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When monoclonal antibodies are exposed to an air-water interface, they form aggregates, which negatively impacts their performance. Until now, the detection and characterization of interfacial aggregation have been difficult. Here, we exploit the mechanical response imparted by interfacial adsorption by measuring the interfacial shear rheology of a model antibody, anti-streptavidin immunoglobulin-1 (AS-IgG1), at the air-water interface. Strong viscoelastic layers of AS-IgG1 form when the protein is adsorbed from the bulk solution. Creep experiments correlate the compliance of the interfacial protein layer with the subphase solution pH and bulk concentration. These, along with oscillatory strain amplitude and frequency sweeps, show that the viscoelastic behavior of the adsorbed layers is that of a soft glass with interfacial shear moduli on the order of 10 -3 Pa m. Shifting the creep compliance curves under different applied stresses forms master curves consistent with stress-time superposition of soft interfacial glasses. The interfacial rheology results are discussed in the context of the interface-mediated aggregation of AS-IgG1.

Wet processing of graphene sheets is a potentially interesting route for the economically viable creation of graphene-based composites. In the present work, flow dichroism and small-angle light scattering are used to investigate the dispersion of functionalized graphene sheets in a suspension and their response to shear flow. In line with expectations from scaling theory at rest, the functionalized graphene sheets are present as Brownian flat sheets, and there is no evidence of significant crumpling. More surprisingly, we find that the rate-dependent orientation of these molecularly thin sheets can be described by numerical predictions for hard spheroidal sheets, making quantitative predictions of the flow-induced orientation possible. Further comparison of the flow-induced orientation of thick gold decahedra with the thin graphene sheets shows that, except for effects of polydispersity, the flow-induced orientation is predicted well quantitatively. Adequate prediction of the effects of flow on the orientation of graphene sheets makes it possible to design wet processed graphene-based composite materials.

Particle-laden interfaces can be used to stabilize a variety of high-interface systems, from foams over emulsions to polymer blends. The relation between the particle interactions, the structure and rheology of the interface, and the stability of the system remains unclear. In the present work, we experimentally investigate how micron-sized, near-hard-sphere-like particles affect the mechanical properties of liquid interfaces. In particular, by comparing dried and undried samples, we investigate the effect of aggregation state on the properties of the particle-laden liquid interface and its relation to the stability of the corresponding Pickering emulsions. Partially aggregated suspensions give rise to a soft-solid-like response under shear, whereas for stable PMMA particulate layers a liquid-like behavior is observed. For interfacial creep-recovery measurements, we present an empirical method to correct for the combined effect of the subphase drag and the compliance of the double-wall ring geometry, which makes a significant contribution to the apparent elasticity of weak interfaces. We further demonstrate that both undried and dried PMMA particles can stabilize emulsions for months, dispelling the notion that particle aggregation, in bulk or at the interface, is required to create stable Pickering emulsions. Our results indicate that shear rheology is a sensitive probe of colloidal interactions but is not necessarily a predictor of the stability of interfaces, e.g., in quiescent Pickering emulsions, as in the latter the response to dilatational deformations can be of prime importance.

Measuring thicknesses in thin films with high spatial and temporal resolution is of prime importance for understanding the structure and dynamics in thin films and membranes. In the present work, we introduce fluorescence-interferometry, a method that combines standard reflected light thin film interferometry with simultaneous fluorescence measurements. We apply this method to the thinning dynamics and phase separation in free-standing inverse phospholipid bilayer films. The measurements were carried out using a standard fluorescence microscope using multichannel imaging and yielded subnanometer resolution, which is applied to optically measure the discrete thickness variations across phase-separated membranes., Competing Interests: The authors declare no competing financial interest.

The thermal motion of polymer chains in a crowded environment is anisotropic and highly confined. Whereas theoretical and experimental progress has been made, typically only indirect evidence of polymer dynamics is obtained either from scattering or mechanical response. Toward a complete understanding of the complicated polymer dynamics in crowded media such as biological cells, it is of great importance to unravel the role of heterogeneity and molecular individualism. In the present work, we investigate the dynamics of synthetic polymers and the tube-like motion of individual chains using time-resolved fluorescence microscopy. A single fluorescently labeled polymer molecule is observed in a sea of unlabeled polymers, giving access to not only the dynamics of the probe chain itself but also to that of the surrounding network. We demonstrate that it is possible to extract the characteristic time constants and length scales in one experiment, providing a detailed understanding of polymer dynamics at the single chain level. The quantitative agreement with bulk rheology measurements is promising for using local probes to study heterogeneity in complex, crowded systems.

