Controlling CaCO3 Particle Size with {Ca2+}:{CO3 2-} Ratios in Aqueous Environments.

The effect of stoichiometry on the new formation and subsequent growth of CaCO3 was investigated over a large range of solution stoichiometries (10-4 < r aq < 104, where r aq = {Ca2+}:{CO3 2-}) at various, initially constant degrees of supersaturation (30 < Ωcal < 200, where Ωcal = {Ca2+}{CO3 2-}/K sp), pH of 10.5 ± 0.27, and ambient temperature and pressure. At r aq = 1 and Ωcal < 150, dynamic light scattering (DLS) showed that ion adsorption onto nuclei (1-10 nm) was the dominant mechanism. At higher supersaturation levels, no continuum of particle sizes is observed with time, suggesting aggregation of prenucleation clusters into larger particles as the dominant growth mechanism. At r aq ≠ 1 (Ωcal = 100), prenucleation particles remained smaller than 10 nm for up to 15 h. Cross-polarized light in optical light microscopy was used to measure the time needed for new particle formation and growth to at least 20 µm. This precipitation time depends strongly and asymmetrically on r aq. Complementary molecular dynamics (MD) simulations confirm that r aq affects CaCO3 nanoparticle formation substantially. At r aq = 1 and Ωcal ≫ 1000, the largest nanoparticle in the system had a 21-68% larger gyration radius after 20 ns of simulation time than in nonstoichiometric systems. Our results imply that, besides Ωcal, stoichiometry affects particle size, persistence, growth time, and ripening time toward micrometer-sized crystals. Our results may help us to improve the understanding, prediction, and formation of CaCO3 in geological, industrial, and geo-engineering settings.

Depletion-Induced Chiral Chain Formation of Magnetic Spheres.

Experimental evidence is presented for the spontaneous formation of chiral configurations in bulk dispersions of magnetized colloids that interact by a combination of anisotropic dipolar interactions and isotropic depletion attractions. The colloids are superparamagnetic silica spheres, magnetized and aligned by a carefully tuned uniform external magnetic field; isotropic attractions are induced by using poly(ethylene oxide) polymers as depleting agents. At specific polymer concentrations, sphere chains wind around each other to form helical structures-of the type that previously have only been observed in simulations on small sets of unconfined dipolar spheres with additional isotropic interactions.

Self-assembly of charged colloidal cubes.

In this work, we show how and why the interactions between charged cubic colloids range from radially isotropic to strongly directionally anisotropic, depending on tuneable factors. Using molecular dynamics simulations, we illustrate the effects of typical solvents to complement experimental investigations of cube assembly. We find that in low-salinity water solutions, where cube self-assembly is observed, the colloidal shape anisotropy leads to the strongest attraction along the corner-to-corner line, followed by edge-to-edge, with a face-to-face configuration of the cubes only becoming energetically favorable after the colloids have collapsed into the van der Waals attraction minimum. Analysing the potential of mean force between colloids with varied cubicity, we identify the origin of the asymmetric microstructures seen in experiment.

Activation of Human Monocytes by Colloidal Aluminum Salts.

Subunit vaccines often contain colloidal aluminum salt-based adjuvants to activate the innate immune system. These aluminum salts consist of micrometer-sized aggregates. It is well-known that particle size affects the adjuvant effect of particulate adjuvants. In this study, the activation of human monocytes by hexagonal-shaped gibbsite (ø = 210 ± 40 nm) and rod-shaped boehmite (ø = 83 ± 827 nm) was compared with classical aluminum oxyhydroxide adjuvant (alum). To this end, human primary monocytes were cultured in the presence of alum, gibbsite, or boehmite. The transcriptome and proteome of the monocytes were investigated by using quantitative polymerase chain reaction and mass spectrometry. Human monocytic THP-1 cells were used to investigate the effect of the particles on cellular maturation, differentiation, activation, and cytokine secretion, as measured by flow cytometry and enzyme-linked immunosorbent assay. Each particle type resulted in a specific gene expression profile. IL-1ß and IL-6 secretion was significantly upregulated by boehmite and alum. Of the 7 surface markers investigated, only CD80 was significantly upregulated by alum and none by gibbsite or boehmite. Gibbsite hardly activated the monocytes. Boehmite activated human primary monocytes equally to alum, but induced a much milder stress-related response. Therefore, boehmite was identified as a promising adjuvant candidate.

Experimental Evidence for Algebraic Double-Layer Forces.

