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The effectiveness of water flooding oil recovery depends to an important extent on the competitive wetting of oil and water on the solid rock matrix. Here, we use macroscopic contact angle goniometry in highly idealized model systems to evaluate how brine salinity affects the balance of wetting forces and to infer the microscopic origin of the resultant contact angle alteration. We focus, in particular, on two competing mechanisms debated in the literature, namely, double-layer expansion and divalent cation bridging. Our experiments involve aqueous droplets with a variable content of chloride salts of Na + , K + , Ca 2+ , and Mg 2+ , wetting surfaces of muscovite and amorphous silica, and an environment of ambient decane containing small amounts of fatty acids to represent polar oil components. By diluting the salt content in various manners, we demonstrate that the water contact angle on muscovite, not on silica, decreases by up to 25° as the divalent cation concentration is reduced from typical concentrations in seawater to zero. Decreasing the ionic strength at a constant divalent ion concentration, however, has a negligible effect on the contact angle. We discuss the consequences for the interpretation of core flooding experiments and the identification of a microscopic mechanism of low salinity water flooding, an increasingly popular, inexpensive, and environment-friendly technique for enhanced oil recovery.

We studied the effects of shear and its history on suspensions of carbon black (CB) in lithium ion battery electrolyte via simultaneous rheometry and electrical impedance spectroscopy. Ketjen black (KB) suspensions showed shear thinning and rheopexy and exhibited a yield stress. Shear step experiments revealed a two time scale response. The immediate effect of decreasing the shear rate is an increase in both viscosity and electronic conductivity. In a much slower secondary response, both quantities change in the opposite direction, leading to a reversal of the initial change in the conductivity. Stepwise increases in the shear rate lead to similar responses in the opposite direction. This remarkable behavior is consistent with a picture in which agglomerating KB particles can stick directly on contact, forming open structures, and then slowly interpenetrate and densify. The fact that spherical CB particles show the opposite slow response suggests that the fractal structure of the KB primary units plays an important role. A theoretical scheme was used to analyze the shear and time-dependent viscosity and conductivity. Describing the agglomerates as effective hard spheres with a fractal architecture and using an effective medium approximation for the conductivity, we found the changes in the derived suspension structure to be in agreement with our qualitative mechanistic picture. This behavior of KB in flow has consequences for the properties of the gel network that is formed immediately after the cessation of shear: both the yield stress and the electronic conductivity increase with the previously applied shear rate. Our findings thus have clear implications for the operation and filling strategies of semisolid flow batteries.

Establishing and maintaining concentration gradients that are stable in space and time is critical for applications that require screening the adsorption behavior of organic or inorganic species onto solid surfaces for wide ranges of fluid compositions. In this work, we present a design of a simple and compact microfluidic device based on steady-state diffusion of the analyte, between two control channels where liquid is pumped through. The device generates a near-linear distribution of concentrations. We demonstrate this via experiments with dye solutions and comparison to finite-element numerical simulations. In a subsequent step, the device is combined with total internal reflection ellipsometry to study the adsorption of (cat)ions on silica surfaces from CsCl solutions at variable pH. Such a combined setup permits a fast determination of an adsorption isotherm. The measured optical thickness is compared to calculations from a triple layer model for the ion distribution, where surface complexation reactions of the silica are taken into account. Our results show a clear enhancement of the ion adsorption with increasing pH, which can be well described with reasonable values for the equilibrium constants of the surface reactions.

Surfactant adsorption in a three-phase system and its influence on wetting properties are relevant in various applications. Here, we report a hitherto not observed phenomenon, namely the retraction of an aqueous drop on hydrophilic solid substrates (which we refer to as 'autophobing') in ambient oil containing water-insoluble fatty acids, caused by the deposition of these fatty acids from the ambient oil onto the solid substrate. AFM measurements confirm that the surfactant is deposited on the solid by the moving contact line. This leads to a more hydrophobic substrate, the retraction of the contact line and a concomitant increase in the contact angle. The deposition process is enabled by the formation of a reaction product between deprotonated fatty acids and Ca(2+) ions at the oil/water interface. We investigate how the transition to a new equilibrium depends on the concentrations of the fatty acids, the aqueous solute, the chain lengths of the fatty acid, and the types of alkane solvent and silica or mica substrates. This phenomenon is observed on both substrates and for all explored combinations of fatty acids and solvents and thus appears to be generic. In order to capture the evolution of the contact angle, we develop a theoretical model in which the rate of adsorption at the oil-water interface governs the overall kinetics of autophobing, and transfer to the solid is determined by a mass flux balance (similar to a Langmuir Blodgett transfer).

