Repulsive Electrostatic Interactions Research Articles

Adsorption dynamics, diffusion and isotherm models of poly(NIPAm/LMSH) nanocomposite hydrogels for the removal of anionic dye Amaranth from an aqueous solution

To investigate diffusion model and adsorption mechanism of hydrogel for the removal of anionic dye Amaranth from aqueous solution, poly(N-isopropylacrylamide)(abbreviated as PNIPAm)/clay lithium magnesium silicate hydrate (abbreviated as LMSH) nanocomposite hydrogels with various clay percentage of LMSH/NIPAm (named as NPX hydrogel) were prepared. Adsorption kinetics of NPX samples were investigated under different experimental conditions (including solution pH, initial concentration of Amaranth dye solution and clay percentage of LMSH/NIPAm). Based on the adsorption experiments, adsorption dynamics, diffusion mechanisms and adsorption isotherms of NPX samples in Amaranth solution were analyzed through pseudo first-order model, pseudo second-order model, film diffusion model, intra-particle diffusion model and different isotherm models. The adsorption kinetics showed that in acidic (pH=2) Amaranth solution NPX nanocomposite hydrogel was more effective for the removal of Amaranth dye. With increasing clay percentage of LMSH/NIPAm from 5 to 40wt.%, adsorption capacity of Amaranth dye onto NPX samples decreased due to shrunk pore effect of NPX nanocomposite hydrogels and enhanced electrostatic repulsive interactions between NPX samples and Amaranth molecules. Adsorption dynamics indicated pseudo second-order model was more suitable for the investigated adsorption process. The adsorption rate-controlling step mainly came from film diffusion, but not the only factor. Adsorption isotherm indicated the adsorption process from monolayer adsorption to multilayer adsorption. According to Dubinin-Radushkevich isotherm model (abbreviated as D-R model), the calculated mean free energy implied chemisorption nature between NPX nanocomposite hydrogel and Amaranth. Based on adsorption mechanism of NPX nanocomposite hydrogel on Amaranth established, the conclusion confirms the prospect of NPX nanocomposite hydrogel as effective adsorbent to dispose real dyeing wastewater.

Evidences of Changes in Surface Electrostatic Charge Distribution during Stabilization of HPV16 Virus-Like Particles

The stabilization of human papillomavirus type 16 virus-like particles has been examined by means of different techniques including dynamic and static light scattering, transmission electron microscopy and electrophoretic mobility. All these techniques provide different and often complementary perspectives about the aggregation process and generation of stabilized virus-like particles after a period of time of 48 hours at a temperature of 298 K. Interestingly, static light scattering results point towards a clear colloidal instability in the initial systems, as suggested by a negative value of the second virial coefficient. This is likely related to small repulsive electrostatic interactions among the particles, and in agreement with relatively small absolute values of the electrophoretic mobility and, hence, of the net surface charges. At this initial stage the small repulsive interactions are not able to compensate binding interactions, which tend to aggregate the particles. As time proceeds, an increase of the size of the particles is accompanied by strong increases, in absolute values, of the electrophoretic mobility and net surface charge, suggesting enhanced repulsive electrostatic interactions and, consequently, a stabilized colloidal system. These results show that electrophoretic mobility is a useful methodology that can be applied to screen the stabilization factors for virus-like particles during vaccine development.

Small-Angle Neutron Scattering Study of Interplay of Attractive and Repulsive Interactions in Nanoparticle-Polymer System.

