged Nanoparticles.

Oppositely charged nanoparticles precipitate rapidly only at the point of electroneutrality, wherein their charges are macroscopically compensated. We investigated the aggregation and precipitation of oppositely charged nanoparticles at concentrations ranging from 10 to 10-3 mm (based on gold atoms) by using UV/Vis measurements. We employed solutions of equally sized (4.6 nm) gold nanoparticles, which were functionalized and stabilized with either positively or with negatively charged alkanethiols. Results showed that oppositely charged nanoparticles do not precipitate if their concentration is below a certain threshold even if the electroneutrality condition is fulfilled. This finding suggests a universal behavior of chemical systems comprising oppositely charged building blocks such as ions and charged nanoparticles.

Existence of a Precipitation Threshold in the Electrostatic Precipitation of Oppositely Charged Nanoparticles

AbstractOppositely charged nanoparticles precipitate rapidly only at the point of electroneutrality, wherein their charges are macroscopically compensated. We investigated the aggregation and precipitation of oppositely charged nanoparticles at concentrations ranging from 10 to 10−3 mm (based on gold atoms) by using UV/Vis measurements. We employed solutions of equally sized (4.6 nm) gold nanoparticles, which were functionalized and stabilized with either positively or with negatively charged alkanethiols. Results showed that oppositely charged nanoparticles do not precipitate if their concentration is below a certain threshold even if the electroneutrality condition is fulfilled. This finding suggests a universal behavior of chemical systems comprising oppositely charged building blocks such as ions and charged nanoparticles.

Insight on Methane Foam Stability and Texture via Adsorption of Surfactants on Oppositely Charged Nanoparticles.

We report the phase behavior of a dispersion of alumina-coated silica nanoparticles in the presence of an anionic surfactant (sodium fatty alcohol polyoxyethylene ether sulfate), and then describe the influence of surfactant/nanoparticle concentration ratio on the stability of methane foam as a potential fluid for enhanced oil recovery application. The surface tension of the methane/aqueous phase interface, surface charge, and size of the particle aggregates and amount of surfactant adsorption were characterized as a function of surfactant/nanoparticle ratio. Five adsorption stages, which are described in terms of the extent and type of the surfactant coverage on the nanoparticle surface, explain the behavior of the solution at different surfactant/nanoparticle ratios. The static foam generation experiments were conducted to monitor the variation of the foam stability and texture over the defined adsorption stages. The surface tension trends illustrate that the affinity of nanoparticles for the gas-liquid interface is strongly affected by the adsorption extent of AES molecules on the particle surface. At high surfactant/nanoparticle ratio, the adsorbed surfactant bilayer causes a high hydrophilicity of the particles that significantly pushed the particles away from the gas-liquid interface. At the most hydrophobic state of the particles which occurred at the ratio of 0.2, the foam structure collapsed quickly. The most stable foam with fine texture was found at surfactant/nanoparticle ratio less than 0.008 at which the particles are partially covered with surfactants and have smaller aggregate size. The findings provide a better understanding of the interaction between oppositely charged nanoparticle/surfactant pairs and how that interaction affects foam stability. It is demonstrated that substitution of absolute concentration by surfactant/nanoparticle ratio can truly govern the foam stability and texture. The results can be beneficial to predict the foam behavior in its numerous applications and whether interactions will be synergistic, antagonistic, or neutral.

Doubly pH Responsive Emulsions by Exploiting Aggregation of Oppositely Charged Nanoparticles and Polyelectrolytes.

We present a simple and modular approach to realize highly stable pH responsive Pickering emulsion from mixtures of commercially available oppositely charged nanoparticle and polyelectrolyte. While highly charged nanoparticles and polyelectrolytes when used solely do not stabilize emulsions, we show that the electrostatic attraction between oppositely charged nanoparticles and polyelectrolytes can be exploited to formulate emulsions with long-term stability of up to 8 months. The Ludox CL nanoparticles and poly(4-styrenesulfonate) sodium salt (PSS) when dispersed in aqueous solution at pH 2-11 form particle polyelectrolyte complexes (PPCs) due to heteroaggregation. These complexes are effective in stabilizing oil-in-water Pickering emulsions. We demonstrate that this is due to the formation of weakly charged complexes that are surface active and hence readily adsorbed to the oil-water interface created during emulsification. We show that the composition of nanoparticles and polyelectrolytes in the mixture as well as the pH can be tuned to control the average diameter of the emulsions droplets. Immediate destabilization and doubled responsiveness of the emulsions stabilized by particle polyelectrolyte complexes are illustrated by changing the pH of the stable emulsions formed at intermediate pH to either 1 or 13. The aggregation behavior of nanoparticle-polyelectrolyte mixtures and the effect of various parameters such as mixing fraction, pH, and energy input on the formation of Pickering emulsions is discussed. Furthermore, we show that the formation of near charge neutral aggregates that exhibit optimal wetting conditions is a requirement to accomplish emulsion formation. The visualization of particle polyelectrolyte complexes around the emulsion droplets, their morphology prior to emulsification, and their wetting properties are also investigated to elucidate the mechanism of emulsification.

