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The impact of solution stoichiometry, upon formation of BaSO4 crystals in 0.02 M NaCl suspensions, on the development of particle size was investigated using dynamic light scattering (DLS). Measurements were performed on a set of suspensions prepared with predefined initial supersaturation, based on the quotient of the constituent ion activity product {Ba2+}{SO42-} over the solubility product Ksp (Ωbarite = {Ba2+}{SO42-}/Ksp = 100, 500, or 1000-11,000 in steps of 1000), and ion activity solution stoichiometries (raq = {Ba2+}:{SO42-} = 0.01, 0.1, 1, 10 and 100), at circumneutral pH of 5.5-6.0, and ambient temperature and pressure. DLS showed that for batch experiments, crystal formation with varying raq was best investigated at an initial Ωbarite of 1000 and using the forward detection angle. At this Ωbarite and set of raq, the average apparent hydrodynamic particle size of the largest population present in all suspensions increased from ∼200 to ∼700 nm within 10-15 min and was independently confirmed by transmission electron microscopy (TEM) imaging. Additional DLS measurements conducted at the same conditions in flow confirmed that the BaSO4 formation kinetics were very fast for our specifically chosen conditions. The DLS flow measurements, monitoring the first minute of BaSO4 formation, showed strong signs of aggregation of prenucleation clusters forming particles with a size in the range of 200-300 nm for every raq. The estimated initial bulk growth rates from batch DLS results show that BaSO4 crystals formed fastest at near-stoichiometric conditions and more slowly at nonstoichiometric conditions. Moreover, at extreme SO4-limiting conditions, barite formation was slower compared to Ba-limiting conditions. Our results show that DLS can be used to investigate nucleation and growth at carefully selected experimental and analytical conditions. The combined DLS and TEM results imply that BaSO4 formation is influenced by solution stoichiometry and may aid to optimize antiscalant efficiency and regulate BaSO4 (scale) formation processes.

Lanthanide-doped (nano)crystals are an important class of materials in luminescence thermometry. The working mechanism of these thermometers is diverse but most often relies on variation of the ratio of emission intensities from two thermally coupled excited states with temperature. At low temperatures, nonradiative coupling between the states can be slow compared to radiative decay, but, at higher temperatures, the two states reach thermal equilibrium due to faster nonradiative coupling. In thermal equilibrium, the intensity ratio follows Boltzmann statistics, which gives a convenient model to calibrate the thermometer. Here, we investigate multiple strategies to shift the onset of thermal equilibrium to lower temperatures, which enables Boltzmann thermometry in a wider dynamic range. We use Eu3+-doped microcrystals as a model system and find that the nonradiative coupling rates increase for host lattices with higher vibrational energies and shorter lanthanide–ligand distances, which reduces the onset temperature of thermal equilibrium by more than 400 K. We additionally reveal that thermometers with excited states coupled by electric-dipole transitions have lower onset temperatures than those with magnetic-dipole-coupled states due to selection rules. These insights provide essential guidelines for the optimization of Boltzmann thermometers to operate in an extended temperature range.

Fungal and bacterial pathogens causing lung infections often use lectins to mediate adhesion to glycoconjugates at the surface of host tissues. Given the rapid emergence of resistance to the treatments in current use, β-propeller lectins such as FleA from Aspergillus fumigatus, SapL1 from Scedosporium apiospermum, and BambL from Burkholderia ambifaria have become appealing targets for the design of anti-adhesive agents. In search of novel and cheap anti-infectious agents, we synthesized multivalent compounds that can display up to 20 units of fucose, the natural ligand. We obtained nanomolar inhibitors that are several orders of magnitude stronger than their monovalent analogue according to several biophysical techniques (i.e., fluorescence polarization, isothermal titration calorimetry, and bio-layer interferometry). The reason for high affinity might be attributed to a strong aggregating mechanism, which was examined by analytical ultracentrifugation. Notably, the fucosylated inhibitors reduced the adhesion of A. fumigatus spores to lung epithelial cells when administered 1 h before or after the infection of human lung epithelial cells. For this reason, we propose them as promising anti-adhesive drugs for the prevention and treatment of aspergillosis and related microbial lung infections.