The phase behavior of nanoparticle (silica)-polymer (polyethylene glycol) system without and with an electrolyte (NaCl) has been studied. It is observed that nanoparticle-polymer system behaves very differently in the presence of electrolyte. In the absence of electrolyte, the nanoparticle-polymer system remains in one-phase even at very high polymer concentrations. On the other hand, a re-entrant phase behavior is found in the presence of electrolyte, where one-phase (individual) system undergoes two-phase (nanoparticle aggregation) and then back to one-phase with increasing polymer concentration. The regime of two-phase system has been tuned by varying the electrolyte concentration. The polymer concentration range over which the two-phase system exists is significantly enhanced with the increase in the electrolyte concentration. These systems have been characterized by small-angle neutron scattering (SANS) experiments of contrast-marching the polymer to the solvent. The data are modeled using a two-Yukawa potential accounting for both attractive and repulsive parts of the interaction between nanoparticles. The phase behavior of nanoparticle-polymer system is explained by interplay of attractive (polymer-induced attractive depletion between nanoparticles) and repulsive (nanoparticle-nanoparticle electrostatic repulsion and polymer-polymer repulsion) interactions present in the system. In the absence of electrolyte, the strong electrostatic repulsion between nanoparticles dominates over the polymer-induced depletion attraction and the nanoparticle system remains in one-phase. With addition of electrolyte, depletion attraction overcomes electrostatic repulsion at some polymer concentration, resulting into nanoparticle aggregation and two-phase system. Further addition of polymer increases the polymer-polymer repulsion which eventually reduces the strength of depletion and hence re-entrant phase behavior. The effects of varying electrolyte concentration on the phase behavior of nanoparticle-polymer system are understood in terms of modifications in nanoparticle-nanoparticle and polymer-polymer interactions. The nanoparticle aggregates in two-phase systems are found to have surface fractal morphology.

Influence of the structure on the collapse of poly(N-isopropylacrylamide)-based microgels: an insight by quantitative dielectric analysis.

The collapse of poly(N-isopropylacrylamide)/poly(acrylic acid) semi-interpenetrating polymer network (PNIPAM/PAA SIPN) and poly(N-isopropylacrylamide-co-acrylic acid) (P(NIPAM-co-AA)) microgel suspensions is studied by dielectric spectroscopy in a frequency range from 40 Hz to 110 MHz as a function of temperature. Dielectric measurements show that the structure affects the relaxation behavior of microgels: two relaxations (micro-Brownian motion and interfacial polarization at low frequency and counterion polarization at high frequency) are observed in the SIPN microgel whose charges mainly exist in domains and one relaxation (interfacial polarization) is observed in the copolymer microgel whose charges distribute in the whole network. A dielectric model is proposed to describe the collapsed microgel suspensions, from which some parameters, such as the volume fraction and the permittivity of microgels, were calculated using Hanai's equation. The temperature dependencies of these parameters show that the SIPN microgel has better low-temperature swelling properties and thermal responsiveness. This is caused by different polymer-solvent and electrostatic repulsion interactions in different microgels. Compared with pure PNIPAM, the relationship of volume phase transition temperature (VPTT) is VPTTP(NIPAM-co-AA) > VPTTPNIPAM/PAA SIPN > VPTTPNIPAM, and it is explained from the viewpoint of interaction. Besides, the activation energy data prove that the structure influences the electrical properties of microgels, which is consistent with the results obtained from quantitative dielectric analysis.

Non-monotonic temperature response of polymer mediated interactions.

In a recent publication, Feng et al. [Feng et al., Nat. Mater., 2015, 14, 61] reported a very interesting re-entrant solidification behaviour of colloidal particles in an aqueous solution containing polyethylene oxide (PEO). In this system, a crystalline colloidal phase, which is present at low temperatures, melts to a homogeneous fluid upon increasing the temperature. Further raising the temperature, however, eventually gives rise to a flocculated colloidal phase. Feng et al. proposed that the low-temperature crystalline phase is caused by polymer depletion while, at higher temperature, an increased attraction between polymers and particles leads to bridging attractions, and colloidal flocculation. The intermediate temperature regime sees the colloidal interactions dominated by charge repulsion, giving rise to a fluid phase. In the model by Feng et al., polymers are treated as hard spheres, which interact with the colloids via a phenomenological, temperature dependent potential. In this work, we develop a more detailed polymer density functional treatment, based on a model for aqueous PEO solutions that was originally developed by Karlström [Karlström, J. Phys. Chem., 1985, 89, 4962] for bulk solutions. In this model, monomers are assumed to be in either of two classes of states, labelled A and B, where B is more solvophobic than A. On the other hand, the degeneracy of the B states exceed that of A, causing the population of solvophobic monomers to increase with temperature. If the colloidal particles are also solvophobic, then this model displays the same qualitative temperature response as was observed by Feng et al. That is, at low temperatures, A type monomers predominate and one observes depletion interactions, whereas polymer bridging dominates at higher temperatures, due to the attraction between B-type monomers and the colloidal surface. Interestingly, the intermediate temperature regime is characterized by a polymer mediated interaction between colloids which is repulsive. That is, according to our model the homogeneous fluid phase would form even in the absence of repulsive electrostatic interactions. We emphasize that our model does not rely upon any temperature-dependent interactions. Furthermore, all possible polymer configurations are accounted for, subject to a mean-field Boltzmann weight. Finally, we show that interactions between colloids, mediated by neutral non-grafted polymers, generally follow the trend: attraction ⇒ repulsion (or vanishing interaction) ⇒ attraction as the surface affinity toward monomers proceeds from repulsive to attractive.