We studied both global and local effects of cylindrical confinement on the diffusive behavior of hard sphere (HS) colloids. Using confocal scanning laser microscopy (CSLM) and particle tracking, we measured the mean squared displacement (MSD) of 1 micron sized silica particles in water-glycerol. This combination of fluid and setup allowed us to measure MSDs in a 4-dimensional parameter space, defined by the HS volume fraction (Φ: 0.05-0.39), cylinder radius (R: 2.5-20 micron), distance to the wall (z) and lagtime (τ: 0.03-60 s). MSDs for the entire cylinder confirm earlier findings that both narrowing the cylinder and populating it cause a slower dynamics. Additionally a decrease in R was found to cause a stronger ordering of the fluid. The effect of confinement on dynamics was further examined as a function of (z) location. For the largest cylinder (with minor curvature), we found that the strong decrease in MSD near the wall, becomes much less pronounced for higher Φ. Analyzing the radial (r) and azimuthal (θ) components, we found pronounced differences in the z-dependence that were 'hidden' in the total MSD. Near the wall, the r-MSD shows a much steeper z-dependence while at larger z, it shows a remarkable anti-correlation with the (peaked) density n(z). Also the dependence of the r-MSD on lagtime correlates with n(z): diffusive in between layers, but subdiffusive inside layers. These observations bring earlier findings together, while also shedding new light on the diffusive dynamics of concentrated colloids in narrow capillaries.

We analyze a recently introduced approach for the sorting of aqueous drops with biological content immersed in oil, using a microfluidic chip that combines the functionality of electrowetting with the high throughput of two-phase flow microfluidics. In this electrostatic sorter, three co-planar electrodes covered by a thin dielectric layer are placed directly below the fluidic channel. Switching the potential of the central electrode creates an electrical guide that leads the drop to the desired outlet. The generated force, which deflects the drop, can be tuned via the voltage. The working principle is based on a contrast in conductivity between the drop and the continuous phase, which ensures successful operation even for drops of highly conductive biological media like phosphate buffered saline. Moreover, since the electric field does not penetrate the drop, its content is protected from electrical currents and Joule heating. A simple capacitive model allows quantitative prediction of the electrostatic forces exerted on drops. The maximum achievable sorting rate is determined by a competition between electrostatic and hydrodynamic forces. Sorting speeds up to 1200 per second are demonstrated for conductive drops of 160 pl in low viscosity oil.

Soft microgel particles inherently possess qualities of both polymers as well as particles. We review the similarities and differences between soft microgel particles and stiff colloids at fluid-fluid interfaces. We compare two fundamental aspects of particle-laden interfaces namely the adsorption kinetics and the interactions between adsorbed particles. Although it is well established that the transport of both hard particles and microgels to the interface is driven by diffusion, the analysis of the adsorption kinetics needs reconsideration and a proper equation of state relating the surface pressure to the adsorbed mass should be used. We review the theoretical and experimental investigations into the interactions of particles at the interface. The rheology of the interfacial layers is intimately related to the interactions, and the differences between hard particles and microgels become pronounced. The assembly of particles into the layer is another distinguishing factor that separates hard particles from soft microgel particles. Microgels deform substantially upon adsorption and the stability of a microgel-stabilized emulsion depends on the conformational changes triggered by external stimuli., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The equilibrium shape of a drop in contact with solid surfaces can undergo continuous or discontinuous transitions upon changes in either drop volume or surface energies. In many instances, such transitions involve the motion of the three-phase contact line and are thus sensitive to contact angle hysteresis. Using a combination of electrowetting-based experiments and numerical calculations, we demonstrate for a generic sphere-plate confinement geometry how contact angle hysteresis affects the mechanical stability of competing axisymmetric and nonaxisymmetric drop conformations and qualitatively changes the character of transitions between them.

An analysis of the dynamics of colloids in shear flow can be challenging because of the superposition of diffusion and advection. We present a method that separates the two motions, starting from the time-dependent particle coordinates. The restriction of the tracking to flow lanes and the subtraction of estimated advective displacements are combined in an iterative scheme that eventually makes the spatial segmentation redundant. Tracking errors due to the neglect of lateral diffusion are avoided, while drifts parallel and perpendicular to the flow are eliminated. After explaining the principles of our method, we validate it against both computer simulations and experiments. A critical overall test is provided by the mean square displacement function at high Peclet numbers (up to 50). We demonstrate via simulations how the measurement accuracy depends on diffusion coefficients and flow rates, expressed in units of camera pixels and frames. Also, sample-specific issues are addressed: inaccuracies in the velocity profile for dilute suspensions (volume fraction ≤0.03) and tracking errors for concentrated ones (VF ≥ 0.3). An analysis of experiments with colloidal spheres flowing through microchannels corroborates these findings and indicates perspectives for studies on transport, mixing, or rheology in microfluidic environments.

Colloidal suspensions flowing through microchannels were studied for the effects of both the shear flow and the proximity of walls on the particles' self-diffusion. Use of hydrostatic pressure to pump micron-sized silica spheres dispersed in water-glycerol mixture through poly(dimethylsiloxane) channels with a cross section of 30×24μm(2), allowed variation in the local Peclet number (Pe) from 0.01 to 50. To obtain the diffusion coefficients, image-time series from a confocal scanning laser microscope were analyzed with a method that, after finding particle trajectories, subtracts the instantaneous advective displacements and subsequently measures the slopes of the mean squared displacement in the flow (x) and shear (y) directions. For dilute suspensions, the thus obtained diffusion coefficients (D(x) and D(y)) are close to the free diffusion coefficient at all shear rates. In concentrated suspensions, a clear increase with the Peclet number (for Pe > 10) is found, that is stronger for D(x) than for D(y). This effect of shear-induced collisions is counteracted by the contribution of walls, which cause a strong local reduction in D(x) and D(y).

