Colloidal Phase Research Articles

In Situ X-ray Scattering Reveals Coarsening Rates of Superlattices Self-Assembled from Electrostatically Stabilized Metal Nanocrystals Depend Nonmonotonically on Driving Force.

Self-assembly of colloidal nanocrystals (NCs) into superlattices (SLs) is an appealing strategy to design hierarchically organized materials with promising functionalities. Mechanistic studies are still needed to uncover the design principles for SL self-assembly, but such studies have been difficult to perform due to the fast time and short length scales of NC systems. To address this challenge, we developed an apparatus to directly measure the evolving phases in situ and in real time of an electrostatically stabilized Au NC solution before, during, and after it is quenched to form SLs using small-angle X-ray scattering. By developing a quantitative model, we fit the time-dependent scattering patterns to obtain the phase diagram of the system and the kinetics of the colloidal and SL phases as a function of varying quench conditions. The extracted phase diagram is consistent with particles whose interactions are short in range relative to their diameter. We find the degree of SL order is primarily determined by fast (subsecond) initial nucleation and growth kinetics, while coarsening at later times depends nonmonotonically on the driving force for self-assembly. We validate these results by direct comparison with simulations and use them to suggest dynamic design principles to optimize the crystallinity within a finite time window. The combination of this measurement methodology, quantitative analysis, and simulation should be generalizable to elucidate and better control the microscopic self-assembly pathways of a wide range of bottom-up assembled systems and architectures.

Copper Speciation in Wine Growing-Drain Waters: Mobilization, Transport, and Environmental Diffusion

Copper (Cu) has been used to treat vines for a long time, which has led to its accumulation in vineyard soils. In the present work, the mobilization of copper from these soils and its transport, and diffusion outside the plots by drain water were investigated. For this, the distribution of copper between the dissolved and colloidal phases, and within the colloidal phase, of these waters was determined using an investigation strategy based on the coupling between a size separation technique, asymmetric flow field-flow fractionation, and several detectors. First, the total copper concentrations in water from different drains were monitored over a period of 2 years: Cu was mainly found in the fraction of < 450 nm. Then, the distribution of copper on the size continuum was more closely studied in water from one of the drains, sampled over a winter period. Between 45 and 75% of Cu was found in the 2–450 nm colloidal fraction. The <450 nm colloidal phase of the drain waters was found to be mainly composed of humic acids (~15 to 60 mg L−1) and clay-rich particles (~100 to 650 mg (Al) L−1). These particles also contained (hydr)oxides of iron and manganese. The concentrations of Fe and Mn were approximately 100 to 200 times lower than those of Al. The majority of humic acids had an apparent molar mass of ≤ 10 kDa. They were distributed along the size continuum: (i) in a population with an average size of ~20 nm, probably consisting of supramolecular entities, and (ii) associated with clay-rich particles with a size of ~120–200 nm. Copper was found to be complexed with humic acids and associated with clays via clay-humic complexes. Copper mobilization from the soil to the water and its transport to the drain water appeared governed by the soil humidity level and the rainfall.

Structural Properties of Casein Micelles with Adjusted Micellar Calcium Phosphate Content.

Micellar calcium phosphate (MCP) content of skim milk was modified by pH adjustment followed by dialysis. Turbidity, casein micelle size and partitioning of Ca and caseins between the colloidal and soluble phases of milk were determined. Protein structure was characterised by Fourier transform infrared (FTIR) spectroscopy and proton nuclear magnetic resonance (1H NMR), whereas organic and inorganic phosphorus were studied by phosphorus-31 nuclear magnetic resonance (31P NMR). The sample with the lowest MCP content (MCP7) exhibited the smallest particle size and turbidity, measuring 83 ± 8 nm and 0.08 ± 0.01 cm-1, respectively. Concentrations of soluble caseins increased with decreasing MCP levels. At ~60% MCP removal, FTIR analysis indicated a critical stage of structural rearrangement and 31P NMR analysis showed an increase in signal intensity for Ca-free Ser-P, which further increased as MCP concentration was further reduced. In conclusion, this study highlighted the importance of MCP in maintaining micellar structure and its impact on the integrity of casein micelle.