Controllable Bulk Heterojunction Morphology by Self-Assembly of Oppositely Charged Nanoparticles

Using kinetic Monte Carlo simulations of a simple coarse-grained model, we demonstrate that the self-assembly of oppositely charged nanoparticles is a promising approach to design efficient bulk heterojunction (BHJ) solar cells. Simulations are performed starting from a random configuration of oppositely charged nanoparticles in solution for a range of concentrations. Interconnected percolated morphologies form at high nanoparticle concentrations, when the aggregate growth ceases after certain time. If only Coulombic interactions are present, the observed morphologies have very high interfacial area but too small domain size, whereas optimum values of both the interfacial area and domain size are desired for BHJ. We therefore propose and establish that an additional hydrophobic attraction between nanoparticles of same type is desired to obtain the ideal BHJ morphology. We also discuss the effects of solvent dielectric constant and the size- and charge-asymmetry of nanoparticles, which may provide addition...

Multidrug encapsulation within self-assembled 3D structures formed by biodegradable nanoparticles

Polymer nanoparticles (NPs) have recently attracted increasing attention and represent one of the main and important novelties in nanomedicine. In particular, they exhibit several advantages like the ability to tailor and sustain the release of hydrophobic drugs, high biocompatibility and degradability, together with the possibility to be highly cell selective. However, the usage of NPs in several diseases can be limited by their route of administration: in fact their diffuse distribution in tissues and organs does not allow to address them specifically in the target situ limiting therapeutic outcome and increasing potential side effects. In this work we studied the self-assembly of opposite charged polymer nanoparticles able to retain aqueous solutions, with the aim of creating self-assembled macrostructures that can release both hydrophobic and hydrophilic compounds. NPs were synthesized with a two-steps process starting from ε-caprolactone and hydroxyethyl methacrylate to create biodegradable macromonomers which were then co-polymerized in an emulsion polymerization with methacrylic acid and either a positive charged surfmer (HEMA-Ch+) or a negative one (HEMA-SO3−). The feasibility to assemble these NPs into macrostructures was studied and the structures of the final products as well as their ability to release mimetic drugs were evaluated.

Silica-coating as protective shell for the risk management of nanoparticles

Nanoparticles (NPs) surface functionalization with silica (SiO2) has attracted high attention due to hydrophilicity, biocompatibility, chemical and thermal stability of silica. The present work is addressed to the production and characterization of SiO2-coatings on titanium dioxide (TiO2) and silver (Ag) NPs dispersed in aqueous solutions (commercial nanosols) with the aim to manage the potential risk that such NPs could generate in occupational exposure scenarios. A colloidal approach, based on principles of heterocoagulation in which opposite charged NPs are forced to coagulate in hierarchical structures, imposed by their relative size and weight ratio, was followed. The results were compared with a chemical approach, based on nucleation of silica phase from silica precursor solutions on the surfaces of TiO2 or Ag NPs seeds. In order to increase the adhesion of silica on TiO2 and Ag surfaces, heterocoagulated sols were spray-dried and subsequently redispersed in water to check the feasibility of such approach at industrial level. Physicochemical properties such as zeta potential, electrical conductivity, particle-size distribution, specific surface area and morphology of the samples produced with different SiO2:TiO2 and SiO2:Ag weight ratios were collected and compared. Indirect evidences of silica coating were obtained.

Dissociation of hydrophobic and charged nano particles in aqueous guanidinium chloride and urea solutions: A molecular dynamics study

It has been a long history that urea and guanidinium chloride (GdmCl) are used as agents for denaturing proteins. The underlying mechanism has been extensively studied in the past several decades. However, the question regarding why GdmCl is much stronger than urea has seldom been touched. Here, through molecular dynamics simulations, we show that a 4 M GdmCl solution is more able than 7 M urea solution to dissociate both hydrophobic and charged nano-particles (NP). Both urea and GdmCl affect the NPs' aggregation through direct binding to the NP surface. The advantages of GdmCl originate from the net charge of bound guanidinium ions which can generate a local positively charged environment around hydrophobic and negatively charged NPs. This effective coating can introduce Coulombic repulsion between all the NPs. Urea shows certain ability to dissociate hydrophobic NPs. However, in the case of charged NPs, urea molecules located between two opposite-charged NPs will form ordered hydrogen bonds, acting like "glue" which prevents separation of the NPs. Although urea can form hydrogen bonds with either hydrophilic amino acids or the protein backbone, which are believed to contribute to protein denaturation, our findings strongly suggest that this property does not always contribute positively to urea's denaturation power.