Understanding the adsorption dynamics of soft microgel particles is a key step in designing such particles for potential applications as stimuli-responsive Pickering stabilizers for foams or emulsions. In this study we experimentally determine an equation of state (EOS) for poly (N-isopropylacrylamide) (PNIPAM) microgel particles adsorbed onto an air-water interface using a Langmuir film balance. We detect a finite surface pressure at very low surface concentration of particles, for which standard theories based on hard disk models predict negligible pressures, implying that the particles must deform strongly upon adsorption to the interface. Furthermore, we study the evolution of the surface pressure due to the adsorption of PNIPAM particles as a function of time using pendant drop tensiometry. The equation of state determined in the equilibrium measurements allows us to extract the adsorbed amount as a function of time. We find a mixed-kinetic adsorption that is initially controlled by the diffusion of particles towards the interface. At later stages, a slow exponential relaxation indicates the presence of a coverage-dependent adsorption barrier related to crowding of particles at the interface.

Precise control and manipulation of individual drops are crucial in many lab-on-a-chip applications. We present a novel hybrid concept for channel-based discrete microfluidics with integrated electrowetting functionality by incorporating co-planar electrodes (separated by a narrow gap) in one of the microchannel walls. By combining the high throughput of channel-based microfluidics with the individual drop control achieved using electrical actuation, we acquire the strengths of both worlds. The tunable strength of the electrostatic forces enables a wide range of drop manipulations, such as on-demand trapping and release, guiding, and sorting of drops in the microchannel. In each of these scenarios, the retaining electrostatic force competes with the hydrodynamic drag force. The conditions for trapping can be predicted using a simple model that balances these forces.

We present a concept of a wetting defect of continuously variable strength based on electrowetting, along with a capillary force sensor adapted for the characterization of macroscopically heterogeneous surfaces. Patterned electrodes submerged under an insulating layer are used to generate potential wells for drops of electrically conductive liquids on the solid surface, with a well depth that scales with the diameter of the drop and square of the applied alternating (AC) voltage. We characterize the strength of the electrowetting trap and the hysteretic motion of the drop along the surface, using a simple force sensor based on optical imaging of a thin bendable capillary. A force resolution of approximately 0.1 μN is achieved.

The adsorption of surface active species to liquid-liquid and to solid-liquid interfaces can have dramatic effects in microfluidics. In this paper we show how electrowetting on dielectric can be used to monitor a dynamic liquid-liquid interfacial tension (IFT) with a time resolution of O(1 s) using amplitude modulation of the AC voltage. This straightforward method, which requires less than a microlitre of sample, is demonstrated for aqueous drops containing Triton X-100 surfactant on a Teflon AF-coated substrate and with heptane as the immiscible oil ambient. Under these conditions, next to extracting the oil-water IFT (γ(ow)), also the effective water-substrate IFT difference (Δγ(ws)) can be obtained from the oil-water IFT and the Young's angle. Both γ(ow) and γ(ws) decrease over time due to adsorption. The measured dynamic oil-water IFT compares well to results of pendant drop experiments.

How the diffusive dynamics of colloidal spheres changes in the vicinity of a particle-coated surface is of importance for industrial challenges such as fouling and sedimentation as well as for fundamental studies into confinement effects. We addressed this question by studying colloidal dynamics in a partially coated surface layer, using video microscopy. Particle mean squared displacement (MSD) functions were measured as a function of a (local) effective volume fraction (EVF), which was varied by making use of gravity settling. Comparison of MSDs at the bare and coated surfaces for EVF of 0.2-0.4 revealed that at the latter surface the motion amplitudes are strongly reduced, accompanied by a sharp transition from diffusive to nearly caged motion. This clearly indicates that the surface-attached particles cannot be taken into account via volume fraction and that their immobility has a distinct effect. For EVF > 0.45, the caging becomes dominated by the suspended particles, making the dynamics at the bare and coated surfaces similar., (© 2011 American Chemical Society)

We study the formation of layers of metal stearates at the interface between a decane solution of stearic acid and aqueous salt solutions of variable composition and pH by monitoring the evolution of their mechanical, optical, and chemical properties as a function of time after formation of the interface. For values of the pH below the pK(a) of stearic acid hardly any interfacial activity is observed. For pH > pK(a), stearic acid deprotonates at the interface and forms metal stearates, eventually leading to the formation of macroscopic solid layers. Dynamic interfacial tension measurements reveal that the process takes place in several stages, which we attribute to the successive formation of dilute and dense monolayers followed by three-dimensional growth. In the presence of divalent ions, the solid layers display a significant increase in the dilatational storage modulus. Experiments performed with an aqueous phase containing multiple cation species (artificial seawater) give rise to particularly pronounced growth of solid layers, which preferentially incorporate Ca(2+) as revealed by X-ray photoelectron and infrared spectroscopy. Our results highlight in particular the importance of the complex synergistic effects of simultaneously present monovalent and divalent cation species on the interfacial adsorption.