Surface-mediated spontaneous emulsification of the acylated peptide semaglutide

Acylated peptides composed of glucagon-like peptide-1 receptor agonists modified with a fatty acid side chain are an important class of therapeutics for type 2 diabetes and obesity but are susceptible to an unusual physical instability in the presence of hydrophobic surfaces, i.e., spontaneous emulsification, also known as ouzo formation in practice. In this work, light scattering, small-angle X-ray scattering, and circular dichroism measurements are used to characterize the physical properties of the semaglutide colloidal phase, including size distribution, shape, secondary structure, internal structure, and internal composition, as a function of solution physico-chemical conditions. The existence and size of the colloids formed are successfully predicted by a classical Rayleigh model, which identifies the parameters controlling their size and formation. Colloid formation is found to be catalyzed by hydrophobic surfaces, and formation rates are modeled as an autocatalytic reaction, enabling the formation of a master curve for various surfaces that elucidates the mechanism. Surfaces differ due to differences in surface wettability, which can be correlated with Hansen solubility parameters. This work provides insights into this unusual colloidal phenomenon and guides the peptide synthesis process and drug product formulation in the pharmaceutical industry.

Interparticle interaction-dependent jamming in colloids: insights into glass transition and morphology modulation during rapid evaporation-induced assembly.

Understanding the role of interparticle interactions in jamming phenomena is essential for gaining insights into the intriguing glass transition behavior observed in atomic and molecular systems. In this study, we investigate the jamming behavior of colloids with tunable interparticle interactions during evaporation-induced assembly (EIA). By manipulating the interaction among charged colloids using cationic polyethyleneimine (PEI) through electro-sorption and subsequent free polymer induced repulsion, we observe distinct jamming behavior in silica colloids during EIA, depending on the interparticle interactions. Silica colloids with strong repulsive interactions exhibit a repulsive colloidal glass state with a volume fraction of silica colloids in supraparticle ϕ ∼ 0.70. On the other hand, PEI-mediated attractive interactions among silica colloids lead to an attractive colloidal glass phase with a significantly lower ϕ ∼ 0.43. Free polymer induced repulsion of colloids at higher PEI concentration once again results in a repulsive glassy state with ϕ ∼ 0.61. Furthermore, we revealed that interparticle interactions not only influence the jamming behavior but also play a significant role in shaping the morphology of self-assembled structures during EIA, and the assembled structure undergoes a morphological reentrant transition from a doughnut-like shape to a spherical form and again back to a doughnut-like configuration. Jamming-dependent evolution of micropores and dynamics of the confined PEI have been probed using positron annihilation lifetime spectroscopy (PALS) and broadband dielectric spectroscopy (BDS). PALS reveals distinct variations in the micropores of the supraparticles with different PEI loadings, confirming the impact of jamming on the evolution of the micropores within the supraparticles. BDS measurements uncover non-monotonic dynamics of PEI molecules confined in the evolved pore network. It is revealed that the reentrant jamming behavior of colloids, modulated by PEI, holds profound significance for the long-term stability of supraparticles.

Role of interaction range on the microstructure and dynamics of attractive colloidal systems.

Colloidal gelation phase diagram has been traditionally characterized using three key factors: particle volume fraction, strength of attraction, and range of attraction. While there's a rich body of literature on the role of attraction strength and particle volume fraction, majority of studies have been limited to short range interactions. Using Brownian dynamics simulations, we explored the effect that the range of attractions has on the microstructure and dynamics of both weakly and strongly attractive colloidal systems. Although gelation occurs significantly faster at high attraction strength, by an order of magnitude compared to low strength, we did not observe any clear trend in gelation-rate with respect to a change in the range of interaction. However, as the attraction range increases in both systems, the final structure undergoes a transition from a single connected network to a fluid of dense clusters. This results in a new gelation phase boundary for long range attractive colloids.

Wildland-urban interface wildfire increases metal contributions to stormwater runoff in Paradise, California.