The synthesis of nanoparticle clusters, also referred to as colloidal clusters or colloidal molecules, is being studied intensively as a model system for small molecule interactions as well as for the directed self-assembly of advanced materials. This paper describes a technique for the interfacial assembly of planar colloidal clusters using a combination of top-down lithographic surface modification and bottom-up Langmuir-Blodgett deposition. Micrometer sized polystyrene latex particles were deposited onto a chemically modified substrate from a decane-water interface with Langmuir-Blodgett deposition. The surface of the substrate contained hydrophilic domains of various size, spacing, and shape, while the remainder of the substrate was hydrophobic. Particles selectively deposited onto hydrophilic regions from the decane-water interface. The number of deposited particles depended on the size of each patch, thereby demonstrating that tuning cluster size is possible by engineering patch geometry. Following deposition, the clusters were permanently bonded with temperature annealing and then removed from the substrate via sonication. The permanently bonded planar colloidal clusters were stable in an aqueous environment and at a decane-water interface laden with isotropic colloidal particles. The method is a simple and fast way to synthesize colloidal clusters with few limitations on particle chemistry, composition, and shape.

Deposition of linear DNA molecules is a critical step in many single-molecule genomic approaches including DNA mapping, fiber-FISH, and several emerging sequencing technologies. In the ideal situation, the DNA that is deposited for these experiments is absolutely linear and uniformly stretched, thereby enabling accurate distance measurements. However, this is rarely the case, and furthermore, current approaches for the capture and linearization of DNA on a surface tend to require complex surface preparation and large amounts of starting material to achieve genomic-scale mapping. This makes them technically demanding and prevents their application in emerging fields of genomics, such as single-cell based analyses. Here we describe a simple and extremely efficient approach to the deposition and linearization of genomic DNA molecules. We employ droplets containing as little as tens of picograms of material and simply drag them, using a pipet tip, over a polymer-coated coverslip. In this report we highlight one particular polymer, Zeonex, which is remarkably efficient at capturing DNA. We characterize the method of DNA capture on the Zeonex surface and find that the use of droplets greatly facilitates the efficient deposition of DNA. This is the result of a circulating flow in the droplet that maintains a high DNA concentration at the interface of the surface/solution. Overall, our approach provides an accessible route to the study of genomic structural variation from samples containing no more than a handful of cells.

The von Willebrand factor (VWF) is a human plasma protein that plays a key role in the initiation of the formation of thrombi under high shear stress in both normal and pathological situations. It is believed that VWF undergoes a conformational transition from a compacted, globular to an extended form at high shear stress. In this paper, we develop and employ an approach to visualize the large-scale conformation of VWF in a (pressure-driven) Poiseuille flow of water-glycerol buffers with wide-field single molecule fluorescence microscopy as a function of shear stress. Comparison of the imaging results for VWF with the results of a control with λ-phage double-stranded DNA shows that the detection of individual VWF multimers in flow is feasible. A small fraction of VWF multimers are observed as visibly extended along one axis up to lengths of 2.0 μm at high applied shear stresses. The size of this fraction of molecules seems to exhibit an apparent dependency on shear stress. We further demonstrate that the obtained results are independent of the charge of the fluorophore used to label VWF. The obtained results support the hypothesis of the conformational extension of VWF in shear flow.