We discuss a microfluidic system in which (programmable) local electric fields originating from embedded and protected electrodes are used to control the formation and merging of droplets in a microchannel. The creation of droplets-on-demand (DOD) is implemented using the principle of electrowetting. Combined with hydrodynamic control, the droplet size and formation frequency can be varied independently. Using two synchronized DOD injectors, merging-on-demand (MOD) is achieved via electrocoalescence. The efficiency of MOD is 98% based on hundreds of observations. These two functionalities can be activated independently.

Two-phase flow microfluidics is emerging as a popular technology for a wide range of applications involving high throughput such as encapsulation, chemical synthesis and biochemical assays. Within this platform, the formation and merging of droplets inside an immiscible carrier fluid are two key procedures: (i) the emulsification step should lead to a very well controlled drop size (distribution); and (ii) the use of droplet as micro-reactors requires a reliable merging. A novel trend within this field is the use of additional active means of control besides the commonly used hydrodynamic manipulation. Electric fields are especially suitable for this, due to quantitative control over the amplitude and time dependence of the signals, and the flexibility in designing micro-electrode geometries. With this, the formation and merging of droplets can be achieved on-demand and with high precision. In this review on two-phase flow microfluidics, particular emphasis is given on these aspects. Also recent innovations in microfabrication technologies used for this purpose will be discussed.

Video microscopy and particle tracking were used to measure the spatial dependence of the diffusion coefficient (D(α)) of colloidal particles in a closed cylindrical cavity. Both the height and radius of the cylinder were equal to 9.0 particle diameters. The number of trapped particles was varied between 1 and 16, which produced similar results. In the center of the cavity, D(α) turned out to be 0.75D(0) measured in bulk liquid. On approaching the cylindrical wall, a transition region of about 3 particle diameters wide was found in which the radial and azimuthal components of D(α) decrease to respective values of 0.1D(0) and 0.4D(0), indicating asymmetrical diffusion. Hydrodynamic simulations of local drag coefficients for hard spheres produced very good agreement with experimental results. These findings indicate that the hydrodynamic particle-wall interactions are dominant and that the complete 3D geometry of the confinement needs to be taken into account to predict the spatial dependence of diffusion accurately.

Electrowetting (EW) is widely used in digital microfluidics for the manipulation of drops sandwiched between two parallel plates. In contrast, demonstrations of closed microfluidic channels enhanced with EW functionality are scarce. Here, we report a simple, low-cost method to construct such microchannels enclosed between two glass plates, each of which comprises electrodes and insulating layers. Our method uses soft imprint lithography with thiolene precursors to design the channel geometry. UV exposure is used to seal the chips permanently and a silanization treatment renders all inner channel surfaces hydrophobic. Compared to earlier polydimethylsiloxane-based designs, this method allows us to make microchannels with smaller dimensions (down to 10 microns), lower aspect ratios (down to height/length=1/10), and symmetric electrodes both on the top and the bottom of the channel. We demonstrate the new capabilities with two examples: (i) EW-enhanced drop generation in a flow focusing geometry allows precise and continuous control on drop diameter in the range approximately 1-15 microns while maintaining monodispersity; (ii) EW allows tuning of the excess water pressure needed to displace oil in a microchannel, leading to spontaneous imbibition at EW number eta>0.89.

Vascular endothelial cells form the inner lining of all blood vessels and play a central role in vessel physiology and disease. Endothelial cells are highly responsive to the mechanical stimulus of fluid shear stress that is exerted by blood flowing over their surface. In this study, the immediate micromechanical response of endothelial cells to physiological shear stress was characterized by tracking of ballistically injected, sub-micron, fluorescent particles. It was found that the mean squared displacement (MSD) of the particles decreases by a factor 1.5 within 10 min after the onset of shear stress. This decrease in particle motion is transient, since the MSD returns to control values within 15-30 min after the onset of shear. The immediate micromechanical stiffening is dependent on activation of the vascular endothelial growth factor receptor (VEGFR)-2, because inhibition of the receptor abrogates the micromechanical response. This work shows that the cytoskeleton is actively involved in the acute, functional response of endothelial cells to shear stress.

Using particle tracking microrheology, we studied the glass transition in dense suspensions of thermosensitive microgel particles. These suspensions can be tuned reversibly between the glass state at low temperature and the liquid state at high temperature. In the glass state, the ensemble averaged mean squared displacements (MSDs) of added fluorescent tracer particles depend on the age of the suspension. We also determine the local viscoelastic moduli, G' and G", from the MSDs using the Generalized Stokes-Einstein Relation and compare them to the bulk moduli, measured using conventional rheometry. With particle tracking, one probes the viscoelastic moduli in a lower frequency range than with macrorheology, which makes it possible to determine the mean relaxation time that is inaccessible with macrorheology. In the glass state, the mean relaxation time increases linearly with the age of the sample and the short time particle displacement distributions are non-Gaussian, indicating inhomogeneity of the system. The observed difference between conventional and microrheology is explained quantitatively assuming that the tracer particles are surrounded by a viscoelastic liquid shell, different from the bulk.