The internal energy of capacitive porous carbon electrodes was determined experimentally as a function of applied potential in aqueous salt solutions. Both the electrical work and produced heat were measured. The potential dependence of the internal energy is explained in terms of two contributions, namely the field energy of a dielectric layer of water molecules at the surface and the potential energy of ions in the pores. The average electric potential of the ions is deduced, and its dependence on the type of salt suggests that the hydration strength limits how closely ions can approach the surface.

Ultrafiltration membranes are important porous materials to produce freshwater in an increasingly water-scarce world. A recent approach to generate porous membranes is solvent transfer induced phase separation (STrIPS). During STrIPS, the interplay of liquid-liquid phase separation and nanoparticle self-assembly results in hollow fibers with small surface pores, ideal structures for applications as filtration membranes. However, the underlying mechanisms of the membrane formation are still poorly understood, limiting the control over structure and properties. To address this knowledge gap, we study the nonequilibrium dynamics of hollow fiber structure evolution. Confocal microscopy reveals the distribution of nanoparticles and monomers during STrIPS. Diffusion simulations are combined with measurements of the interfacial elasticity to investigate the effect of the solvent concentration on nanoparticle stabilization. Furthermore, we demonstrate the separation performance of the membrane during ultrafiltration. To this end, polyelectrolyte multilayers are deposited on the membrane, leading to tunable pores that enable the removal of dextran molecules of different molecular weights (>360 kDa, >60 kDa, >18 kDa) from a feed water stream. The resulting understanding of STrIPS and the simplicity of the synthesis process open avenues to design novel membranes for advanced separation applications.

Phosvitins is a key egg yolk protein and can often be found in food emulsions. It is highly phosphorylated and hence phosvitins contain a large number of negatively charged amino acid groups, for pH > pI. Due to the presence of these phophoserines, phosvitins bind to positively charged multivalent ions. Its amphipolar structure makes phosvitin also an efficient emulsion stabilizer. The ion binding and emulsifying abilities of phosvitins are influenced by environmental conditions such as pH and ionic strength. Various physicochemical properties of phosvitins such as size and charge under various conditions, and how they self-assemble via multivalent ions are not well-understood. To gain more insight into these physical characteristics, we performed high brilliance synchrotron small angle X-ray scattering (SAXS) on phosvitin solutions. The structure factor S(q) obtained from the SAXS profiles showed that the double layer interactions between charged phosvitin assemblies are strongly affected by pH and ionic strength of the buffer. The effects of multivalent ions (Mg2+, Fe3+) on the size and structure of phosvitin were also investigated. Our results revealed that the aggregation of phosvitin mediated by metal ions is induced by electrostatic attraction and only occurs beyond a threshold cation concentration, where phosvitin loses long-range electrostatic double layer repulsions. These findings help understanding the effects of metal ions and pH on phosvitin in more complex environments such as food emulsions.

Hypothesis: Colloidal molecules with anisotropic shapes and interactions are powerful model systems for deciphering the behavior of real molecules and building units for creating materials with designed properties. While many strategies for their assembly have been developed, they typically yield a broad distribution or are limited to a specific type. We hypothesize that the shape and relative sizes of colloidal particles can be exploited to efficiently direct their assembly into colloidal molecules of desired valence. Experiments: We exploit electrostatic self-assembly of negatively charged spheres made from either polystyrene or silica onto positively charged hematite cubes. We thoroughly analyze the role of the shape and size ratio of particles on the cluster size and yield of colloidal molecules. Findings: Using a combination of experiments and simulations, we demonstrate that cubic particle shape is crucial to generate high yields of distinct colloidal molecules over a wide variety of size ratios. We find that electrostatic repulsion between the satellite spheres is important to leverage the templating effect of the cubes, leading the spheres to preferentially assemble on the facets rather than the edges and corners of the cube. The sixfold symmetry of cubes favors the assembly of molecules with six, four, and two satellite spheres at appropriate size ratios and interaction strength. Furthermore, we reveal that our protocol is not affected by the specific choice of the material of the colloidal particles. Finally, we show that the permanent magnetic dipole moment of the hematite cubes can be utilized to separate colloidal molecules from non-assembled satellite particles. Our simple and effective strategy might be extended to other templating particle shapes, thereby greatly expanding the library of colloidal molecules that can be achieved with high yield and purity.