The two-particle interaction between 3.1-μm-diameter polystyrene latex particles at a decane-water interface was measured with time-shared optical tweezers. The water subphase contained either 0.103 mM RbCl or 0.0342 mM MgCl2, which have hydrated cations of different size but identical anions. The choice of both the anion and the concentrations makes a comparison with published data on NaCl possible and also isolates the effect of the nature of the cation on the electrostatic interaction. The measured magnitude of the dipolar force and the relative changes as a function of electrolyte were in quantitative agreement with predictions from a recently published model that uses the Langevin-Poisson-Boltzmann equation including steric effects and the polarization saturation of the medium to predict the dipolar interaction (Frydel, D.; Oettel, M. Phys. Chem. Chem. Phys. 2011, 13, 4109-4118). These results support the hypothesis that a condensed layer of counterions contributes to the electrostatic interaction between colloidal particles at an oil-water interface. Although it has been suggested that the electrostatic interactions between particles at liquid interfaces could serve as a sensitive probe of the structural details of the electric double layer, both the model predictions and experimental measurements showed a maximum change of only ~25% in the magnitude of the interaction with a change in electrolyte under the conditions tested. The ability to resolve this small change was confounded by the heterogeneous nature of the interaction. Thus, despite the apparent importance of the choice of electrolyte, the subtlety of competing effects makes it unlikely that colloidal force measurements could be used to probe the fine structure of the electric double layer.

The effect of using a viscoelastic suspending medium on the in-plane hydrodynamic interaction between two equally sized spheres in shear flow is studied experimentally to understand flow-induced assembly behavior (i.e., string formation). A counterrotating device equipped with a Couette geometry is used together with quantitative videomicroscopy. To evaluate the effects of differences in rheological properties of the suspending media, fluids have been selected that highlight specific constitutive features. These include a reference Newtonian fluid (N), a constant-viscosity, high-elasticity Boger fluid (BF), a wormlike micellar surfactant solution with a single dominant relaxation time (WMS), and a broad spectrum shear-thinning elastic polymer solution (ST). As expected, the trajectories are symmetric in the Newtonian fluid. In the BF, the midpoints of the spheres are observed to remain in the same plane before and after the interaction, as in the Newtonian fluid, although the path lines are in this case no longer symmetric. Interactions in the ST and WMS are highly asymmetric. Two fundamentally different kinds of path lines are observed in the WMS and ST: reversing and open trajectories. The type of trajectory depends on the initial configuration of the spheres with respect to each other and on the shear rate. On the basis of the obtained results, shear-thinning of the viscosity seems to be the key rheological parameter that determines the overall nature of the interactions, rather than the relative magnitude of the normal stress differences.

The hydrophilic nature of graphene oxide sheets can be tailored by varying the carbon to oxygen ratio. Depending on this ratio, the particles can be deposited at either a water-air or a water-oil interface. Upon compression of thus-created Langmuir monolayers, the sheets cover the entire interface, assembling into a strong, compact layer of tiled graphene oxide sheets. With further compression, the particle layer forms wrinkles that are reversible upon expansion, resembling the behavior of an elastic membrane. In the present work, we investigate under which conditions the structure and properties of the interfacial layer are such that free-standing films can be obtained. The interfacial rheological properties of these films are investigated using both compressional experiments and shear rheometry. The role of surface rheology in potential applications of such tiled films is explored. The rheological properties are shown to be responsible for the efficiency of such layers in stabilizing water-oil emulsions. Moreover, because of the mechanical integrity, large-area monolayers can be deposited by, for example, Langmuir-Blodgett techniques using aqueous subphases. These films can be turned into transparent conductive films upon subsequent chemical reduction.

Several technological applications, consumer products, and biological systems derive their functioning from the presence of a complex fluid interface with viscoelastic interfacial rheological properties. Measurements of the "excess" rheological properties of such an interface are complicated by the intimate coupling of the bulk and interfacial flows. In the present work, analytical, numerical, and experimental results of the interfacial flow fields in a magnetic rod interfacial stress rheometer (ISR) are presented. Mathematical solutions are required to correct the experimentally determined apparent interfacial shear moduli and phase angles for the drag exerted by the surrounding phases, especially at low Boussinesq numbers. Starting from the Navier-Stokes equations and using the generalized Boussinesq-Scriven equation as a suitable boundary condition, the problem is solved both analytically and numerically. In addition, experimental data of the interfacial flow field are reported, obtained by following the trajectories of tracer particles at the interface with time. Good agreement is found between the three methods, indicating that both the analytical solution and the numerical simulations give an adequate description of the flow field and the resulting local interfacial shear rate at the rod. Based on these results, an algorithm to correct the experimental data of the ISR is proposed and evaluated, which can be extended to different types of interfacial shear rheometers and geometries. An increased accuracy is obtained and the measurement range of the ISR is expanded toward viscosities and elastic moduli of smaller magnitude.