The 2018 Camp Fire was a large late-year (November) wildfire that produced an urban firestorm in the Town of Paradise, California, USA, and destroyed more than 18 000 structures. Runoff from burned wildland areas is known to contain ash, which can transport contaminants including metals into nearby watersheds. However, due to historically infrequent occurrences, the effect of wildland-urban interface (WUI) fires, such as the Camp Fire, on surface water quality has not been well-characterized. Therefore, this study investigated the effects of widespread urban burning on surface water quality in major watersheds of the Camp Fire area. Between November 2018 and May 2019, 140 surface water samples were collected, including baseflow and stormflow, from burned and unburned watersheds with varying extent of urban development. Samples were analyzed for total and filter-passing metals, dissolved organic carbon, major anions, and total suspended solids. Ash and debris from the Camp Fire contributed metals to downstream watersheds via runoff throughout the storm season. Increases in concentration up to 200-fold were found for metals Cr, Cu, Ni, Pb, and Zn in burned watersheds compared to pre-fire values. Total concentrations of Al, Cd, Cu, Pb, and Zn exceeded EPA aquatic habitat acute criteria by up to 16-fold for up to five months after the fire. To assess possible transport mechanisms and bioavailability, a subset of 18 samples was analyzed using four filters with nominal pore sizes ranging from 0.22 to 1.2 μm to determine the particulate size distribution of metals. Trace and major metals (Al, Ba, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, and Zn) were found mostly associated with larger grain sizes (>0.45 μm), and some metals (Al, Cr, Fe, and Pb) also included a substantial colloidal phase (0.22 to 0.45 μm). This study suggests that fires in the wildland-urban interface increase metal concentrations, mainly through particulate driven transport. The metals with the largest increases are likely from anthropogenic disaster materials, though biomass ash also is a major contributor to water quality. The increase in metals following WUI burning may have adverse ecological impacts.

Temperature-Modulated Reversible Clustering of Gold Nanorods Driven by Small Surface Ligands.

Temperature-modulated colloidal phase of plasmonic nanoparticles is a convenient playground for resettable soft-actuators or colorimetric sensors. To render reversible clustering under temperature change, bulky ligands are required, especially if anisotropic morphologies are of interest. This study showcases thermoresponsive gold nanorods by employing small surface ligands, bis (p-sulfonatophenyl) phenyl-phosphine dihydrate dipotassium salt (BSPP) and native cationic surfactant. Temperature-dependent analysis in real-time allowed to describe the structural features (interparticle distance and cluster size) as well as thermal parameters, melting and freezing temperatures. These findings suggest that neither covalent Au-S bonds nor bulky ligands are required to obtain a robust thermoresponsive system based on anisotropic gold nanoparticles, paving the way to stimuli-responsive nanoparticles with a wide range of sizes and geometries.

Development of Polymer-Encapsulated, Amine-Functionalized Zinc Ferrite Nanoparticles as MRI Contrast Agents.

The need for stable and well-defined magnetic nanoparticles is constantly increasing in biomedical applications; however, their preparation remains challenging. We used two different solvothermal methods (12 h reflux and a 4 min microwave, MW) to synthesize amine-functionalized zinc ferrite (ZnFe2O4-NH2) superparamagnetic nanoparticles. The morphological features of the two ferrite samples were the same, but the average particle size was slightly larger in the case of MW activation: 47 ± 14 nm (Refl.) vs. 63 ± 20 nm (MW). Phase identification measurements confirmed the exclusive presence of zinc ferrite with virtually the same magnetic properties. The Refl. samples had a zeta potential of -23.8 ± 4.4 mV, in contrast to the +7.6 ± 6.8 mV measured for the MW sample. To overcome stability problems in the colloidal phase, the ferrite nanoparticles were embedded in polyvinylpyrrolidone and could be easily redispersed in water. Two PVP-coated zinc ferrite samples were administered (1 mg/mL ZnFe2O4) in X BalbC mice and were compared as contrast agents in magnetic resonance imaging (MRI). After determining the r1/r2 ratio, the samples were compared to other commercially available contrast agents. Consistent with other SPION nanoparticles, our sample exhibits a concentrated presence in the hepatic region of the animals, with comparable biodistribution and pharmacokinetics suspected. Moreover, a small dose of 1.3 mg/body weight kg was found to be sufficient for effective imaging. It should also be noted that no toxic side effects were observed, making ZnFe2O4-NH2 advantageous for pharmaceutical formulations.