According to conventional wisdom, electric double-layer forces normally decay exponentially with separation distance. Here, we present experimental evidence of algebraically decaying double-layer interactions. We show that algebraic interactions arise in both strongly overlapping as well as counterion-only regimes, albeit the evidence is less clear for the former regime. In both of these cases, the disjoining pressure profile assumes an inverse square distance dependence. At small separation distances, another algebraic regime is recovered. In this regime, the pressure decays as the inverse of separation distance.

Convectively Assembled Monolayers of Colloidal Cubes: Evidence of Optimal Packings.

We employ a system of cubic colloids with rounded corners to study the close-packed monolayers that form via convective assembly. We show that by controlled solvent evaporation large densely packed monolayers of colloidal cubes are obtained. Using scanning electron microscopy and particle-tracking algorithms, we investigate the local order in detail and show that the obtained monolayers possess their predicted close-packed optimal packings, the Λ0-lattice and the Λ1-lattice, as well as the simple square-lattice and disordered packings. We further show that shape details of the cube corners are important for the final packing symmetry, where the frequency of the Λ1-lattice increases with decreasing roundness of the corners, whereas the frequency of the Λ0-lattice is unaffected. The formation of both optimal packings is found to be a consequence of the out-of-equilibrium formation process, which leads to small shifts in rows of cubes, thereby transforming the Λ1-lattice into the Λ0-lattice.

Wet-Chemical Synthesis of Chiral Colloids.

We disclose a method for the synthesis of chiral colloids from spontaneously formed hollow sugar-surfactant microtubes with internally confined mobile colloidal spheres. Key feature of our approach is the grafting of colloid surfaces with photoresponsive coumarin moieties, which allow for UV-induced, covalent clicking of colloids into permanent chains, with morphologies set by the colloid-to-tube diameter ratio. Subsequent dissolution of tube confinement yields aqueous suspensions that comprise bulk quantities of a variety of linear chains, including single helical chains of polystyrene colloids. These colloidal equivalents of chiral (DNA) molecules are intended for microscopic study of chiral dynamics on a single-particle level.

Inward growth by nucleation: Multiscale self-assembly of ordered membranes.

Striking morphological similarities found between superstructures of a wide variety of seemingly unrelated crystalline membrane systems hint at the existence of a common formation mechanism. Resembling systems such as multiwalled carbon nanotubes, bacterial protein shells, or peptide nanotubes, the self-assembly of SDS/ß-cyclodextrin complexes leads to monodisperse multilamellar microtubes. We uncover the mechanism of this hierarchical self-assembly process by time-resolved small- and ultrasmall-angle x-ray scattering. In particular, we show that symmetric crystalline bilayers bend into hollow cylinders as a consequence of membrane line tension and an anisotropic elastic modulus. Starting from single-walled microtubes, successive nucleation of new cylinders inside preexisting ones drives an inward growth. As both the driving forces that underlie the self-assembly behavior and the resulting morphologies are common to systems of ordered membranes, we believe that this formation mechanism has a similarly general applicability.

Interactions between amphoteric surfaces with strongly overlapping double layers.

The entropic repulsion between strongly overlapping electrical double-layers from two parallel amphoteric plates is described via the Donnan equilibrium in the limit of zero electric field. The plates feature charge-regulation and the inter-plate solution is in equilibrium with a reservoir of a monovalent electrolyte solution. A finite electric potential and disjoining pressure is found at contact between the plates, due to a complete discharging of the plates. For low potentials, the decay of potential and pressure is fully governed by a characteristic length scale and the contact potential. Additionally, for large separations we find a universal inverse square decay of disjoining pressure, irrespective of the contact potential. The results of the Donnan theory show quantitative agreement with self-consistent field computations that solve the full Poisson equation.

Self-organization in dipolar cube fluids constrained by competing anisotropies.

For magnetite spherical nanoparticles, the orientation of the dipole moment in the crystal does not affect the morphology of either zero field or field induced structures. For non-spherical particles however, an interplay between particle shape and direction of the magnetic moment can give rise to unusual behaviors, in particular when the moment is not aligned along a particle symmetry axis. Here we disclose for the first time the unique magnetic properties of hematite cubic particles and show the exact orientation of the cubes' dipole moment. Using a combination of experiments and computer simulations, we show that dipolar hematite cubes self-organize into dipolar chains with morphologies remarkably different from those of spheres, and demonstrate that the emergence of these structures is driven by competing anisotropic interactions caused by the particles' shape anisotropy and their fixed dipole moment. Furthermore, we have analytically identified a specific interplay between energy, and entropy at the microscopic level and found that an unorthodox entropic contribution mediates the organization of particles into the kinked nature of the dipolar chains.