The effects of thermally reduced graphene sheets (TRG) on the phase separation in poly[(α-methyl styrene)-co-(acrylonitrile)]/poly(methyl-methacrylate) blends were monitored using melt rheology, conductivity spectroscopy, and electron microscopic techniques. The TRG were incorporated in the single-phase material by solution mixing. The composite samples were then allowed to phase separate in situ. The thermodynamics of phase separation have been investigated by monitoring the evolution of the storage modulus (G') as a function of temperature as the system passes through the binodal and the spinodal lines of the phase diagram. The phase separation kinetics were probed by monitoring the evolution of G' as a function of time at a quench depth well in the spinodal region. It was observed that TRG significantly influenced the phase separation temperature, the shape of the phase diagram and the rate of phase separation. The state of dispersion of TRG in the blends was assessed using electron microscopy and conductivity spectroscopy measurements. Interestingly, the composite samples (monophasic) were virtually insulators at room temperature, whereas highly conducting materials were obtained as a result of phase separation in the biphasic materials.

Particle shape plays an important role in controlling the optical, magnetic, and mechanical properties of nanoparticle suspensions as well as nanocomposites. However, characterizing the size, shape, and the associated polydispersity of nanoparticles is not straightforward. Electron microscopy provides an accurate measurement of the geometric properties, but sample preparation can be laborious, and to obtain statistically relevant data many particles need to be analyzed separately. Moreover, when the particles are suspended in a fluid, it is important to measure their hydrodynamic properties, as they determine aspects such as diffusion and the rheological behavior of suspensions. Methods that evaluate the dynamics of nanoparticles such as light scattering and rheo-optical methods accurately provide these hydrodynamic properties, but do necessitate a sufficient optical response. In the present work, three different methods for characterizing nonspherical gold nanoparticles are critically compared, especially taking into account the complex optical response of these particles. The different methods are evaluated in terms of their versatility to asses size, shape, and polydispersity. Among these, the rheo-optical technique is shown to be the most reliable method to obtain hydrodynamic aspect ratio and polydispersity for nonspherical gold nanoparticles for two reasons. First, the use of the evolution of the orientation angle makes effects of polydispersity less important. Second, the use of an external flow field gives a mathematically more robust relation between particle motion and aspect ratio, especially for particles with relatively small aspect ratios.

A simple and versatile method for making chemically patterned anisotropic colloidal particles is proposed and demonstrated for two different types of patterning. Using a combination of thermo/mechanical stretching followed by a wet chemical treatment of a sterically stabilized latex, both patchy ellipsoidal particles with sticky interactions near the tips as well as particles with tunable fluorescent patterns could be easily produced. The potential of such model colloidal particles is demonstrated, specifically for the case of directed self-assembly.

In this manuscript, the determination of solubility of crystalline drug nanosuspensions by a range of methods is critically investigated. As the determinations of solubility were performed in the presence of the solubilizing nanosuspension stabilizer d-α-tocopherol polyethylene glycol 1000 succinate (TPGS), the potential effects of this excipient on the measurements were studied first. Solubility data of nanosuspensions of itraconazole, loviride, phenytoin and naproxen were generated using different methodologies. Data obtained using separation-based methodologies (centrifugation, filtration and ultracentrifugation) proved to be of limited use, due to poor nanoparticle separation efficiencies and/or significant adsorption of TPGS onto the nanoparticle surfaces. Light scattering and turbidity were found to be more suitable for the determination of nanosuspension solubility. The obtained data show that, unlike earlier reports, the solubility increases due to nanosizing are small, with measured increases of only 15%. These solubility increases are in fair agreement with what would be predicted based on the Ostwald-Freundlich equation.

Within the field of nanotechnology, nanoparticles are one of the most prominent and promising candidates for technological applications. Self-assembly of nanoparticles has been identified as an important process where the building blocks spontaneously organize into ordered structures by thermodynamic and other constraints. However, in order to successfully exploit nanoparticle self-assembly in technological applications and to ensure efficient scale-up, a high level of direction and control is required. The present review critically investigates to what extent self-assembly can be directed, enhanced, or controlled by either changing the energy or entropy landscapes, using templates or applying external fields.

