Colloidal Model System Research Articles

Fluorimetric detection of distinct lyotropic anion interactions on nanoscopic surfaces

The molecular structure, stability and function of proteins, nucleic acids, and many other colloidal entities including nanomaterials depend greatly on their highly specific response towards surrounding solvent molecules and inorganic ions. In order to earn an unambiguous mechanistic insight into the origin of these effects, water-soluble fluorescent carbon nanomaterials having amide groups in a hydrophobic microenvironment were successfully employed as the model colloidal system in this research study. Quantum dots with acidic functionalities were first of all prepared using a simple carbon precursor. Subsequently, chemical modification of carbon quantum dots (CQDs) was carried out with isopropylamine to impart protein-like amide richness to the nanoparticle surface. Moreover, the prepared CQDs were found to be highly fluorescent. Fluorescence intensity, interestingly, showed unique modulation patterns on incubation with different types of anions. Lipophilic chaotropic anions such as I−, SCN−, and Br− showed concentration-dependent fluorescence quenching whereas hydrophilic kosmotropic anions like SO42− had almost no impact on the nanomaterial fluorescence. This striking observation in the case of chaotropic anions can be correlated to their strong partitioning affinity for the amide groups on the nanomaterial surface. High charge density anions like sulphate, on the other hand, are mostly excluded from the colloidal interfaces. The current study emphasizes the fact that the functional groups available on the surface of macromolecules as well as anion's inherent thermodynamic parameters in a solvent play a pivotal role in the observed anion specificity.

Chaining of hard disks in nematic needles: particle-based simulation of colloidal interactions in liquid crystals

Colloidal particles suspended in liquid crystals can exhibit various effective anisotropic interactions that can be tuned and utilized in self-assembly processes. We simulate a two-dimensional system of hard disks suspended in a solution of dense hard needles as a model system for colloids suspended in a nematic lyotropic liquid crystal. The novel event-chain Monte Carlo technique enables us to directly measure colloidal interactions in a microscopic simulation with explicit liquid crystal particles in the dense nematic phase. We find a directional short-range attraction for disks along the director, which triggers chaining parallel to the director and seemingly contradicts the standard liquid crystal field theory result of a quadrupolar attraction with a preferred {45^{circ }} angle. Our results can be explained by a short-range density-dependent depletion interaction, which has been neglected so far. Directionality and strength of the depletion interaction are caused by the weak planar anchoring of hard rods. The depletion attraction robustly dominates over the quadrupolar elastic attraction if disks come close. Self-assembly of many disks proceeds via intermediate chaining, which demonstrates that in lyotropic liquid crystal colloids depletion interactions play an important role in structure formation processes.

Dynamical processes of interstitial diffusion in a two-dimensional colloidal crystal

In two-dimensional (2D) solids, point defects, i.e., vacancies and interstitials, are bound states of topological defects of edge dislocations and disclinations. They are expected to play an important role in the thermodynamics of the system. Yet very little is known about the detailed dynamical processes of these defects. Two-dimensional colloidal crystals of submicrometer microspheres provide a convenient model solid system in which the microscopic dynamics of these defects can be studied in real time using video microscopy. Here we report a study of the dynamical processes of interstitials in a 2D colloidal crystal. The diffusion constants of both mono- and diinterstitials are measured and found to be significantly larger than those of vacancies. Diinterstitials are clearly slower than monointerstitials. We found that, by plotting the accumulative positions of five- and sevenfold disclinations relative to the center-of-mass position of the defect, a sixfold symmetric pattern emerges for monointerstitials. This is indicative of an equilibrium behavior that satisfies local detailed balance that the lattice remains elastic and can be thermally excited between lattice configurations reversibly. However, for diinterstitials the sixfold symmetry is not observed in the same time window, and the local lattice distortions are too severe to recover quickly. This observation suggests a possible route to creating local melting of a lattice (similarly one can create local melting by creating divacancies). This work opens up an avenue for microscopic studies of the dynamics of melting in colloidal model systems.

Tuning Material Properties of Nanoemulsion Gels by Sequentially Screening Electrostatic Repulsions and Then Thermally Inducing Droplet Bridging.