In situ observation of self-assembly of sugars and surfactants from nanometres to microns.

The hierarchical self-assembly of sugar and surfactant molecules into hollow tubular microstructures was characterized in situ with high resolution small-angle X-ray scattering spanning more than three orders of magnitude of spatial scales. Scattering profiles reveal that aqueous host-guest inclusion complexes self-assemble into multiple equally spaced curved bilayers forming a collection of concentric hollow cylinders. Scattering data can be described by a simple theoretical model of the microtubes. The interlamellar distance was found to be surprisingly large. Moreover, we report that the multi-walled structure of the microtubes swells as the concentration or the temperature is varied.

Observation of solid-solid transitions in 3D crystals of colloidal superballs.

Self-organization in anisotropic colloidal suspensions leads to a fascinating range of crystal and liquid crystal phases induced by shape alone. Simulations predict the phase behaviour of a plethora of shapes while experimental realization often lags behind. Here, we present the experimental phase behaviour of superball particles with a shape in between that of a sphere and a cube. In particular, we observe the formation of a plastic crystal phase with translational order and orientational disorder, and the subsequent transformation into rhombohedral crystals. Moreover, we uncover that the phase behaviour is richer than predicted, as we find two distinct rhombohedral crystals with different stacking variants, namely hollow-site and bridge-site stacking. In addition, for slightly softer interactions we observe a solid-solid transition between the two. Our investigation brings us one step closer to ultimately controlling the experimental self-assembly of superballs into functional materials, such as photonic crystals.

Depletion controlled surface deposition of uncharged colloidal spheres from stable bulk dispersions.

The competition between surface adsorption and bulk aggregation was investigated for silica colloids dispersed in cyclohexane in contact with hydrophobized silica substrates. Central to this study is that the colloids and surfaces have the same material and surface properties. Colloid-colloid and colloid-surface interactions were controlled by addition of polymers providing depletion interaction. Bulk instability was determined by turbidity and viscosity measurements and surface adsorption by ellipsometry measurements. At increasing polymer concentration, strong surface adsorption occurred at polymer concentrations below that required for bulk phase separation. Complementary Monte Carlo simulations with the use of a new weak depletion theory support quantitatively the experimental observation of the existence of an interval of interaction strength at which aggregation in bulk is negligible while surface adsorption is substantial.

Reconfigurable assembly of superparamagnetic colloids confined in thermo-reversible microtubes.

Structural transformations of superparamagnetic colloids confined within self-assembled microtubes are studied by systematically varying tube-colloid size ratios and external magnetic field directions. A magnetic field parallel to microtubes may stretch non-linear chains like zigzag chains into linear chains. Non-parallel fields induce new structures including repulsive chains of single colloids, kinked chains and repulsive dimers, which are not observed for unconfined magnetic colloids in the bulk. The formed colloidal structures are confirmed via model calculations which account for tube-colloid size ratio effects and their reconfigurability with the field direction. Furthermore, structures are formed that allow controllable switching between a helical and a non-helical state. All observed field-induced transformations in microtubes are reversible provided the microtubes are not completely filled with colloids. In addition, we demonstrate magnetic field-responsive 2D crystallization by extending control over colloidal configurations in single microtubes to multiple well-aligned microtubes.

A thermodynamic gauge for mobile counter-ions from colloids and nanoparticles.

A thermodynamic equilibrium sensor is proposed that measures the ratio of the number of elementary charges z to the mass m of charged solutes such as charged colloids and nanoparticles. The sensor comprises a small, membrane-encapsulated salt solution volume that absorbs neutral salt molecules in response to the release of mobile counter-ions by charge carriers in the surrounding suspension. The sensor state emerges as a limiting case of the equilibrium salt imbalance, and the ensuing osmotic pressure difference, between arbitrary salt and suspension volumes. A weight concentration of charge carriers c is predicted to significantly increase the sensor's salt number density from its initial value ρs,0 to ρRs, according to the relation (ρRs/ρs,0)(2)-1=zc/mρs,0, under the assumption that the mobile ions involved in the thermodynamic sensor-suspension equilibrium are ideal and homogeneously distributed.

Shape-sensitive crystallization in colloidal superball fluids.