Hyperconjugative and Electrostatic Interactions as Anomeric Triggers in Archetypical 1,4-Dioxane Derivatives.

The anomeric effect accounts for the greater thermodynamic stability of axially arranged six-membered heterocycles holding an electronegative substituent at the C1 position. Within a frame of no general consensus, two different theories are typically claimed to justify this effect mostly based on either hyperconjugative or electrostatic factors. Here we report a theoretical-experimental study of the role of both as anomeric triggers in two archetypical 1,4-dioxane derivatives, using a suitable combination of spectroscopic (IR and vibrational circular dichroism) and computational techniques for the analysis of the solvation environment effect in their anomeric choices. VCD and IR spectroscopies are used as conformer-discriminating tools: a detailed analysis of the evolution of the spectral profiles allows assessing the theoretically predicted changes in the experimental α/β ratios when changing the polar solvent, which are fully explained on the basis of an extensive NBO energy partition scheme that provides a detailed view of the role of hyperconjugative and electrostatic interactions as anomeric regulators. Our results suggest that the anomeric equilibrium cannot be described by a single stereoelectronic effect but by the combined contribution of hyperconjugation and electrostatic repulsions, so that the β-anomeric choice in polar solvents is markedly driven by the strong attenuation of electrostatic repulsive interactions that occurs in solution.

Size-controlled and redox-responsive supramolecular nanoparticles.

Control over the assembly and disassembly of nanoparticles is pivotal for their use as drug delivery vehicles. Here, we aim to form supramolecular nanoparticles (SNPs) by combining advantages of the reversible assembly properties of SNPs using host–guest interactions and of a stimulus-responsive moiety. The SNPs are composed of a core of positively charged poly(ethylene imine) grafted with β-cyclodextrin (CD) and a positively charged ferrocene (Fc)-terminated poly(amidoamine) dendrimer, with a monovalent stabilizer at the surface. Fc was chosen for its loss of CD-binding properties when oxidizing it to the ferrocenium cation. The ionic strength was shown to play an important role in controlling the aggregate growth. The attractive supramolecular and repulsive electrostatic interactions constitute a balance of forces in this system at low ionic strengths. At higher ionic strengths, the increased charge screening led to a loss of electrostatic repulsion and therefore to faster aggregate growth. A Job plot showed that a 1:1 stoichiometry of host and guest moieties gave the most efficient aggregate growth. Different stabilizers were used to find the optimal stopper to limit the growth. A weaker guest moiety was shown to be less efficient in stabilizing the SNPs. Also steric repulsion is important for achieving SNP stability. SNPs of controlled particle size and good stability (up to seven days) were prepared by fine-tuning the ratio of multivalent and monovalent interactions. Finally, reversibility of the SNPs was confirmed by oxidizing the Fc guest moieties in the core of the SNPs.

Poly(N,N-dimethylaminoethyl methacrylate) Brushes: pH-Dependent Switching Kinetics of a Surface-Grafted Thermoresponsive Polyelectrolyte.

The temperature-dependent switching behavior of poly(N,N-dimethylaminoethyl methacrylate) brushes in alkaline, neutral, and acidic solutions is examined. A novel microscopic laser temperature-jump technique is employed in order to study characteristic thermodynamic and kinetic parameters. Static laser micromanipulation experiments allow one to determine the temperature-dependent variation of the swelling ratio. The data reveal a strong shift of the volume phase transition of the polymer brushes to higher temperatures when going from pH = 10 to pH = 4. Dynamic laser micromanipulation experiments offer a temporal resolution on a submillisecond time scale and provide a means to determine the intrinsic rate constants. Both the swelling and the deswelling rates strongly decrease in acidic solutions. Complementary experiments using in situ atomic force microscopy show an increased polymer layer thickness at these conditions. The data are discussed on the basis of pH-dependent structural changes of the polymer brushes including protonation of the amine groups and conformational rearrangements. Generally, repulsive electrostatic interactions and steric effects are assumed to hamper and slow down temperature-induced switching in acidic solutions. This imposes significant restrictions for smart polymer surfaces, sensors, and devices requiring fast response times.