Characterization of porosity in periodic 3D nanostructures using spectroscopic scatterometry

Periodic nanostructures have important applications in nanophotonics and nanostructured materials as they provide various properties that are advantageous compared to conventional solid materials. However, there is a lack of metrology techniques that are suitable for large-scale manufacturing, as the traditional tools used in nanotechnology have limited throughput and depth resolution. In this work, we use spectroscopic scatterometry as a fast and low-cost alternative to characterize the porosity of three-dimensional (3D) periodic nanostructures. In this technique, the broadband reflectance of the structure is measured and fitted with physical models to predict the structure porosity. The process is demonstrated using 3D periodic nanostructures fabricated using colloidal phase lithography at various exposure dosages. The measured reflectance data are compared with an optical model based on finite-difference time-domain and transfer-matrix methods, which show qualitative agreement with the structure porosity. We found that this technique has the potential to further develop into an effective method to effectively predict the porosity of 3D nanostructures and can lead to real-time process control in roll-to-roll nanomanufacturing.

Simple and Complex Substrates (Sugar, Acetate and Milk Whey) for In Situ Bioremediation of Groundwater with Nitrate and Actinide Contamination

The complex contamination of groundwater near radioactive waste repositories by nitrates and actinides is a common problem for many nuclear fuel cycle facilities. One of the effective methods to remove nitrates and reduce actinide migration activity is bioremediation through the activation of native microbial communities by soluble electron donors and carbon sources. This work evaluated the effectiveness of using simple and complex electron donors to remove nitrate in the microbial community in an aquifer near the B2 storage of the Siberian Chemical Combine (Seversk, Siberia). The addition of sugar and milk whey led to the maximum efficiency of nitrate-ion removal and a decrease in the redox potential of the system, creating optimal conditions for the immobilization of actinide. Special attention was paid to the behavior of uranium, plutonium, neptunium, and americium under conditions simulating groundwater when sugar, acetate, and milk whey were added and when microbial metabolic products were formed. Neither microbial metabolites nor organic solutions were found to have a significant effect on the leaching of neptunium. At the same time, for plutonium, a decrease in yield was observed when rocks were treated with organic solutions were compared to groundwater treatment without them. Plutonium leaching is significantly affected by rock composition. In rocks with a low clay fraction content, its yield can reach 40%. At the same time, microbial metabolites can increase americium (Am) desorption from rocks with a low clay fraction content. Additionally, particle size analysis was performed using a step-by-step filtration approach, aiming to evaluate the risks that are associated with colloidal phase formation. It was shown that microbiological stimulation resulted in particle enlargement, substantially diminishing the presence of actinides in the form of dissolved or sub-50 nm nanoparticles. This outcome significantly reduced the potential for colloidal and pseudocolloidal transfer, thereby lowering associated risks.

Separation, characterization, and antiviral activity of colloidal phase state of Maxing Shigan Decoction