Nanoemulsions are widely used in applications such as food products, cosmetics, pharmaceuticals, and enhanced oil recovery for which the ability to engineer material properties is desirable. Moreover, nanoemulsions are emergent model colloidal systems because of the ease in synthesizing monodisperse samples, flexibility in formulations, and tunable material properties. In this work, we study a nanoemulsion system previously developed by our group in which gelation occurs through thermally induced polymer bridging of droplets. We show here that the same system can undergo a sol–gel transition at room temperature through the addition of salt, which screens the electrostatic interaction and allows the system to assemble via depletion attraction. We systematically study how the addition of salt followed by a temperature jump can influence the resulting microstructures and rheological properties of the nanoemulsion system. We show that the salt-induced gel at room temperature can dramatically restructure when the temperature is suddenly increased and achieves a different gelled state. Our results offer a route to control the material properties of an attractive colloidal system by carefully tuning the interparticle potentials and sequentially triggering the colloidal self-assembly. The control and understanding of the material properties can be used for designing hierarchically structured hydrogels and complex colloid-based materials for advanced applications.

Thermally and pH-responsive gelation of nanoemulsions stabilized by weak acid surfactants

Nanoemulsions are widely used in applications such as in food products, pharmaceutical ingredients and cosmetics. Moreover, nanoemulsions have been a model colloidal system due to their ease of synthesis and the flexibility in formulations that allows one to engineer the inter-droplet potentials and thus to rationally tune the material microstructures and rheological properties. In this article, we study a nanoemulsion system in which the inter-droplet interactions are modulated by temperature and pH. We develop a nanoemulsion suspension in which the droplets are stabilized by weak acid surfactants whose charged state can be independently controlled by temperature and pH, leading to a responsive electrostatic repulsion. Moreover, the additional poly(ethylene glycol) segment (PEG) on the surfactant gives rise to a temperature responsive attraction between droplets via PEG-PEG association and ion-dipole interaction. The interplay of these three interactions gives rise to non-monotonic trends in material properties and structures as a function of temperature. The underlying mechanism resulting in these trends is obtained by carefully characterizing the nanoemulsion droplets and studying the molecular interactions. Such mechanistic understanding also provides guidance to modulate the inter-droplet potential using pH and ionic strength. Moreover, the molecular understanding of the weak acid surfactant also sheds light on the destabilization of the nanoemulsion droplets triggered by a switch in pH. The control of the competition of attractive and repulsive interactions using external stimuli opens up the possibility to design complex nanoemulsion-based soft materials with controllable structures and rheological properties.

Fluorescein ether-ester dyes for labeling of fluorinated methacrylate nanoparticles

Fluorescent core-shell particles are used as versatile fluorophores in confocal microscopy based image analysis and as a colloidal model system to study short and long-range interactions. Bright and stable microspherical probes are proposed as promising materials, especially in bioimaging applications. The release of dyes from fluorescent polymer microspheres is undesirable. Covalent linking of dyes within polymeric spheres during the polymerization process can solve the problem of dye leaching. This requires, e.g. the introduction of reactive groups into the dyes. Its more lipophilic ester-ether derivatives considerably reduced fluorescence. The fluorescent quantum yield of prepared nanoparticles was determined to be below 10%. As-prepared nanoparticles exhibited a low refractive index (1.293–1.349), hence their use is recommended. Scanning electron microscope (SEM) images and the fluorescence correlation spectroscopy (FCS) measurements confirmed high polydispersity of synthesized particles (40–230 nm), and are in agreement with the dynamic light scattering (DLS) and nanoparticle tracking analysis (NTA) results (hydrodynamic diameters 203 ± 9, 548 ± 50, 146 ± 2 nm). The zeta potential of fluorescent 1H,1H-heptafluoro-n-butyl methacrylate (HFBMA) shell nanoparticles (NPs) with propargyl ether-esters, 2-methyl allyl ether-esters and allyl ether-esters of fluorescein was -44.5,-14, -44.7 mV, respectively. The values are different despite the slight difference in the structure of ester-ether derivatives.

Colloidal Organosilica Spheres for Three-Dimensional Confocal Microscopy.

We describe the synthesis and application of 3-(trimethoxysilyl)propyl methacrylate (TPM) particles as a colloidal model system for three-dimensional (3D) confocal scanning laser microscopy. The effect of the initial TPM concentration on the growth and polydispersity of the particles and a recently developed solvent transfer method to disperse particles in a refractive index and density-matching solvent mixture are reviewed and discussed. To fully characterize the system as a colloidal model, we measure the pair potential between the TPM particles directly using optical tweezers. Finally, we use 3D confocal microscopy to image a sedimentation-diffusion equilibrium of TPM particles to characterize the phase behavior and particle dynamics through successful detection and tracking of all particles in the field of view.