Pickering emulsions stabilized by ethyl cellulose nanoparticles have recently received –great attention for their remarkable stability and numerous industrial applications. De- spite this, the exact stabilization mechanism of such Pickering emulsions is still not fully understood. Both the stabilization of the emulsion by particle adsorption at the inter- face and through network formation in the continuous phase (leading to a yield stress) have been suggested. In this work we study soybean oil-in-water emulsions stabilized by ethyl cellulose nanoparticles and find, by the use of confocal microscopy and interfa- cial tension measurements, that the main stabilization mechanism of this nanoparticle- stabilized emulsions is the adsorption of the particles at the interface, instead of forming a network in the continuous phase. At the same time, oscillatory rheology measurements reveal that the emulsions exhibit a yield stress well below the random close-packing limit for hard spheres, suggesting short-range interactions between the droplets caused by the presence of the particles at the interface. The presence of the particles at the interface in combination with the observed rheological behavior of an attractive emulsion gives a strong indication for a particle-bridged stabilized emulsions.

The growth of two-dimensional platelets of the CdX family (X = S, Se, or Te) in an organic solvent requires the presence of both long- and short-chain ligands. This results in nanoplatelets of atomically precise thickness and long-chain ligand-stabilized Cd top and bottom surfaces. The platelets show a bright and spectrally pure luminescence. Despite the enormous interest in CdX platelets for optoelectronics, the growth mechanism is not fully understood. Riedinger et al. studied the reaction without a solvent and showed the favorable role for short-chain carboxylates for growth in two dimensions. Their model, based on the total energy of island nucleation, shows favored side facet growth versus growth on the top and bottom surfaces. However, several aspects of the synthesis under realistic conditions are not yet understood: Why are both short- and long-chain ligands required to obtain platelets? Why does the synthesis result in both isotropic nanocrystals and platelets? At which stage of the reaction is there bifurcation between isotropic and 2D growth? Here, we report an in situ study of the CdSe nanoplatelet reaction under practical synthesis conditions. We show that without short-chain ligands, both isotropic and mini-nanoplatelets form in the early stage of the process. However, most remaining precursors are consumed in isotropic growth. Addition of acetate induces a dramatic shift toward nearly exclusive 2D growth of already existing mini-nanoplatelets. Hence, although myristate stabilizes mini-nanoplatelets, mature nanoplatelets only grow by a subtle interplay between myristate and acetate, the latter catalyzes fast lateral growth of the side facets of the mini-nanoplatelets.

Significance Particles of all shapes and sizes flowing through tight spaces are ever present in applications across length scales ranging from blood flow through tissue capillaries to industrial-scale processes. To date, separating these particles relies on methods employing external force fields. Currently underexplored, omnipresent fluid–structure interactions hold the key to shape-based separation independent of external intervention. By leveraging experiments, theory, and simulations, we show how the symmetry of a particle determines its overall trajectory: In particular, mirror-symmetric particles, both strongly and weakly confined, follow a universal path. We propose minimalistic scaling relations to describe how particle shape affects the parameterization of the universal path. These findings could be used to “program” particle trajectories in lab-on-a-chip devices and industrial separation processes., Comprehensive understanding of particle motion in microfluidic devices is essential to unlock additional technologies for shape-based separation and sorting of microparticles like microplastics, cells, and crystal polymorphs. Such particles interact hydrodynamically with confining surfaces, thus altering their trajectories. These hydrodynamic interactions are shape dependent and can be tuned to guide a particle along a specific path. We produce strongly confined particles with various shapes in a shallow microfluidic channel via stop flow lithography. Regardless of their exact shape, particles with a single mirror plane have identical modes of motion: in-plane rotation and cross-stream translation along a bell-shaped path. Each mode has a characteristic time, determined by particle geometry. Furthermore, each particle trajectory can be scaled by its respective characteristic times onto two master curves. We propose minimalistic relations linking these timescales to particle shape. Together these master curves yield a trajectory universal to particles with a single mirror plane.