This study focused on the separation, characterization, content determination, and antiviral efficacy research on colloidal particles with different sizes in Maxing Shigan Decoction(MXSG). The mixed colloidal phase of MXSG was initially separated into small colloidal particle segment(S), medium colloidal particle segment(M), and big colloidal particle segment(B) using ultrafiltration. Further fine separation was performed using size-exclusion chromatography. Dynamic light scattering(DLS) and transmission electron microscopy(TEM) were employed to characterize the size and morphology of the separated colloidal particles. UPLC-MS/MS was used to determine the content of ephedrine, amygdalin, glycyrrhizic acid, and the EDTA complexometric titration was used to measure the calcium(Ca~(2+)) content in different colloidal phases. Finally, a respiratory syncytial virus(RSV) infection mouse model was established using intranasal administration. The experimental groups included a blank group, a model group, a ribavirin group, an MXSG group, an S group, an M group, and a B group. Oral administration was given for treatment, and pathological changes in mouse lung tissue and organ indices were evaluated. The results of the study showed that the distribution of ephedrine, amygdalin, glycyrrhizic acid, and Ca~(2+) content was not uniform among different colloidal segments. Among them, the B segment had the highest proportions of the three components, except for Ca~(2+), accounting for 46.35%, 53.72%, and 92.36%, respectively. Size-exclusion chromatography separated colloidal particles with uniform morphology in the size range of 100-500 nm. Compared to the S and M segments, the B segment showed an increased lung index inhibition rate(38.31%), spleen index, and thymus index in RSV-infected mice, and it improved the infiltration of inflammatory cells and lung injury in the lung tissue of mice. The complex components in MXSG form colloidal particles of various sizes and morphologies through heating, and small-molecule active components such as ephedrine, amygdalin, glycyrrhizic acid, and Ca~(2+) participate in the assembly to varying degrees. The main material basis for the antiviral effect of MXSG is the colloidal particles with certain particle sizes formed by the assembly of active components during the heating process.

Thermotropic Colloidal Liquid‐Crystalline Hydroxyapatite Nanorod Hybrids Containing a Forklike Mesogen

AbstractWe here report the development of new thermotropic colloidal liquid‐crystalline (LC) organic/inorganic hybrids consisting of a hydroxyapatite (HAp)/poly(acrylic acid) (PAA) nanorod and a dendritic forklike mesogen. Complexation of the HAp/PAA nanorod covered with negatively charged PAA and a cationic forklike mesogen through electrostatic interactions and cation metathesis results in the surface modification of the HAp/PAA nanorod with the forklike mesogen. While the HAp/PAA nanorod forms a lyotropic colloidal LC phase in the aqueous dispersion, the HAp/PAA nanorod modified with the forklike mesogen exhibits thermotropic colloidal LC phases in the solvent‐free states. The biomineral‐based organic/inorganic colloidal liquid crystals exhibiting thermotropic LC properties have potential for the development of new stimuli‐responsive sustainable materials.

Iron colloidal transport mechanisms and sequestration of As, Ni, and Cu along AMD-induced environmental gradients

Colloids are common in mine waters and their chemistry and interactions are critical aspects of metal(loid)s cycling. Previous studies mostly focus on the colloidal transport of metal(loid)s in zones where rivers and soil profiles receive acid mine drainage (AMD). However, there is limited knowledge of the colloid and the associated toxic element behavior as the effluent flows through the coal waste dump, where a geochemical gradient is produced due to AMD reacting with waste rocks which have high acid-neutralization effects. Here, we investigated the geochemistry of Fe and co-occurring elements As, Ni, and Cu along the coal waste dump, in aqueous, colloidal, and precipitate phases, using micro/ultrafiltration combined with STEM, AFM-nanoIR, SEM-EDS, XRD, and FTIR analysis. The results demonstrated that a fast attenuation of H+, SO42−, and metal(loid)s happened as the effluent flowed through the waste-rock dump. The Fe, As, Ni, and Cu were distributed across all colloidal sizes and primarily transported in the nano-colloidal phase (3 kDa–0.1 μm). An increasing pH induced a higher percentage of large Fe colloid fractions (> 0.1 μm) associated with greater sequestration of trace metals, and the values for As from 39.5 % to 54.4 %, Ni from 40.8 % to 75.7 %, and Cu from 43.7 % to 56.0 %, respectively. The Fe-bearing colloids in AMD upstream (pH ≤ 3.0) were primarily composed of Fe–O–S and Fe–O–C with minor Al–Si–O and Ca–O–S, while in less acidic and alkaline sections (pH ≥ 4.1), they were composed of Fe–O with minor Ca–O–S. The iron colloid agglomerates associated with As, Ni, and Cu precipitated coupling the transformation of jarosite, and schwertmannite to ferrihydrite, goethite, and gypsum. These results demonstrate that the formation and transformation of Fe-bearing colloids response to this unique geochemical gradient help to understand the natural metal(loid)s attenuation along the coal waste dump.