Acoustic characterisation of pH dependant reversible micellar casein aggregation

Ultrasound and light-based measurements were used to monitor changes in agitated and quiescent solution characteristics such as particle size distribution during casein aggregation and redistribution in a model colloidal system. The precipitation of casein micelles was controlled by adjusting the pH of the solution to alter the stability of the micelles. The studied dispersions were prepared at high pH, taken through the isoelectric point to precipitate and then re-dispersed by further lowering the pH at specific intervals. The isoelectric point was determined by zeta potential measurement at each specific pH interval. The isoelectric point of the casein dispersions was in the region of pH 4.3–4.7. Changes in the particle size of this reversible casein system were successfully measured acoustically. The dissolution rate and solution kinetics were subsequently monitored in a wide pH range using a combination of acoustic and light-based methods.

Thermophoresis of a Colloidal Rod: Contributions of Charge and Grafted Polymers.

In this study, we investigated the thermodiffusion behavior of a colloidal model system as a function of the Debye length, λDH, which is controlled by the ionic strength. Our system consists of an fd-virus grafted with poly(ethylene glycol) (PEG) with a molecular mass of 5000 g mol-1. The results are compared with recent measurements on a bare fd-virus and with results of PEG. The diffusion coefficients of both viruses are comparable and increase with the increasing Debye length. The thermal diffusion coefficient, DT, of the bare virus increases strongly with the Debye length, whereas DT of the grafted fd-virus shows only a very weak increase. The Debye length dependence of both systems can be described with an expression derived for charged rods using the surface charge density and an offset of DT as adjustable parameters. It turns out that the ratio of the determined surface charges is inverse to the ratio of the surfaces of the two systems, which means that the total charge remains almost constant. The determined offset of the grafted fd-virus describing the chemical contributions is the sum of DT of PEG and the offset of the bare fd-virus. At high λDH, corresponding to the low ionic strength, the ST values of both colloidal model systems approach each other. This implies a contribution from the polymer layer, which is strong at short λDH and fades out for the longer Debye lengths, when the electric double layer reaches further than the polymer chains and therefore dominates interactions with the surrounding water.

The solute mechanical properties impact on the drying of dairy and model colloidal systems.

The evaporation of colloidal solutions is frequently observed in nature and in everyday life. The investigation of the mechanisms taking place during the desiccation of biological fluids is currently a scientific challenge with potential biomedical and industrial applications. In the last few decades, seminal works have been performed mostly on dried droplets of saliva, urine and plasma. However, the full understanding of the drying process in biocolloids is far from being achieved and, notably, the impact of solute properties on the morphological characteristics of the evaporating droplets, such as colloid segregation, skin formation and crack pattern development, is still to be elucidated. For this purpose, the use of model colloidal solutions, whose rheological behavior is more easily deducible, could represent a significant boost. In this work, we compare the drying of droplets of whey proteins and casein micelles, the two main milk protein classes, to that of dispersions of silica particles and polymer-coated silica particles, respectively. The mechanical behavior of such biological colloids and model silica dispersions was investigated through the analysis of crack formation, and the measurements of their mechanical properties using indentation testing. The study reveals numerous analogies between dairy and the corresponding model systems, thus confirming the latter as a plausible powerful tool to highlight the signature of the matter at the molecular scale during the drying process.

A new look at effective interactions between microgel particles

Thermoresponsive microgels find widespread use as colloidal model systems, because their temperature-dependent size allows facile tuning of their volume fraction in situ. However, an interaction potential unifying their behavior across the entire phase diagram is sorely lacking. Here we investigate microgel suspensions in the fluid regime at different volume fractions and temperatures, and in the presence of another population of small microgels, combining confocal microscopy experiments and numerical simulations. We find that effective interactions between microgels are clearly temperature dependent. In addition, microgel mixtures possess an enhanced stability compared to hard colloid mixtures - a property not predicted by a simple Hertzian model. Based on numerical calculations we propose a multi-Hertzian model, which reproduces the experimental behavior for all studied conditions. Our findings highlight that effective interactions between microgels are much more complex than usually assumed, displaying a crucial dependence on temperature and on the internal core-corona architecture of the particles.