Growth of gold nanoparticles at gelatin-silica bio-interfaces

The growth of gold nanoparticles via chemical reduction of HAuCl4 dispersed in gelatin-silicate mixtures was studied. Gelatin leads to densely packed nanoparticles whereas open colloidal aggregates with tight boundaries are formed within silica. Within the bio-hybrid systems, gold species are located within the gelatin-silicate particles and/or within the gelatin phase, depending on the preparation conditions. These various localizations and their impact on the final nanoparticle structure are discussed considering attractive and repulsive electrostatic interactions existing between the three components. These data suggest that bio-hybrid systems are interesting and versatile interfaces to study crystallization processes in confined environments.

Reversible Bacterial Adhesion on Mixed Poly(dimethylaminoethyl methacrylate)/Poly(acrylamidophenyl boronic acid) Brush Surfaces.

A simple and versatile method for the preparation of surfaces to control bacterial adhesion is described. Substrates were first treated with two catechol-based polymerization initiators, one for thermal initiation and one for visible-light photoinitiation. Graft polymerization in sequence of dimethylaminoethyl methacrylate (DMAEMA) and 3-acrylamidebenzene boronic acid (BA) from the surface-bound initiators to form mixed polymer brushes on the substrate was then carried out. The PDMAEMA grafts were thermally initiated and the PBA grafts were visible-light-photoinitiated. Gold, poly(vinyl chloride) (PVC), and poly(dimethylsiloxane) (PDMS) were used as model substrates. X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR), and ellipsometry analysis confirmed the successful grafting of PDMAEMA/PBA mixed brushes. We demonstrated that the resulting surfaces showed charge-reversal properties in response to change of pH. The transition in surface charge at a specific pH allowed the surface to be reversibly switched from bacteria-adhesive to bacteria-resistant. At pH 4.5, below the isoelectric points (IEP, pH 5.3) of the mixed brushes, the surfaces are positively charged and the negatively charged Gram-positive S. aureus adheres at high density (2.6 × 10(6) cells/cm(2)) due to attractive electrostatic interactions. Subsequently, upon increasing the pH to 9.0 to give negatively charged polymer brush surface, ∼90% of the adherent bacteria are released from the surface, presumably due to repulsive electrostatic interactions. This approach provides a simple method for the preparation of surfaces on which bacterial adhesion can be controlled and is applicable to a wide variety of substrates.

Fluorine and sulfur co-doped amorphous carbon films to achieve ultra-low friction under high vacuum

Fluorine and sulfur co-doped amorphous carbon (a-C:S:F) films were synthesized from C2H2 and SF6 plasma mixture, and the bonding states of S and F in films were scrutinized. The a-C:S:F films exhibited a more ordered carbon structure than hydrogenated films. The friction behavior of films was tested against GCr15 bearing steel balls under high vacuum (HV) conditions. Ultra-low steady-state friction coefficient (0.01–0.02) was achieved for a-C:S:F films containing about 2.0 at.% H, depending on the concentrations of S and F in films. Graphite-like transfer layer on the ball surface provided a low-adhesive sliding surface terminated by –CF2- and –CF3 groups. The electrostatic repulsive interaction between the F-terminated transfer layer and the S- and F-terminated carbon structure was probably responsible for the ultra-low friction behavior. Intriguingly, the sp2-C clusters containing ‘thiophene-S’ (–C–S–C–) structure in films might contribute to the low friction when sliding against an highly fluorinated surface. These results demonstrate that the lubricating properties of a-C films in vacuum can be achieved through the S and F co-doping, which is of great significance for developing a-C films as vacuum lubricants.