Colloidal and solid phase partitioning between ferrihydrite, humic acid and copper coprecipitates

Our understanding of the interactions between Fe oxides, humic acids (C), and Cu precipitation products in the environment are limited by our ability to measure specific forms and chemical interactions. Here, we examine the effect of solution pH, Fe:C molar ratio from 1:0 to 1:3, and Cu concentration on dissolved and colloidal Cu concentrations after sorption (SOR) or coprecipitation (CPT) reactions. This included specifically measuring the colloidal phases formed using asymmetrical flow field flow fractionation coupled to a total organic carbon analyzer and an inductively coupled plasma mass spectrometer. In the case of 1:0 Fe:C reactions, more Cu was associated with bulk solids and colloidal solids in CPT reaction products, particularly at pH 5 and 6. As C content increased, precipitation reactions led to more Cu retained in the bulk solid phase at lower pH, but more in the dissolved and colloidal phase at higher pH. Of the colloids formed at pH 7, about 10% of the dissolved Cu is present as Fe–C–Cu ternary phases, with the remainder as Cu–C or inorganic Cu phases, yet at pH 6, only Fe–Cu colloids were observed. Applying an additivity approach while using a NICA-Donnan C complexation model combined with a ferrihydrite surface complexation model, the model often predicts higher than observed dissolved Cu in CPT reactions with no C present, but lower than observed dissolved Cu with C present. In applying the model specifically to colloidal phases, much lower concentrations of colloid bound Cu is predicted than observed in the 1:0 Fe:C scenario, but as C content increases, more colloidal Cu is predicted than observed. Given the availability and lability of Cu in environmental systems is assumed to correspond to dissolved Cu, this work notes some differences in the dissolved and colloidal phases formed in different contexts.

PH control on organic and organo-mineral colloids carrying major and trace elements in leachates of wetland sludge deposits

Emission of colloids from treatment wetlands solid deposit (SD) may affect the speciation, toxicity and transfer of organic and inorganic pollutants, thereby controlling the associated environmental risks. This study investigated the nature of the colloids and their influence on the leaching of major and trace elements over a wide range of pH between 2 and 12. Results evidenced the mobilization of high quantity of organic carbon leached from the SD and Al-Fe colloidal minerals embedded by large organic molecules. Based on their varying affinity for the different colloidal phases, three groups of chemical species were established: (i) elements with low affinity for colloidal phases, mainly released in truly dissolved fraction (<3kDa) as inorganic species (Na, Rb, As, Sb, S, P, V); (ii) element strongly affected by the detachment of large colloids (>30 kDa), preferentially associated to organic colloids (Li, Ca, Mg, Sr, Ba, Mn, Zn) or to mineral colloids (Pb, Cr, Sc, Y); and (iii) element with high affinity for large and truly dissolved organic molecules (Cu, Co, Cd, Ni). Differences observed in the partitioning of elements can be attributed to variations in the pH/Eh of the solutions, the nature of the colloidal phases, and the ionic properties of the considered elements. Small pH variations were found to modify drastically the speciation of the elements solubilized with potential effect on their (bio)availability. Results obtained on this study can be used to enhance wastewater treatment through constructed wetland process and improve recovery technics applied on solid deposits (agriculture, compounds extraction…).

Minimal conditions for solidification and thermal processing of colloidal gels

Colloidal gelation is used to form processable soft solids from a wide range of functional materials. Although multiple gelation routes are known to create gels of different types, the microscopic processes during gelation that differentiate them remain murky. A fundamental question is how the thermodynamic quench influences the microscopic driving forces of gelation, and determines the threshold or minimal conditions where gels form. We present a method that predicts these conditions on a colloidal phase diagram, and mechanistically connects the quench path of attractive and thermal forces to the emergence of gelled states. Our method employs systematically varied quenches of a colloidal fluid over a range of volume fractions to identify minimal conditions for gel solidification. The method is applied to experimental and simulated systems to test its generality toward attractions with varied shapes. Using structural and rheological characterization, we show that all gels incorporate elements of percolation, phase separation, and glassy arrest, where the quench path sets their interplay and determines the shape of the gelation boundary. We find that the slope of the gelation boundary corresponds to the dominant gelation mechanism, and its location approximately scales with the equilibrium fluid critical point. These results are insensitive to potential shape, suggesting that this interplay of mechanisms is applicable to a wide range of colloidal systems. By resolving regions of the phase diagram where this interplay evolves in time, we elucidate how programmed quenches to the gelled state could be used to effectively tailor gel structure and mechanics.