Endogenous granules (EGs) that consist of lipid droplets and mitochondria have been commonly used to assess intracellular mechanical properties via multiple particle tracking microrheology (MPTM). Despite their widespread use, the nature of interaction of EGs with the cytoskeletal network and the type of forces driving their dynamics--both of which are crucial for the interpretation of the results from MPTM technique--are yet to be resolved. In this report, we study the dynamics of endogenous granules in mammalian cells using particle tracking methods. We find that the ensemble dynamics of EGs is diffusive in three types of mammalian cells (endothelial cells, smooth muscle cells and fibroblasts), thereby suggesting an apparent universality in their dynamical behavior. Moreover, in a given cell, the amplitude of the mean-squared displacement for EGs is an order of magnitude larger than that of injected particles. This observation along with results from ATP depletion and temperature intervention studies suggests that cytoskeletal active forces drive the dynamics of EGs. To elucidate the dynamical origin of the diffusive-like nonthermal motion, we consider three active force generation mechanisms--molecular motor transport, actomyosin contractility and microtubule polymerization forces. We test these mechanisms using pharmacological interventions. Experimental evidence and model calculations suggest that EGs are intimately linked to microtubules and that microtubule polymerization forces drive their dynamics. Thus, endogenous granules could serve as non-invasive probes for microtubule network dynamics in mammalian cells.

We used video microscopy and particle tracking to study the dynamics of confined hard-sphere suspensions. Our fluids consisted of 1.1-microm-diameter silica spheres suspended at volume fractions of 0.33-0.42 in water-dimethyl sulfoxide. Suspensions were confined in a quasiparallel geometry between two glass surfaces: a millimeter-sized rough sphere and a smooth flat wall. First, as the separation distance (H) is decreased from 18 to 1 particle diameter, a transition takes place from a subdiffusive behavior (as in bulk) at large H, to completely caged particle dynamics at small H. These changes are accompanied by a strong decrease in the amplitude of the mean-square displacement (MSD) in the horizontal plane parallel to the confining surfaces. In contrast, the global volume fraction essentially remains constant when H is decreased. Second, measuring the MSD as a function of distance from the confining walls, we found that the MSD is not spatially uniform but smaller close to the walls. This effect is the strongest near the smooth wall where layering takes place. Although confinement also induces local variations in volume fraction, the spatial variations in MSD can be attributed only partially to this effect. The changes in MSD are predominantly a direct effect of the confining surfaces. Hence, both the wall roughness and the separation distance (H) influence the dynamics in confined geometries.

We studied the dynamics of two types of intracellular probe particles, ballistically injected latex spheres and endogenous granules, in tumor cell lines of different metastatic potential: breast tumor cells (MCF-7 malignant, MCF-10A benign) and pancreas adenocarcinoma (PaTu8988T malignant, PaTu8988S benign). For both tissue types and for both probes, the mean squared displacement (MSD) function measured in the malignant cells was substantially larger than in the benign cells. Only a few cells were needed to characterize the tissue as malignant or benign based on their MSD, since variations in MSD within the same cell line were relatively small. These findings suggest that intracellular particle tracking (IPT) can serve as a simple and reliable method for characterization of cell states obtained from a small amount of cell sample. Mechanical analysis of the same cell lines with atomic force microscopy (AFM) in force-distance mode revealed that AFM could distinguish between the benign and malignant breast cancer cells but not the pancreatic tumor cell lines. This underlines the potential value of IPT as a complementary nanomechanical tool for studying cell-state-dependent mechanical properties.

We report the utility of structured elastomeric membranes (SEMs) as a multifunctional microfluidic tool. These structured membranes are part of a two-layer microfluidic device, analogous to membrane valves, with the novelty that they incorporate topographical features on the roof of the fluid channel. We demonstrate that when the topographical features are recessed into the roof of the fluid channel, actuation of the membrane leads to effective confinement of fluids down to femtolitres in preformed microfluidic containers. Thus, the SEMs in this case function as fluidic traps that could be coupled to microfluidic networks for rapid and repeated flushing of solvents. Alternatively, when the topographical features on the roof protrude into the fluid channel, we demonstrate that the SEMs can be used to pattern proteins and cells in microchannels. Thus in this case, the SEMs serve as fluidic stamps for functionalizing microchannel surfaces. In addition, we show that the trap or pattern shape and size can be manipulated simply by varying the topography on the elastomeric membrane. Since SEMs, membrane valves and pumps use similar fabrication technology, we believe that SEMs can be integrated into microfluidic large-scale circuits for biotechnological applications.

Colloidal particles embedded in the cytoplasm of living mammalian cells have been found to display remarkable heterogeneity in their amplitude of motion. However, consensus on the significance and origin of this phenomenon is still lacking. We conducted experiments on Hmec-1 cells loaded with about 100 particles to reveal the intracellular particle dynamics as a function of both location and time. Central quantity in our analysis is the amplitude (A) of the individual mean-squared displacement (iMSD), averaged over a short time. Histograms of A were measured, (1) over all particles present at the same time and (2) for individual particles as a function of time. Both distributions showed significant broadening compared to particles in Newtonian liquid, indicating that the particle dynamics varies with both location and time. However, no systematic dependence of A on intracellular location was found. Both the (strong) spatial and (weak) temporal variations were further analyzed by correlation functions of A . Spatial cross correlations were rather weak down to interparticle distances of 1 microm , suggesting that the precise intracellular probe distribution is not crucial for observing a dynamic behavior that is representative for the whole cell. Temporal correlations of A decayed at approximately 10 s , possibly suggesting an intracellular reorganization at this time scale. These findings imply (1) that both individual particle dynamics and the ensemble averaged behavior in a given cell can be measured if there are enough particles per cell and (2) that the amplitude and power-law exponent of iMSDs can be used to reveal local dynamics. We illustrate this by showing how superdiffusive and subdiffusive behaviors may be hidden under an apparently diffusive global dynamics.