Counterion condensation on polyelectrolyte chains adsorbed on charged surfaces

Abstract We developed a Monte Carlo systematic study into the effect of counterion condensation on the polyelectrolyte adsorption process on charged surfaces. Polyelectrolyte is modeled as a full-flexible chain whose size is characterized by the equilibrium bond length and the number of monomers per chain. The small anions and cations are explicitly modeled. The adsorption proceeds with a non-trivial counterion condensation degree on the polyelectrolyte chain. When the polyelectrolyte coverage degree on the surface is low, the chain looses most of its counterions (anions), due to their electrostatic repulsion with the negatively charged surface. This effect is more evident when the equilibrium bond length is shorter. Counterions are recondensed as coverage degree increases, and this is attributed to two main energetic reasons: first, the chains adsorbed cause shielding of anion-surface repulsive electrostatic interaction; second, the repulsive interaction between chains adsorbed on the surface is shielded by the condensed counterions on these chains. The amount of polyelectrolyte adsorbed and degree of condensation counterions reaches a plateau as a function of the number of chains added to the simulation box. At this point surface charge is overcompensated in a similar magnitude for the different chain types. However, the adsorbed chains keep most of their condensed counterions when the equilibrium bond length is shorter. Additionally, we study the size effect (number of monomer per chain) on the condensation degree on adsorbed polyelectrolyte. Condensation is highly dependent on a low chain size (low than 60 monomers approximately) since end effects are important. With a higher chain size, counterion condensation and charge reversal show a negligible correlation with chain size.

Dispersion Stability of TiO2-H2O Nanofluids Containing Mixed Nanotubes and Nanosheets

Abstract Titanium dioxide nanotubes (TiNTs) and nanosheets (TiNSs) were synthesized according to the hydrothermal synthesis method. TiO2-H2O binary nanofluids were prepared by dispersing certain amount of both TiNTs and TiNSs in deionized water. Stabilities of nanofluids of different total concentrations were observed visually 1 hour later after preparation to classify stable and unstable nanofluids among nanofluids containing different ratios of TiNTs and TiNSs. Sedimentation heights variations with time were measured to indicate sedimentation velocities of nanoparticles of nanofluids of different concentrations as well. The preliminary results revealed that binary nanofluids stabilities could be improved effectively when concentration ratios of TiNTs to TiNSs are at suitable range compared with TiNTs or TiNSs alone, otherwise stabilities were deteriorated seriously. We consider the phenomenon is possibly concerned with electrostatic repulsion and depletion interactions in binary nanofluids.

Characterization of post-translationally modified peptides by hydrophilic interaction and reverse phase liquid chromatography coupled to quadrupole-time-of-flight mass spectrometry

This work explores the use of both hydrophilic interaction liquid chromatography (HILIC) and reverse phase liquid chromatography (RPLC) for the separation and subsequent characterization of bovine caseinomacropeptide (CMP) phosphopeptides and O-glycopeptides using a quadrupole-time-of-flight (QTOF) mass spectrometer with electrospray ionization. Two neutral, ethylene bridged hybrid (BEH) amide and polyhydroxyethyl aspartamide (PHEA), and a zwitterionic, sulfobetaine (ZIC), stationary phases were used for the HILIC mode, whilst an octadecylsilane (C18) stationary phase was employed for the RPLC separation. Overall, developed HILIC-QTOF method using the ZIC or BEH amide stationary phases resulted to be the most efficient methods to separate and characterize post-translationally modified (PTM) peptides without the need of any previous fractionation or derivatization step. The separation of phosphopeptides and differently sialylated O-glycopeptides in the ZIC stationary phase was dominated by an electrostatic repulsion interaction mechanism between the negatively charged phosphate groups or sialic acid moieties and the negatively charged terminal sulfonate group of the stationary phase, whereas the separation of either non-modified peptides or neutral O-glycopeptides both free of basic amino acids was based on a partitioning mechanism. In neutral amide columns, the separation was mainly dominated by hydrophilic partitioning, leading to a higher retention of the post-translationally modified peptides than the unmodified counterparts due to the hydrophilicity provided by the phosphate groups and/or O-glycans. As a consequence, HILIC-ESI-QTOF MS operating in the positive ion mode is a powerful tool for the characterization of underivatized O-glycopeptides and phosphopeptides.