Hypothesis The shape of colloidal particles affects the structure of colloidal dispersions. The effect of the cube shape on the thermodynamics of colloidal cube dispersions has not yet been studied experimentally. Static light scattering measurements on colloidal cubic silica shells at finite concentrations allows us to measure the structure factor of colloidal cube fluids and to test theoretical predictions for the equation of state of hard convex superballs. Experiments Hollow silica nanocubes of varying concentrations in N,N,-dimethylformamide were studied with static light scattering. The structure factor was extracted from the scattering curves using experimental form factors. From this experimental structure factor, the specific density of the particles, and the osmotic compressibility were obtained. This osmotic compressibility was then compared to a theoretical equation of state of hard superballs. Findings The first experimental structure factors of a stable cube fluid are presented. The osmotic compressibility of the cube fluid can be described by the equation of state of a hard superball fluid, showing that silica cubes in N,N,-dimethylformamide with LiCl effectively interact as hard particles.

There is a large debate on the destabilization mechanism of emulsions. We present a simple technique using mechanical compression to destabilize oil-in-water emulsions. Upon compression of the emulsion, the continuous aqueous phase is squeezed out, while the dispersed oil phase progressively deforms from circular to honeycomb-like shapes. The films that separate the oil droplets are observed to thin and break at a critical oil/water ratio, leading to coalescence events. Electrostatic interactions and local droplet rearrangements do not determine film rupture. Instead, the destabilization occurs like an avalanche propagating through the system, starting at areas where the film thickness is smallest., 16 pages, 5 figures

Bicontinuous particle-stabilized emulsions (bijels) are networks of interpenetrating oil/water channels with applications in catalysis, tissue engineering, and energy storage. Bijels can be generated by arresting solvent transfer induced phase separation (STrIPS) via interfacial jamming of nanoparticles. However, until now, STrIPS bijels have only been formed with silica nanoparticles of low surface charge densities, limiting their potential applications in catalysis and fluid transport. Here, we show how strongly charged silica nanoparticles can stabilize bijels. To this end, we carry out a systematic study employing dynamic light scattering, zeta potential, acid/base titrations, turbidimetry, surface tension, and confocal microscopy. We find that moderating the adsorption of oppositely charged surfactants on the particles is crucial to facilitate particle dispersibility in the bijel casting mixture and bijel stabilization. Our results potentially introduce a general understanding for bijel fabrication with different inorganic nanoparticle materials of variable charge density.

Biological microswimmers such as bacteria show collective motion that is made possible by an intricate interplay of sensing and signaling. Ketzetzi et al. reproduce this phenomenon in a catalytic system undergoing, for instance, cooperative speed-ups and dynamic reconfiguration of microswimmer chains.Cooperative motion in biological microswimmers is crucial for their survival as it facilitates adhesion to surfaces, formation of hierarchical colonies, efficient motion, and enhanced access to nutrients. Here, we confine synthetic, catalytic microswimmers along one-dimensional paths and demonstrate that they too show a variety of cooperative behaviours. We find that their speed increases with the number of swimmers, and that the activity induces a preferred distance between swimmers. Using a minimal model, we ascribe this behavior to an effective activity-induced potential that stems from a competition between chemical and hydrodynamic coupling. These interactions further induce active self-assembly into trains where swimmers move at a well-separated, stable distance with respect to each other, as well as compact chains that can elongate, break-up, become immobilized and remobilized. We identify the crucial role that environment morphology and swimmer directionality play on these highly dynamic chain behaviors. These activity-induced interactions open the door toward exploiting cooperation for increasing the efficiency of microswimmer motion, with temporal and spatial control, thereby enabling them to perform intricate tasks inside complex environments.