We integrate a sensitive microfluidic comparator into a T-junction device and report measurements of the excess pressure drop due to a single moving droplet confined in a rectangular microchannel. We specifically focus on drops that are not coated with surfactants and study the effects of drop size, droplet viscosity and capillary number on their hydrodynamic resistance. In the capillary number range of approximately 10(-3)-10(-2), we find two distinct regimes for hydrodynamic resistance behavior based on drop size. In regime I associated with small drops (drop length/channel width approximately <4), we find that the pressure drop is independent of the drop size and the capillary number, and depends weakly on the ratio of the viscosities of the two immiscible phases. In regime II, associated with large drops (drop length/channel width > approximately 4), depending on the viscosity ratio of the two phases, the hydrodynamic resistance could increase, decrease or remain unchanged with drop size. We present a simple model that qualitatively captures these experimental trends. This model reveals that the pressure drop in regime I is dominated by the dissipation due to the end caps, and in regime II by both the end caps and the central body of the droplet. Such fundamental understanding will enable the design of large-scale energy-efficient fluidic circuits by minimizing the overall pressure drop in a network and may also provide insights into controlling droplet traffic to build functional passively-driven two-phase microfluidic technologies.

We explore the possibilities of electrowetting (EW) as a tool to assess the elastic properties of aqueous jellifying materials present in the form of a small droplet on a hydrophobic substrate. We monitored the EW response of aqueous solutions of gelatin (2-10 wt %) in ambient oil for various temperatures (8-40 degrees C) below and above the gel point. Whereas the drops remained approximately spherical cap-shaped under all conditions, the voltage-induced reduction of the contact angle became progressively less pronounced upon entering the gel state at lower temperatures. We modeled the decrease in contact angle by minimizing the total energy of the drops consisting of interfacial energies, electrostatic energy, and the elastic energy due to the deformation of the drop, which was taken into account in a modified Hertz model. This allowed fitting the data and extracting the elastic modulus G, which were found to agree well with macroscopic storage moduli G' obtained with oscillatory shear rheometry. These results show that EW can be used as a tool for characterizing soft materials with the elastic moduli ranging (at least) from 10 to 1000 Pa. Our observations also create interesting perspectives for performing in situ rheological measurement inside microfluidic chips.

Living cells are a fascinating demonstration of nature's most intricate and well-coordinated micromechanical objects. They crawl, spread, contract, and relax-thus performing a multitude of complex mechanical functions. Alternatively, they also respond to physical and chemical cues that lead to remodeling of the cytoskeleton. To understand this intricate coupling between mechanical properties, mechanical function and force-induced biochemical signaling requires tools that are capable of both controlling and manipulating the cell microenvironment and measuring the resulting mechanical response. In this review, the power of microfluidics as a functional tool for research in cell mechanics is highlighted. In particular, current literature is discussed to show that microfluidics powered by soft lithographic techniques offers the following capabilities that are of significance for understanding the mechanical behavior of cells: (i) Microfluidics enables the creation of in vitro models of physiological environments in which cell mechanics can be probed. (ii) Microfluidics is an excellent means to deliver physical cues that affect cell mechanics, such as cell shape, fluid flow, substrate topography, and stiffness. (iii) Microfluidics can also expose cells to chemical cues, such as growth factors and drugs, which alter their mechanical behavior. Moreover, these chemical cues can be delivered either at the whole cell or subcellular level. (iv) Microfluidic devices offer the possibility of measuring the intrinsic mechanical properties of cells in a high throughput fashion. (v) Finally, microfluidic methods provide exquisite control over drop size, generation, and manipulation. As a result, droplets are being increasingly used to control the physicochemical environment of cells and as biomimetic analogs of living cells. These powerful attributes of microfluidics should further stimulate novel means of investigating the link between physicochemical cues and the biomechanical response of cells. Insights from such studies will have implications in areas such as drug delivery, medicine, tissue engineering, and biomedical diagnostics.

We studied the dynamics of ballistically injected latex particles (BIP) inside endothelial cells, using video particle tracking to measure the mean squared displacement (MSD) as a function of lag time. The MSD shows a plateau at short times and a linear behavior at longer times, indicating that the BIP are trapped into a viscoelastic network. To reveal more about the molecular constituents and the dynamics of this actin network, we added a variety of drugs. Latrunculin and Jasplakinolide aimed at intervening with the actin network caused a strong increase in MSD, whereas Taxol aimed at microtubules gave no measurable change in MSD. Additional corroborating information about these drug effects were obtained from MSD amplitude and exponent distributions and from fluorescent staining images of the actin and microtubule networks. Our evidence strongly suggests that BIP are primarily embedded in the actin network. Additional drug interventions aimed at disabling non-thermal forces could not conclusively resolve the nature of the forces driving BIP dynamics.