Guiding the self-assembly of materials by controlling the shape of the individual particle constituents is a powerful approach to material design. We show that colloidal silica superballs crystallize into canted phases in the presence of depletants. Some of these phases are consistent with the so-called "Λ1" lattice that was recently predicted as the densest packing of superdisks. As the size of the depletant is reduced, however, we observe a transition to a square phase. The differences in these entropically stabilized phases result from an interplay between the size of the depletants and the fine structure of the superball shape. We find qualitative agreement of our experimental results both with a phase diagram computed on the basis of the volume accessible to the depletants and with simulations. By using a mixture of depletants, one of which is thermosensitive, we induce solid-to-solid phase transitions between square and canted structures. The use of depletant size to leverage fine features of the shape of particles in driving their self-assembly demonstrates a general and powerful mechanism for engineering novel materials.

Formation and liquid permeability of dense colloidal cube packings.

The liquid permeability of dense random packings of cubic colloids with rounded corners is studied for solid hematite cubes and hollow microporous silica cubes. The permeabilities of these two types of packings are similar, confirming that the micropores in the silica shell of the hollow cubes do not contribute to the permeability. From the Brinkman screening length √k of ∼16 nm, we infer that the relevant pores are indeed intercube pores. Furthermore, we relate the permeability to the volume fraction and specific solid volume of the cubes using the Kozeny-Carman relation. The Kozeny-Carman relation contains a constant that accounts for the topology and size distribution of the pores in the medium. The constant obtained from our study with aspherical particles is of the same order of magnitude as those from studies with spherical and ellipsoidal particles, which supports the notion that the Kozeny-Carman relation is applicable for any dense particle packing with (statistically) isotropic microstructures, irrespective of the particle shape.

Swelling enhanced remanent magnetization of hydrogels cross-linked with magnetic nanoparticles.

Hydrogels that are pH-sensitive and partially cross-linked by cobalt ferrite nanoparticles exhibit remarkable remanent magnetization behavior. The magnetic fields measured outside our thin disks of ferrogel are weak, but in the steady state, the field dependence on the magnetic content of the gels and the measurement geometry is as expected from theory. In contrast, the time-dependent behavior is surprisingly complicated. During swelling, the remanent field first rapidly increases and then slowly decreases. We ascribe the swelling-induced field enhancement to a change in the average orientation of magnetic dipolar structures, while the subsequent field drop is due to the decreasing concentration of nanoparticles. During shrinking, the field exhibits a much weaker time dependence that does not mirror the values found during swelling. These observations provide original new evidence for the markedly different spatial profiles of the pH during swelling and shrinking of hydrogels.

Colloidal iron(III) pyrophosphate particles.

Ferric pyrophosphate is a widely used material in the area of mineral fortification but its synthesis and properties in colloidal form are largely unknown. In this article, we report on the synthesis and characterisation of colloidal iron(III) pyrophosphate particles with potential for application as a food additive in iron-fortified products. We present a convenient and food grade synthetic method yielding stable colloids of nanometre size with a distinctive white colour, a unique characteristic for iron-containing colloids. Physical properties of the colloids were investigated using different techniques, to assess particle crystallinity, surface charge, mass density, refractive index, internal structure, elemental composition and magnetic properties. The findings of this research are especially relevant for food and beverage science and technology and will help develop a more effective use of these fortifiers in colloidal form.

Particle shape anisotropy in pickering emulsions: cubes and peanuts.

We have investigated the effect of particle shape in Pickering emulsions by employing, for the first time, cubic and peanut-shaped particles. The interfacial packing and orientation of anisotropic microparticles are revealed at the single-particle level by direct microscopy observations. The uniform anisotropic hematite microparticles adsorb irreversibly at the oil-water interface in monolayers and form solid-stabilized o/w emulsions via the process of limited coalescence. Emulsions were stable against further coalescence for at least 1 year. We found that cubes assembled at the interface in monolayers with a packing intermediate between hexagonal and cubic and average packing densities of up to 90%. Local domains displayed densities even higher than theoretically achievable for spheres. Cubes exclusively orient parallel with one of their flat sides at the oil-water interface, whereas peanuts preferentially attach parallel with their long side. Those peanut-shaped microparticles assemble in locally ordered, interfacial particle stacks that may interlock. Indications for long-range capillary interactions were not found, and we hypothesize that this is related to the observed stable orientations of cubes and peanuts that marginalize deformations of the interface.