Synthesis and assembly of colloidal cuboids with tunable shape biaxiality

The design and assembly of monodisperse colloidal particles not only advances the development of functional materials, but also provides colloidal model systems for understanding phase behaviors of molecules. This communication describes the gram-scale synthesis of highly uniform colloidal cuboids with tunable dimension and shape biaxiality and their molecular mesogen-like assembly into various mesophasic structures in pristine purity. The synthesis relies on the nanoemulsion-guided generation of ammonium sulfate crystals that template the subsequent silica coating. The shape of the cuboidal particles can be tuned from square platelike, to biaxial boardlike, and to rodlike by independently controlling the length, width and thickness of the particles. We demonstrated the assembly of the cuboidal colloids into highly pure mesoscopic liquid crystal phases, including smectic A, biaxial smectic A, crystal B, discotic, and columnar phases, as well as established a correlation between mesophasic formation and colloidal biaxiality in experiments.

Depletion-interaction-driven assembly of golf ball-like particles for development of colloidal macromolecules

Colloidal molecules created by clustering monodisperse particles are a significant model system of atoms and molecules in colloidal scale. To attain modelling of complex or high-molecular-weight molecules such as hyper-branched polymers and proteins, it is required to develop a new assembling system which can prepare three-dimensionally designed colloidal molecules. In this study, we proposed an approach for complex colloidal molecules created by association between golf ball-like particles and spherical particles via depletion interaction. Several golf ball-like particles joined together, which formed joined particle assemblies at the spherical particles acting as their joints in a depletant solution. The number of golf ball-like particles in a particle assembly was increased by increasing the concentration of the depletant, leading to the formation of branched colloidal chains of the golf ball-like particles. Because the golf ball-like particles in the colloidal chain flexibly rotated at their joints, the conformation of the chains varied in the depletant solution. The present results demonstrated that the golf-ball like particle that can be joined to form colloidal macromolecules with high association number and high flexibility will be a promising building block for complex colloidal model systems.

Local structure in deeply supercooled liquids exhibits growing lengthscales and dynamical correlations

Glasses are among the most widely used of everyday materials, yet the process by which a liquid’s viscosity increases by 14 decades to become a glass remains unclear, as often contradictory theories provide equally good descriptions of the available data. Knowledge of emergent lengthscales and higher-order structure could help resolve this, but this requires time-resolved measurements of dense particle coordinates—previously only obtained over a limited time interval. Here we present an experimental study of a model colloidal system over a dynamic window significantly larger than previous measurements, revealing structural ordering more strongly linked to dynamics than previously found. Furthermore we find that immobile regions and domains of local structure grow concurrently with density, and that these regions have low configurational entropy. We thus show that local structure plays an important role at deep supercooling, consistent with a thermodynamic interpretation of the glass transition rather than a principally dynamic description.

Brownian dynamics of colloidal microspheres with tunable elastic properties from soft to hard

We study the Brownian thermal motion of a colloidal model system made by emulsifying hot liquid α-eicosene wax into an aqueous surfactant solution of sodium dodecyl sulfate (SDS). When this waxy oil-in-water emulsion is cooled below α-eicosene's melting point of Tc ≃ 25 °C, the microscale emulsion droplets solidify, effectively yielding a dispersed particulate system. So, the interiors of these wax droplets can be tuned from a viscous liquid to an elastic solid through very modest changes in absolute temperature. Using the multiple light scattering technique of diffusing wave spectroscopy (DWS), which is very sensitive to small-scale motion and shape fluctuations of dispersed colloidal objects, we show that the thermal fluctuations of the interfaces of these liquid droplets at higher temperature, seen in the DWS intensity–intensity correlation function at early times, effectively disappear when these droplets solidify at lower temperature. Thus, we show that the early-time behavior of this DWS correlation function can be used to probe mechanical properties of viscoelastic soft materials dispersed as droplets.

Vitrification and gelation in sticky spheres.