Understanding the relationship between colloidal building block shape and self-assembled material structure is important for the development of novel materials by self-assembly. In this regard, colloidal superballs are unique building blocks because their shape can smoothly transition between spherical and cubic. Assembly of colloidal superballs under spherical confinement results in macroscopic clusters with ordered internal structure. By utilizing Small Angle X-Ray Scattering (SAXS), we probe the internal structure of colloidal superball dispersion droplets during confinement. We observe and identify four distinct drying regimes that arise during compression via evaporating droplets, and we track the development of the assembled macrostructure. As the superballs assemble, we found that they arrange into the predicted paracrystalline, rhombohedral C1-lattice that varies by the constituent superballs' shape. This provides insights in the behavior between confinement and particle shape that can be applied in the development of new functional materials., 14 pages, 5 figures, supporting info, accepted for publication in JCISOpen

An anisotropic colloidal shape in combination with an externally tunable interaction potential results in a plethora of self-assembled structures with potential applications toward the fabrication of smart materials. Here we present our investigation on the influence of an external magnetic field on the self-assembly of hematite-silica core-shell prolate colloids for two aspect ratios ρ = 2.9 and 3.69. Our study shows a rather counterintuitive but interesting phenomenon, where prolate colloids self-assemble into oblate liquid crystalline (LC) phases. With increasing concentration, particles with smaller ρ reveal a sequence of LC phases involving para-nematic, nematic, smectic, and oriented glass phases. The occurrence of a smectic phase for colloidal ellipsoids has been neither predicted nor reported before. Quantitative shape analysis of the particles together with extensive computer simulations indicate that in addition to ρ, a subtle deviation from the ideal ellipsoidal shape dictates the formation of this unusual sequence of field-induced structures. Particles with ρ = 2.9 exhibit a hybrid shape containing features from both spherocylinders and ellipsoids, which make their self-assembly behavior richer than that observed for either of the “pure” shapes. The shape of the particles with higher ρ matches closely with the ideal ellipsoids, as a result their phase behavior follows the one expected for a “pure” ellipsoidal shape. Using anisotropic building blocks and external fields, our study demonstrates the ramifications of the subtle changes in the particle shape on the field-directed self-assembled structures with externally tunable properties.

An application of angular X-ray cross-correlation analysis (AXCCA) to the scattered intensity distribution measured in 3D reciprocal space from a single-crystalline sample is proposed in this work. Contrary to the conventional application of AXCCA, when averaging over many 2D diffraction patterns collected from different randomly oriented samples is required, the proposed approach provides an insight into the structure of a single specimen. This is particularly useful in studies of defect-rich samples that are unlikely to have the same structure. The application of the method is shown on an example of a qualitative structure determination of a colloidal crystal from simulated as well as experimentally measured 3D scattered intensity distributions.

The rational design of materials requires a fundamental understanding of the mechanisms driving their self-assembly. This may be particularly challenging in highly dense and shape-asymmetric systems. Here we show how the addition of tiny non-adsorbing spheres (depletants) to a dense system of hard disc-like particles (discotics) leads to coexistence between two distinct, highly dense (liquid)-crystalline columnar phases. This coexistence emerges due to the directional-dependent free-volume pockets for depletants. Theoretical results are confirmed by simulations explicitly accounting for the binary mixture of interest. We define the stability limits of this columnar-columnar coexistence and quantify the directional-dependent depletant partitioning. This journal is

Structurally complex hierarchical block copolymer assemblies can be formed in solution via the interplay of multiple assembly pathways. Crystallizable block copolymers can undergo self-assembly, crystallization or phase separation in solution. By selecting appropriate solvency conditions (solvent and temperature) it is possible to induce an interplay between these processes resulting in a complex association behavior. This leads to the formation of assemblies with up to four levels of hierarchical organization. Furthermore, varying the copolymer composition enables to tune the formation mechanism and the morphology of the aggregates.