Molecular dynamics study of the effects of calcium ions on the conformational properties of comb-like poly(acrylic acid-co-methyl allyl polyoxyethylene ether)

All-atom molecular dynamics simulations were employed to study the microscopic conformational properties of three kinds of comb-like poly(acrylic acid-co-methyl allyl polyoxyethylene ether) (P(AA-co-MAPEG)) in solution. Two different systems, which contained single chain and two chains respectively, were studied, and the binding types of calcium ions (Ca2+) to carboxylate groups (–COO−) were analyzed. For the systems containing a single chain, as the concentration of Ca2+ increased, the value of the radius of gyration, Rg, for P(AA-co-MAPEG) (4:1) (4:1 represented the monomer ratios of acrylic acid to polyoxyethylene methyl allyl ether, the same description below) chain sharply decreased in Ca2+ solution because Ca2+ weakened the repulsive electrostatic interactions between the charged –COO− while hardly interacted with –COO− directly (e.g. coordination). And the values of Rg for the P(AA-co-MAPEG) (6:1) chain and P(AA-co-MAPEG) (9:1) chain changed slightly because Ca2+ easily interacted with the –COO−, and the polymer chains exhibited a more rigid conformation. For the systems containing two chains, due to two competing factors, the solvation of –COO− and steric hindrance induced by side chains, it was favorable for P(AA-co-MAPEG) (6:1) chains to approach each other to form intermolecular Ca2+ bridges. For comb-like polyelectrolyte, intermolecular binding was difficult to form than intramolecular binding. And among all the possible intramolecular binding modes, the type of Ca2+ binding to two oxygen atoms of adjacent –COO− was the most favorable.

Construction and Self-Assembly of Single-Chain Polymer Nanoparticles via Coordination Association and Electrostatic Repulsion in Water.

Simultaneous coordination-association and electrostatic-repulsion interactions play critical roles in the construction and stabilization of enzymatic function metal centers in water media. These interactions are promising for construction and self-assembly of artificial aqueous polymer single-chain nanoparticles (SCNPs). Herein, the construction and self-assembly of dative-bonded aqueous SCNPs are reported via simultaneous coordination-association and electrostatic-repulsion interactions within single chains of histamine-based hydrophilic block copolymer. The electrostatic-repulsion interactions are tunable through adjusting the imidazolium/imidazole ratio in response to pH, and in situ Cu(II)-coordination leads to the intramolecular association and single-chain collapse in acidic water. SCNPs are stabilized by the electrostatic repulsion of dative-bonded block and steric shielding of nonionic water-soluble block, and have a huge specific surface area of function metal centers accessible to substrates in acidic water. Moreover, SCNPs can assemble into micelles, networks, and large particles programmably in response to the solution pH. These unique media-sensitive phase-transformation behaviors provide a general, facile, and versatile platform for the fabrication of enzyme-inspired smart aqueous catalysts.

Aggregation of adult and fetal hemoglobin by ingested nitrate anions

The ingested nitrates sourced from tap water, food, chemicals and pharmaceuticals areconverted to nitrites in the body surfaces by bacteria and then, the nitrite ions can lead thestructural changing in hemoglobin. In the present work, aggregation of the purified hemoglobinin adult (HbA) and in fetus or newborn (HbF) in the presence of nitrite ions were studied.Hemoglobin aggregation was performed chemically in the presence of 10 mg/l nitrite ions andexamined by UV-Vis spectrophotometer at 360 nm wavelength. The extrinsic fluorimetricmeasurements indicated that repulsive electrostatic interaction between nitrite anions andnegative charged groups of both types of HbA and HbF molecules leads to expose thehydrophobic patch of the protein molecules. Moreover, the α-helix to β-strand transition in bothtypes of hemoglobins shown by circular dichroism support aggregation process among thisprotein. However, at natural pH, the protonated amino group of Gly in HbF tends to bind tonitrite anions more than the unprotonated forms of Val residue in HbA. The drastic slop ofaggregation plot and shorter lag time of HbF relative to HbA demonstrated more aggregation offormer protein.

A Colloidal Description of Intermolecular Interactions Driving Fibril-Fibril Aggregation of a Model Amphiphilic Peptide.