Vascular cell biology is an area of research with great biomedical relevance. Vascular dysfunction is involved in major diseases such as atherosclerosis, diabetes, and cancer. However, when studying vascular cell biology in the laboratory, it is difficult to mimic the dynamic, three-dimensional microenvironment that is found in vivo. Microfluidic technology offers unique possibilities to overcome this difficulty. In this review, an overview of the recent applications of microfluidic technology in the field of vascular biological research will be given. Examples of how microfluidics can be used to generate shear stresses, growth factor gradients, cocultures, and migration assays will be provided. The use of microfluidic devices in studying three-dimensional models of vascular tissue will be discussed. It is concluded that microfluidic technology offers great possibilities to systematically study vascular cell biology with setups that more closely mimic the in vivo situation than those that are generated with conventional methods.

We studied the mechanical behavior of packed layers of 1-mum-sized silica particles immersed in liquids, upon indentation with a 10-mum glass sphere, attached to the cantilever of an atomic force microscope (AFM). Simultaneously, a confocal scanning laser microscope (CSLM) was used to study the deformations in the material. Our liquids consisted of (nearly) refractive-index-matching water-DMSO mixtures. Particle layers were formed by sedimentation in normal gravity. In the absence of (added) electrolyte, the collective behavior of the layer is reminiscent of that of a simple liquid. Crystal-like structures were observed, with the individual particles showing positional fluctuations. Carefully adding 2 wt % LiCl to this system leads to the formation of a weakly aggregated network, in which the crystal-like order gets lost and the particles lose their mobility. On indenting into these aggregated layers, the CSLM recordings showed imprints that closely resembled the size and shape of the indenter. A more accurate inspection of the structural changes was allowed after localizing all silica particles in three dimensions. Calculated local concentrations and coordination numbers showed that even at the level of these highly local quantities, no deformation gradients could be observed in the vicinity of the probe. Particle image velocimetry analysis suggested that deformation occurs mostly in the lateral directions. On pulling the indenter out, adhesion between the silica particles and the glass indenter became manifest via a distortion of the initially spherical dent and lower coordination numbers under the dent. Together all these behaviors indicate that the aggregated layers behave like yield-stress materials, which are solidlike up to a critical stress and liquidlike above it. The results of this study also illustrate the potential of the AFM-CSLM combination to study the detailed 3D deformation in other types of systems, like granular packings or more open particle networks.

We studied spontaneous emulsification (SE) at Water/Oil (W/O) interfaces, using several types of aqueous reservoirs immersed in dodecane plus Span80 surfactant. Above a threshold surfactant concentration C(SE), aqueous satellite droplets are formed at the W/O interface. Varying the aqueous reservoir size, from below 100 microm (droplets) to centimeters (macroscopic phases), allowed investigating SE with complementary techniques. Release (rates) and size distributions for SE droplets were measured with microscopy. For gelled aqueous phases, water expulsion due to SE was quantified. Values for C(SE) were measured and were found to be higher for aqueous phases containing gelatin and/or NaCl. We also studied water exudation during network building and syneresis in aqueous gelatin gels immersed in dodecane/Span80. Below C(SE) (i.e., in the absence of SE) this process is still responsible for significant physico-chemical changes at the W/O interface. To study these in more detail, we performed atomic force microscopy experiments (in force-distance mode) on macroscopic gels. Both changes in the local elastic response and in the wettability of the AFM tip were detected. Together they suggest the formation of "water pockets" after prolonged (gel) setting times, along with a densification of the interfacial gelatin network.

In this paper, we demonstrate how the simultaneous application of atomic force microscopy (AFM) and confocal scanning laser microscopy (CSLM) can be used to characterize the (local) rheological properties of soft condensed matter at micrometer length scales. Measurement of AFM force curves as a function of the indentation amplitude and speed (magnitude and direction) can produce a "mechanical fingerprint" that contains information about material stiffness, hysteretic losses, and time scales for stress relaxation and/or network recovery. The simultaneous CSLM visualization of changes in the material's structure provides complementary information about how the material accommodates the indentation load. Since these experiments are done on areas of O(100 microm2) on materials having a surface of O(1 cm2), the measurements can be repeated on "fresh" material many times, contrary to traditional rheometers where the whole sample is loaded at once. As a particular example, we consider the case of a network of aggregated water-in-oil (W/O) emulsion droplets, in which the mechanical behavior changes drastically over time. Whereas the freshly prepared material shows a soft plastic behavior, after a time lapse of several weeks, the very same sample shows a much stiffer and elastic response. This drastic change in behavior is clearly reflected both in the signature of the AFM force curves and in (the reversibility of) the structural deformations observed with CSLM. The fact that these drastic mechanical changes take place without significant changes in the structure of the material (before loading) indicates that the stiffening of the droplet network is caused by an increase in the strength of the bonds between droplets. A remarkable finding for the elastic droplet network is that, while the structure recovers completely after the indenter is taken out, there is still an appreciable hysteresis in the force curves, indicating that dissipation also occurs. This hysteresis was not found to depend on the indentation speed.