[Image: see text] Dimple colloids with well-defined cavities were synthesized by a modified dispersion polymerization. The key step in the procedure is the delayed addition of cross-linkers into the reaction mixture. By systematically studying the effect of the delayed addition time and the concentration of the cross-linker on the resulting particle morphology, we identified the dominating driving force that underlies dimple formation. The delayed addition of cross-linkers results in colloids with a core–shell morphology consisting of a core rich in linear polymers and a cross-linked shell. This morphology was confirmed by selectively etching non-cross-linked material using dimethylformamide. With polymerization proceeding, consumption of monomers present in the swollen particles leads to contraction of the particles, which is larger for the core composed of linear polymers compared to the stiffer cross-linked shell. To accommodate this decrease in volume, the outer cross-linked shell has to buckle, resulting in a well-defined dimple. Furthermore, we extended the procedure to incorporate functional monomers, yielding chemically modifiable dimple particles. Subsequently, we showed that by leveraging the core–shell structure, these dimple particles can be used to prepare dumbbell-shaped colloids with one hollow and one solid lobe. These partially hollow anisotropic particles assemble into strings with well-defined orientations in an alternating current electric field.

Fluid-bicontinuous gels are unique materials that allow two distinct fluids to interact through a percolating, rigid scaffold. Current restrictions for their use are the large fluid-channel sizes (>5 µm), limiting the fluid–fluid interaction surface-area, and the inability to flow liquids through the channels. In this work a scalable synthesis route of nanoparticle stabilized fluid-bicontinuous gels with channels sizes below 500 nm and specific surface areas of 2 m2 cm−3 is introduced. Moreover, it is demonstrated that liquids can be pumped through the fluid-bicontinuous gels via electroosmosis. The fast liquid flow in the fluid-bicontinuous gel facilitates their use for molecular separations in continuous-flow liquid–liquid extraction. Together with the high surface areas, liquid flow through fluid-bicontinuous gels enhances their potential as highly permeable porous materials with possible uses as microreaction media, fuel-cell components, and separation membranes.

Cell-surface expressed contactin 1 and neurofascin 155 control wiring of the nervous system and interact across cells to form and maintain paranodal myelin-axon junctions. The molecular mechanism of contactin 1 – neurofascin 155 adhesion complex formation is unresolved. Crystallographic structures of complexed and individual contactin 1 and neurofascin 155 binding regions presented here, provide a rich picture of how competing and complementary interfaces, post-translational glycosylation, splice differences and structural plasticity enable formation of diverse adhesion sites. Structural, biophysical, and cell-clustering analysis reveal how conserved Ig1-2 interfaces form competing heterophilic contactin 1 – neurofascin 155 and homophilic neurofascin 155 complexes whereas contactin 1 forms low-affinity clusters through interfaces on Ig3-6. The structures explain how the heterophilic Ig1-Ig4 horseshoe’s in the contactin 1 – neurofascin 155 complex define the 7.4 nm paranodal spacing and how the remaining six domains enable bridging of distinct intercellular distances.

The characterization of periodic order in assemblies of colloidal particles can be complicated by the coincidence of Bragg diffraction peaks of the structure and minima in the form factor of the particles. Here, we demonstrate a general strategy to overcome this problem that is applicable to all low-dimensional structures. This approach is demonstrated in the application of small-angle X-ray scattering (SAXS) for the characterization of monolayers of colloidal silica superballs prepared using the unidirectional rubbing method. In this method, the ordering of the colloidal superballs is achieved by mechanically rubbing them onto a polydimethylsiloxane (PDMS)-coated surface. Using three differently shaped superballs, ranging from spherical to almost cubic, we show that certain Bragg peaks may not appear in the diffraction patterns due to the presence of minima in the form factor. We show that these missing Bragg peaks can be visualized by imaging the colloidal monolayers at various orientations. Moreover, we argue that the same strategy can be applied to other techniques, such as neutron scattering.