Many drug compounds have limited solubility in water. To enhance the oral bioavailability of such compounds, pharmaceutical formulations target the creation of a supersaturated solution. Release of the compound from ordered mesoporous silica carrier is such a means for reaching supersaturation. Little is known about the evolution of supersaturated intestinal media. The present study reveals the phase transitions of the poorly water-soluble drug itraconazole in simulated intestinal fluid under conditions corresponding to supersaturation. Electron spin resonance of n-doxylstearic acid spin probes evidenced that during supersaturation itraconazole is solubilized inside the hydrophobic core of mixed micelles composed of lecithin and bile salt. Cryogenic transmission electron microscopy revealed that the supersaturated state of itraconazole provokes the formation of nanofibers with a uniform diameter of 12 nm. The nanofiber length determined via dynamic light scattering increases from 220 to 1480 nm after 30 and 90 min, respectively. Nanofibers drastically reduced transepithelial transport of itraconazole across a Caco-2 cell monolayer mimicking the gastrointestinal absorption. Based on our study, we suggest the existence of an optimum intraluminal itraconazole supersaturation at which itraconazole absorption is enhanced but formation of itraconazole nanofibers prevented.

Ordering induced by shear flow can be used to direct the assembly of particles in suspensions. Flow-induced ordering is determined by the balance between a range of forces, such as direct interparticle, Brownian, and hydrodynamic forces. The latter are modified when dealing with viscoelastic rather than Newtonian matrices. In particular, 1D stringlike structures of spherical particles have been observed to form along the flow direction in shear thinning viscoelastic fluids, a phenomenon not observed in Newtonian fluids at similar particle volume fractions. Here we report on the formation of freestanding crystalline patches in planes parallel to the shearing surfaces. The novel microstructure is formed when particles are suspended in viscoelastic, wormlike micellar solutions and only when the applied shear rate exceeds a critical value. In spite of the very low volume fraction (less than 0.01), particles arrange themselves in 2D crystalline patches along the flow direction. This is a bulk phenomenon because 2D crystals form throughout the whole gap between plates, with the gap thickness being much larger than the particle size. Shear flow may hence be an easy method to drive particles into crystalline order in suspensions with viscoelastic properties. The crystalline structure reported here could be used to design new materials with special mechanical, optical, thermal, or electric properties.

Conducting polymeric materials with stable phase microstructures have a range of potential applications. In this work, it is investigated whether phase separation in polymer blends can be used as a tool to create well dispersed conducting filler rich domains in 3D with controlled morphology, potentially resulting in more effective percolation. The effect of amine functionalized multiwall carbon nanotubes (NH(2)-MWCNTs) on the thermally induced phase separation processes in poly[(alpha-methyl styrene)-co-acrylonitrile]/poly(methyl methacrylate) (PalphaMSAN/PMMA) blends was monitored by melt rheology, conductivity spectroscopy, and microscopic techniques. Electron microscopic images revealed that the phase separation resulted in a heterogeneous distribution of NH(2)-MWCNTs in the blends. The migration of NH(2)-MWCNTs is controlled by the thermodynamic forces that drive phase separation and led to an increase in their local concentration in a specific phase resulting in percolative "network-like" structure. Conductivity spectroscopy measurements demonstrated that the blends with 2 wt % NH(2)-MWCNTs that showed insulating properties for a one phasic system revealed highly conducting material in the melt state (two phasic) as a result of phase separation. By quenching this morphology, a highly conducting material with controlled dispersion of MWCNTs can be achieved. Furthermore, the role of NH(2)-MWCNTs in stabilizing the PMMA droplets against flow induced coalescence in 85/15 PalphaMSAN/PMMA blends was also established for the first time. It was observed that at a typical loading of 1.25 wt % NH(2)-MWCNTs the coalescence was completely suppressed on a practical time scale.