Glasses and gels are the two dynamically arrested, disordered states of matter. Despite their importance, their similarities and differences remain elusive, especially at high density, where until now it has been impossible to distinguish them. We identify dynamical and structural signatures which distinguish the gel and glass transitions in a colloidal model system of hard and "sticky" spheres. It has been suggested that "spinodal" gelation is initiated by gas-liquid viscoelastic phase separation to a bicontinuous network and the resulting densification leads to vitrification of the colloid-rich phase, but whether this phase has sufficient density for arrest is unclear [M. A. Miller and D. Frenkel, Phys. Rev. Lett. 90, 135702 (2003) and P. J. Lu et al., Nature 435, 499-504 (2008)]. Moreover alternative mechanisms for arrest involving percolation have been proposed [A. P. R. Eberle et al., Phys. Rev. Lett. 106, 105704 (2011)]. Here we resolve these outstanding questions, beginning by determining the phase diagram. This, along with demonstrating that percolation plays no role in controlling the dynamics of our system, enables us to confirm spinodal decomposition as the mechanism for gelation. We are then able to show that gels can be formed even at much higher densities than previously supposed, at least to a volume fraction of ϕ = 0.59. Far from being networks, these gels apparently resemble glasses but are still clearly distinguished by the "discontinuous" nature of the transition and the resulting rapid solidification, which leads to the formation of inhomogeneous (with small voids) and far-from-equilibrium local structures. This is markedly different from the glass transition, whose continuous nature leads to the formation of homogeneous and locally equilibrated structures. We further reveal that the onset of the attractive glass transition in the form of a supercooled liquid is in fact interrupted by gelation. Our findings provide a general thermodynamic, dynamic, and structural basis upon which we can distinguish gelation from vitrification.

Trapping/Pinning of colloidal microspheres over glass substrate using surface features

Suspensions of micro/nano particles made of Polystyrene, Poly(methyl methacrylate), Silicon dioxide etc. have been a standard model system to understand colloidal physics. These systems have proved useful insights into phenomena such as self-assembly. Colloidal model systems are also extensively used to simulate many condensed matter phenomena such as dynamics in a quenched disordered system and glass transition. A precise control of particles using optical or holographic tweezers is essential for such studies. However, studies of collective phenomena such as jamming and flocking behaviour in a disordered space are limited due to the low throughput of the optical trapping techniques. In this article, we present a technique where we trap and pin polystyrene microspheres ~10 μm over ‘triangular crest’ shaped microstructures in a microfluidic environment. Trapping/Pinning occurs due to the combined effect of hydrodynamic interaction and non-specific adhesion forces. This method allows trapping and pinning of microspheres in any arbitrary pattern with a high degree of spatial accuracy which can be useful in studying fundamentals of various collective phenomena as well as in applications such as bead detachment assay based biosensors.

Communication: Re-entrant limits of stability of the liquid phase and the Speedy scenario in colloidal model systems.

A re-entrant gas-liquid spinodal was proposed as a possible explanation of the apparent divergence of the compressibility and specific heat off supercooling water. Such a counter-intuitive possibility, e.g., a liquid that becomes unstable to gas-like fluctuations on cooling at positive pressure, has never been observed, neither in real substances nor in off-lattice simulations. More recently, such a re-entrant scenario has been dismissed on the premise that the re-entrant spinodal would collide with the gas-liquid coexisting curve (binodal) in the pressure-temperature plane. Here we study, numerically and analytically, two previously introduced one-component patchy particle models that both show (i) a re-entrant limit of stability of the liquid phase and (ii) a re-entrant binodal, providing a neat in silico (and in charta) realization of such unconventional thermodynamic scenario.

Oil-in-water microfluidics on the colloidal scale: new routes to self-assembly and glassy packings.

We have developed norland optical adhesive (NOA) flow focusing devices, making use of the excellent solvent compatibility and surface properties of NOA to generate micron scale oil-in-water emulsions with polydispersities as low as 5%. While current work on microfluidic oil-in-water emulsification largely concerns the production of droplets with sizes on the order of 10s of micrometres, large enough that Brownian motion is negligible, our NOA devices can produce droplets with radii ranging from 2 μm to 12 μm. To demonstrate the utility of these emulsions as colloidal model systems we produce fluorescently labelled polydimethylsiloxane droplets suitable for particle resolved studies with confocal microscopy. We analyse the structure of the resulting emulsion in 3D using coordinate tracking and the topological cluster classification and reveal a new mono-disperse thermal system.

The effect of colloidal aggregates on fat crystal networks.

We investigate the role of a colloidal model system in the crystallization and network formation of lipids. This system consists of fractal fumed silica aggregates. We look at the influence of different solid fat concentrations and fumed silica concentrations on the resulting gel network. Oscillatory rheology shows that the addition of silica to fat-in-oil gels does not significantly affect the magnitude of the storage modulus within the linear viscoelastic region. Interestingly, the range of this region is increased. Differential scanning calorimetry shows that the presence of silica leads to slightly earlier crystallization, though no significant effect on the melting profile of the formed network is found. Based on these observations, we propose that composite gel network structures have been formed. These results show that we have created reduced solid fat alternatives with similar rheological behaviour and thermal properties as the full-fat systems through the addition of colloidal silica.