Critical roles of metal–ligand complexes in the controlled synthesis of various metal nanoclusters

Metal nanoclusters (NCs), an important class of nanoparticles (NPs), are extremely small in size and possess quasi-molecular properties. Due to accurate stoichiometry of constituent atoms and ligands, NCs have strong structure-property relationship. The synthesis of NCs is seemingly similar to that of NPs as both are formed by colloidal phase transitions. However, they are considerably different because of metal-ligand complexes in NC synthesis. Reactive ligands can convert metal salts to complexes, actual precursors to metal NCs. During the complex formation, various metal species occur, having different reactivity and fraction depending on synthetic conditions. It can alter their degree of participation in NC synthesis and the homogeneity of final products. Herein, we investigate the effects of complex formation on the entire NC synthesis. By controlling the fraction of various Au species showing different reactivity, we find that the extent of complex formation alters reduction kinetics and the uniformity of Au NCs. We demonstrate that this concept can be universally applied to synthesize Ag, Pt, Pd, and Rh NCs.

Smectite phase separation is driven by hydration-mediated interfacial charge

Smectite clay minerals have an outsize impact on the response of clay-rich media to common stimuli, such as hydration and ion exchange, motivating extensive effort to understand behaviors resulting from these processes such as swelling and exfoliation. Smectites are common and historic systems for investigating colloidal and interfacial phenomena, with two swelling regimes commonly identified across myriad clays: osmotic swelling at high water activity and crystalline swelling at low water activity. However, no current swelling model seamlessly spans the full ranges of water, salt and clay content encountered in natural or engineered settings. Here, we show that structures previously rationalized as either osmotic or crystalline coexist as a rich array of distinct colloidal phases that differ by water content, layer stacking thickness, and curvature. We present an analytical model for intermolecular potentials among water, salt and clay in both mono- and divalent electrolytes that predicts swelling pressures across high and low water activities. Our results indicate that all clay swelling is osmotic swelling, but that the osmotic pressure of charged mineral interfaces becomes attractive and dominates that of the electrolyte at high clay activities. Global energy minima are often not reached on experimental timescales due to many local energy minima that promote long-lived intermediate states with vast differences in clay, ion, and water mobilities, leading to hyperdiffusive layer dynamics driven by variable hydration-mediated interfacial charge.TeaserDistinct colloidal phases of swelling clays emerge via ion (de)hydration at mineral interfaces that drives hyperdiffusive layer dynamics as metastable smectites approach equilibrium.

Photochromism from wavelength-selective colloidal phase segregation

Phase segregation is ubiquitously observed in immiscible mixtures, such as oil and water, in which the mixing entropy is overcome by the segregation enthalpy1–3. In monodispersed colloidal systems, however, the colloidal–colloidal interactions are usually non-specific and short-ranged, which leads to negligible segregation enthalpy4. The recently developed photoactive colloidal particles show long-range phoretic interactions, which can be readily tuned with incident light, suggesting an ideal model for studying phase behaviour and structure evolution kinetics5,6. In this work, we design a simple spectral selective active colloidal system, in which TiO2 colloidal species were coded with spectral distinctive dyes to form a photochromic colloidal swarm. In this system, the particle–particle interactions can be programmed by combining incident light with various wavelengths and intensities to enable controllable colloidal gelation and segregation. Furthermore, by mixing the cyan, magenta and yellow colloids, a dynamic photochromic colloidal swarm is formulated. On illumination of coloured light, the colloidal swarm adapts the appearance of incident light due to layered phase segregation, presenting a facile approach towards coloured electronic paper and self-powered optical camouflage.