Colloidal particles confined at liquid interfaces have important applications, for example in the stabilization of emulsions and foams. Also the self-assembly of particles at interfaces offers potential for novel applications and structured particle films. As the colloidal interactions of colloidal particles at interfaces differ from those in bulk, colloidal microstructures can be achieved at an interface which cannot be produced in bulk. In the present work the particle shape, surface charge, and wetting properties are varied, and the resulting self-assembly of particles at a fluid interface is studied. Model monodisperse micrometer-sized ellipsoidal particles were prepared by a mechanical stretching method. These particles were chosen to be well-suited for investigation by optical microscopy. When deposited at an interface between two fluids, shape-induced capillary interactions compete with the electrostatic repulsion. Changing the surface charge and the position at the interface can be used to manipulate the experimentally observed self-assembly process. The initial microstructure of charged ellipsoids at a decane-water interface consists of individual ellipsoids coexisting with linear chains of ellipsoids, connected at their tips. The aggregation behavior in these monolayers was investigated by optical microscopy combined with quantitative image analysis and a dominant tip-tip aggregation was observed. Microstructural information was quantified by calculating the pair-distribution and orientation-distribution functions, as a function of time. Compared to particles at an oil-water interface, particles of the same surface chemistry and charge at an air-water interface seem to have weaker electrostatic interactions, and they also have a different equilibrium position at the interface. The latter leads to differences in the capillary forces. The subsequent change in the balance between electrostatic and capillary forces gave rise to very dense networks having as a typical building block ellipsoids connected at their tips in triangular or flower-like configuration. These networks were very stable and did not evolve in time. The resulting monolayers responded elastically and buckled under compression. Furthermore, the mechanical properties of these monolayers, as measured by surface shear rheology, showed that the monolayer of ellipsoids exhibit a substantial surface modulus even at low surface coverage and can be used to create more elastic monolayers compared to aggregate networks of spheres of the same size and surface properties.

The synthesis and selected macroscopic properties of a new model system consisting of poly(N-isopropylacrylamide) (PNIPAM)-coated rod-like fd virus particles are presented. The sticky rod-like colloids can be used to study effect of particle shape on gelation transition, the structure and viscoelasticity of isotropic and nematic gels, and to make both open isotropic as well as ordered nematic particle networks. This model system of rod-like colloids, for which the strength of attraction between the particles is tunable, is obtained by chemically grafting highly monodisperse rod-like fd virus particles with thermoresponsive polymers, e.g. PNIPAM. At room temperature, suspensions of the resulting hybrid PNIPAM-fd are fluid sols which are in isotropic or liquid crystalline phases, depending on the particle concentration and ionic strength. During heating/cooling, the suspensions change reversibly between sol and gel state near a critical temperature of approximately 32 degrees C, close to the lower critical solution temperature of free PNIPAM. The so-called nematic gel, which exhibits a cholesteric feature, can therefore be easily obtained. The gelation behavior of PNIPAM-fd system and the structure of the nematic gel have been characterized by rheology, optical microscopy and small-angle X-ray scattering.

Flow can change the rate at which solutes adsorb on surfaces by changing mass transfer to the surface, but moreover, flow can induce changes in the conformation of macromolecules in solution by providing sufficient stresses to perturb the segmental distribution function. However, there are few studies where the effect of flow on macromolecules has been shown to alter the structure of macromolecules adsorbed on surfaces. We have studied how the local energy dissipation alters the adsorption of gelatin onto polystyrene nanoparticles ( r = 85 nm). The change in the nature of the adsorbed layer is manifest in the change in the ability of the nanoparticles to resist aggregation. Circular dichroism spectroscopy was used to assess conformational changes in gelatin, and dynamic light scattering was used to assess the colloid stability. Experiments were conducted in a vortex jet mixer where energy density and mixing times have been quantified; mixing of the gelatin and unstable nanoparticles occurs on the order of milliseconds. The adsorption of the gelatin provides steric stabilization to the nanoparticles. We found that the stability of the gelatin-adsorbed nanoparticles increased with increasing mixing velocities: when the mixing velocities were changed from 0.9 to 550 m/s, the radius of the nanoclusters (aggregates) formed 12 h after the mixing decreased from 2620 to 600 nm. Increasing temperature also gave rise to similar trends in the stability behavior with increasing temperature, leading to increasing colloid stability. Linear flow birefringence studies also suggested that the velocity fields in the mixer are sufficiently strong to produce conformational changes in the gelatin. These results suggest that the energy dissipation produced by mixing can activate conformational changes in gelatin to alter its adsorption on the surfaces of nanoparticles. Understanding how such conformational changes in gelatin can be driven by local fluid mechanics and how these changes are related to the adsorption behavior of gelatin is very important both industrially and scientifically.