Modulating Layer-by-Layer Assembly of Oppositely Charged Nanoparticles Using a Short Amphiphilic Molecule

Layer-by-layer (LbL) assembly of silica (SiO2) and titania (TiO2) nanoparticles leads to the generation of multifunctional thin films with useful properties. However, favorable film growth for these all-nanoparticle LbL thin films occurs in a narrow pH range. In this work, we widen the processing window of TiO2/SiO2 LbL films by introducing a small amphiphilic molecule, hexylamine (HA), into SiO2 nanoparticle suspensions. Film thickness measurements show that significantly thicker LbL films are obtained after introducing HA into SiO2 nanoparticle suspensions. The zeta potential of SiO2 nanoparticles and that of LbL films are characterized to investigate the role of HA in LbL film assembly. Furthermore, quartz crystal microbalance (QCM) measurements are used to monitor the real-time assembly of LbL films. Our results indicate that HA in SiO2 nanoparticle suspension widens the processing window of LbL assembly by suppressing the negative surface charge of SiO2 nanoparticles and, at the same time, inducing complete charge inversion of LbL films, of which the outermost layer is TiO2 nanoparticles. These two factors lead to the enhanced adsorption of SiO2 nanoparticles and to the formation of TiO2/SiO2 LbL films over a wide pH range. This new approach of using a short amphiphilic molecule is a convenient way of generating all-nanoparticle LbL films over a wide processing window.

Mechanism of the Cooperative Adsorption of Oppositely Charged Nanoparticles

Quartz crystal microbalance experiments were performed to study the kinetics of surface adsorption from solutions containing oppositely charged nanoparticles. A theoretical model was developed according to which formation of dense nanoparticle (NP) monolayers is driven by a cooperative process, in which the already-adsorbed NPs facilitate adsorption of NPs from solution. The kinetic rate constants change with the NP solution concentration and can be used to backtrack adsorption free energies. These energies agree with the predictions of a simple DLVO model.

Size Selection During Crystallization of Oppositely Charged Nanoparticles

Opposites attract (selectively): Oppositely charged nanoparticles characterized by different size distributions form 3D supracrystals (see figure) only if the distributions overlap. Crystal quality decreases rapidly with decreasing degree of overlap, and, irrespective of the ratio of particle diameters/charges, no crystals are observed for non-overlapping distributions.

Cover Picture: Size Selection During Crystallization of Oppositely Charged Nanoparticles (Chem. Eur. J. 9/2009)

AbstractOppositely charged nanoparticles characterized by different size distributions can form 3D supracrystals. In their Communication on page 2032 ff., Grzybowski et al. come to the conclusion that, from both the experimental data and the simulations, the growth of 3D crystals is hindered by entropic effects, owing to finite nanoparticle polydispersities.magnified image

Precipitation of Oppositely Charged Nanoparticles by Dilution and/or Temperature Increase

Mixtures of oppositely charged nanoparticles (NPs) exhibit anomalous solubility behavior and precipitate either upon dilution or upon temperature increase. Precipitation is reversible and can be explained by a thermodynamic model that accounts for changes in the electrostatic interactions due to the adsorption/desorption of counterions from the surface of the NPs. Specifically, decreasing the salt concentration via dilution or increasing the temperature causes dissociation of counterions from the NP surfaces, increasing the magnitude of electrostatic interactions between NPs and resulting in their precipitation. Model predictions of NP solubility are in quantitative agreement with the experimental observations. Such predictions are of practical importance for the preparation of "patchy" electrostatic coatings and ionic-like NP supracrystals.

Ionic-like Behavior of Oppositely Charged Nanoparticles

Mixtures of oppositely charged nanoparticles of various sizes and charge ratios precipitate only at the point of electroneutrality. This phenomenon-specific to the nanoscale and reminiscent of threshold precipitation of ions-is a consequence of the formation of core-and-shell nanoparticle aggregates, in which the shells are composed of like-charged particles and are stabilized by efficient electrostatic screening.

Phase Behavior of Mixtures of Oppositely Charged Nanoparticles: Heterogeneous Poisson−Boltzmann Cell Model Applied to Lysozyme and Succinylated Lysozyme

We study the phase behavior of mixtures of oppositely charged nanoparticles, both theoretically and experimentally. As an experimental model system we consider mixtures of lysozyme and lysozyme that has been chemically modified in such a way that its charge is nearly equal in magnitude but opposite in sign to that of unmodified lysozyme. We observe reversible macroscopic phase separation that is sensitive not only to protein concentration and ionic strength, but also to temperature. We introduce a heterogeneous Poisson-Boltzmann cell model that generally applies to mixtures of oppositely charged nanoparticles. To account for the phase behavior of our experimental model system, in addition to steric and electrostatic interactions, we need to include a temperature-dependent short-ranged interaction between the lysozyme molecules, the exact origin of which is unknown. The strength and temperature dependence of the short-ranged attraction is found to be of the same order of magnitude as that between unmodified lysozyme molecules. The presence of a rather strong short-ranged attraction in our model system precludes the formation of colloidal liquid phases (or complex coacervates) such as those typically found in mixtures of globular protein molecules and oppositely charged polyelectrolytes.