We apply a kinetic analysis platform to study the intermolecular interactions underlying the colloidal stability of dispersions of charged amyloid fibrils consisting of a model amphiphilic peptide (RADA 16-I). In contrast to the aggregation mechanisms observed in the large majority of proteins and peptides, where several elementary reactions involving both monomers and fibrils are present simultaneously, the system selected in this work allows the specific investigation of the fibril-fibril aggregation process. We examine the intermolecular interactions driving the aggregation reaction at pH 2.0 by changing the buffer composition in terms of salt concentration, type of ion as well as type and concentration of organic solvent. The aggregation kinetics are followed by dynamic light scattering, and the experimental data are simulated by Smoluchowski population balance equations, which allow to estimate the energy barrier between two colliding fibrils in terms of the Fuchs stability ratio (W). When normalized on a dimensionless time weighted on the Fuchs stability ratio, the aggregation profiles under a broad range of conditions collapse on a single master curve, indicating that the buffer composition modifies the aggregation kinetics without affecting the aggregation mechanism. Our results show that the aggregation process does not occur under diffusion-limited conditions. Rather, the reaction rate is limited by the presence of an activation energy barrier that is largely dominated by electrostatic repulsive interactions. Such interactions could be reduced by increasing the concentration of salt, which induces charge screening, or the concentration of organic solvent, which affects the dielectric constant. It is remarkable that the dependence of the activation energy on the ionic strength can be described quantitatively in terms of charge screening effects in the frame of the DLVO theory, although specific anion and cation effects are also observed. While anion effects are mainly related to the binding to the positive groups of the fibril surface and to the resulting decrease of the surface charge, cation effects are more complex and involve additional solvation forces.

Influence of the potential well on the breakage rate of colloidal aggregates in simple shear and uniaxial extensional flows.

In this work we build on our previous paper (Harshe, Y. M.; Lattuada, M. Langmuir 2012, 28, 283-292) and compute the breakage rate of colloidal aggregates under the effect of shear forces by means of Stokesian dynamics simulations. A library of clusters made of identical spherical particles covering a broad range of masses and fractal dimension values (from 1.8 to 3.0) was generated by means of a combination of several Monte Carlo methods. DLVO theory has been used to describe the interparticle interactions, and contact forces have been introduced by means of the discrete element method. The aggregate breakage process was investigated by exposing them to well-defined shear forces, generated under both simple shear and uniaxial extensional flow conditions, and by recording the time required to reach the first breakage event. It has been found that the breakage rate of clusters was controlled by the potential well between particles as described by DLVO theory. A semiempirical Arrhenius-type exponential equation that relates the potential well to the breakage rate has been used to fit the simulation results. The dependence of the breakage process on the radius of gyration, on the external shear strength, and on the fractal dimension has been obtained, providing a very general relationship for the breakage rate of clusters. It was also found that the fragment mass distribution is insensitive to the presence of electrostatic repulsive interactions. We also clarify the physical reason for the large difference in the breakage rate of clusters between simple shear and the uniaxial extensional flow using a criterion based on the energy dissipation rate. Finally, in order to answer the question of the minimum cluster size that can break under simple shear conditions, a critical rotation number has been introduced, expressing the maximum number of rotations that a cluster exposed to simple shear could sustain before breakage.

Appropriate salt concentration of nanodiamond colloids for electrostatic self-assembly seeding of monosized individual diamond nanoparticles on silicon dioxide surfaces.

Monosized (∼4 nm) diamond nanoparticles arranged on substrate surfaces are exciting candidates for single-photon sources and nucleation sites for ultrathin nanocrystalline diamond film growth. The most commonly used technique to obtain substrate-supported diamond nanoparticles is electrostatic self-assembly seeding using nanodiamond colloidal suspensions. Currently, monodisperse nanodiamond colloids, which have a narrow distribution of particle sizes centering on the core particle size (∼4 nm), are available for the seeding technique on different substrate materials such as Si, SiO2, Cu, and AlN. However, the self-assembled nanoparticles tend to form small (typically a few tens of nanometers or even larger) aggregates on all of those substrate materials. In this study, this major weakness of self-assembled diamond nanoparticles was solved by modifying the salt concentration of nanodiamond colloidal suspensions. Several salt concentrations of colloidal suspensions were prepared using potassium chloride as an inserted electrolyte and were examined with respect to seeding on SiO2 surfaces. The colloidal suspensions and the seeded surfaces were characterized by dynamic light scattering and atomic force microscopy, respectively. Also, the interaction energies between diamond nanoparticles in each of the examined colloidal suspensions were compared on the basis of the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. From these investigations, it became clear that the appropriate salt concentration suppresses the formation of small aggregates during the seeding process owing to the modified electrostatic repulsive interaction between nanoparticles. Finally, monosized (<10 nm) individual diamond nanoparticles arranged on SiO2 surfaces have been successfully obtained.