A high-throughput experimentation method for studying the dissolution of phenytoin, a poorly water soluble drug, was developed and validated. Solid dispersions with 12 excipients (7 polymers and 5 surfactants) were prepared and tested. Each excipient was screened with three drug loadings: 10, 20, and 40% (w/w). Each solid dispersion was prepared in triplicate, for a total of 108 samples. The drug dissolution was studied in simulated gastric fluid without pepsin plus 1% sodium laurylsulfate. This study led to the identification of three improved formulations, exhibiting an extent of dissolution higher than 90% after both 30 and 60 min. The HTE results could be reproduced at a larger scale using a conventional solvent evaporating method, proving the reliability of the HTE protocol.

The forces between colloidal particles at a decane-water interface, in the presence of low concentrations of a monovalent salt (NaCl) and the surfactant sodium dodecyl sulfate (SDS) in the aqueous subphase, have been studied using laser tweezers. In the absence of electrolyte and surfactant, particle interactions exhibit a long-range repulsion, yet the variation of the interaction for different particle pairs is found to be considerable. Averaging over several particle pairs was hence found to be necessary to obtain a reliable assessment of the effects of salt and surfactant. It has previously been suggested that the repulsion is consistent with electrostatic interactions between a small number of dissociated charges in the oil phase, leading to a decay with distance to the power -4 and an absence of any effect of electrolyte concentration. However, the present work demonstrates that increasing the electrolyte concentration does yield, on average, a reduction of the magnitude of the interaction force with electrolyte concentration. This implies that charges on the water side also contribute significantly to the electrostatic interactions. An increase in the concentration of SDS leads to a similar decrease of the interaction force. Moreover, the repulsion at fixed SDS concentrations decreases over longer times. Finally, measurements of three-body interactions provide insight into the anisotropic nature of the interactions. The unique time-dependent and anisotropic interactions between particles at the oil-water interface allow tailoring of the aggregation kinetics and structure of the suspension structure.

The controlled generation of 2D aggregate networks is studied experimentally using micrometer-sized polystyrene latex particles attached to the oil-water interface. Starting from an initially crystalline monolayer, appropriate combinations of carefully added electrolyte and surfactant enable control over both the fractal dimension and the kinetics of aggregation. Remarkably, the colloidal crystals formed upon first spreading remain stable, even for days, when substantial amounts of electrolyte are added to the aqueous phase. Pressure-area isotherms reveal a slow time evolution of the electrostatic dipole-dipole interaction. When the electrostatic interaction has been sufficiently weakened, aggregation proceeds in well-defined, reproducible manner. The aggregation process is analyzed using quantitative video microscopy. The evolution of the cluster size distribution and its moments is characterized, and static and dynamic scaling exponents are derived to identify the nature of the aggregation process. In the range of concentrations studied here, the kinetics all agree with a "fast", diffusion-limited cluster type of aggregation. However, the fractal dimension strongly depends on the composition of the aqueous subphase. Rather dense structures are found when only electrolyte is used, whereas more open structures are obtained when even small amounts of surfactant are added. It is suggested that this structural dependency is related to the effect of surfactant on the contact angle and its consequences for the anisotropic nature of the capillary interactions.

The behavior of a colloidal suspension of rodlike fd viruses in the nematic phase, subjected to steady state and transient shear flows, is studied. The monodisperse nature of these rods combined with relatively small textural contribution to the overall stress make this a suitable model system to investigate the effects of flow on the nonequilibrium phase diagram. Transient rheological experiments are used to determine the critical shear rates at which director tumbling, wagging, and flow-aligning occurs. The present model system enables us to study the effect of rod concentration on these transitions. The results are in quantitatively agreement with the Doi-Edwards-Hess model. Moreover, we observe that there is a strong connection between the dynamic transitions and structure formation, which is not incorporated in theory.