We studied the mechanical behavior of densely packed (up to approximately 30% v/v), sedimented layers of (1 microm) water-in-oil W/O emulsion droplets, upon indentation with a (10 microm) large spherical probe. In the presence of attractive forces, the droplets form solid like networks which can resist deformation. Adding a polymer to the oil phase was used to control droplet attraction. The droplet layers were assembled via normal gravity settling. Considering that both the network structure and the droplet interactions play a key role, we used a combination of atomic force microscopy (AFM) and confocal scanning laser microscopy (CSLM) to characterize the mechanical behavior. Here the AFM was used both as indentation tool and as force sensor. Indentation experiments were performed via a protocol consisting of approach, waiting, and retract stages. CSLM was used to observe the network structure at micron resolution in real time. Use of refractive index matched fluorescent droplets allowed the visualization of the entire layer. Upon compression with the probe, a markedly nonhomogeneous deformation occurred, evidenced by the formation of a dense corona (containing practically all of the displaced droplets) in the direct vicinity of the probe, as well as more subtle deformations of force-chains at larger distances. Upon decompression, both the imprint of the indenter and the corona remained, even long after the load was released. The force-distance curves recorded with the AFM correspond well to these observations. For each deformation cycle performed on fresh material, the retract curve was much steeper than the approach curve, thus corroborating the occurrence of irreversible compaction. Contrary to classic linear viscoelastic materials, this hysteresis did not show any dependence on the deformation speed. Our force-indentation approach curves were seen to scale roughly as F approximately delta(3/2). The pre-factor was found to increase with the polymer concentration and with the density of the network. These findings suggest that this new AFM-CSLM method could be used for rheological characterization of small volumes of "granular networks" in liquid. Our hypothesis that the mechanical resistance of the networks originates from interdroplet friction forces, which in turn are set by the interdroplet potential forces, is supported by the predictions from a new mechanical model in which the interdroplet bonds are represented by stick-slip elements.

We used atomic force microscopy (AFM) to study the deformation and wetting behavior of large (50-250 microm) emulsion droplets upon mechanical loading with a colloidal glass probe. Our droplets were obtained from water-in-oil emulsions. By adding gelatin to the water prior to emulsification, also droplets with a bulk elasticity were prepared. Systematic variations of surfactant and gelatin concentrations were made, to investigate their effect on the deformation and wetting behavior of the droplets and to identify the contributions of interfacial tension, bulk elasticity, and expelled water. The AFM experiments were performed in force--distance mode and showed on approach a repulsive regime which in many cases was terminated by a jump-in of the probe. In the case of pure water (i.e. gelatin-free) droplets, the repulsive part of the curve showed a good linearity, thus allowing the extraction of an effective droplet spring constant. This quantity was found to decrease on raising the surfactant concentration from below the critical micelle concentration (cmc) to well above the cmc, and its numerical values were found to correspond remarkably well to literature values for the interfacial tension. Our findings indicate that, on gelatin increase inside the droplets, the bulk elasticity gradually becomes dominant and the droplets' stiffness does not depend anymore on surfactant concentration. Also the stability of the droplet interface against wetting, as measured by the force at which the jump-in instability occurs, was enhanced by gelatin. For gelatin concentrations of > or =15 wt %, the droplets were found to behave like purely elastic bodies. Both gelatin and surfactant contribute positively to the stability against interface breakup.

Flow electrification in nonaqueous suspensions has been scarcely reported in the literature but can significantly affect colloidal stability and (phase) behavior, perhaps even without being recognized. We have observed it in shear flow experiments on concentrated binary suspensions of hydrophobized silica particles in chloroform. In this low-polarity solvent, electrical charges on the large-particles' surfaces manifest themselves via long-ranged forces, because hardly any screening can take place through counterions. By shearing the suspension for a prolonged time, we could demonstrate that the effective interactions between the large particles change from weakly attractive (due to the small particles) to strongly repulsive (due to acquired Coulomb interactions). One of the conditions required for flow electrification was the presence of a glass surface in the shear cell. A spectacular manifestation of the phenomenon was observed with confocal video microscopy. First, the formation of large-particle aggregates was seen, while subsequently (over a long shearing time) the aggregates disintegrated into small entities, mostly primary particles. The spatial distribution of these entities in the quiescent state after stopping the flow showed evidence for acquired long-range repulsion. The occurrence of flow electrification was further corroborated by control experiments, where no flow was imposed, antistatic agent was added, or the glass bottom was coated with a conducting (indium tin oxide, ITO) layer: here, the aggregates kept growing until they became very large. To further diagnose the phenomenon, we have also done experiments in which an external electric field was applied (via the ITO layer) to an aggregated suspension. When the lower electrode was given the lowest potential, the aggregates were found to move away from the bottom and disintegrate. The qualitative similarity hereof with the flow electrification experiment suggests that in the latter, the glass acquired negative charges. After prolonged application of an external electric field, we observed segregation into regions enriched in large particles and regions completely depleted of them. In the quiescent fluid these regions exist as isolated units, but in shear flow they merge into bands, a behavior which resembles shear banding.

2D- and 3D-atomic force microscopy (AFM) experiments were performed on single casein micelles (CM) in native state, submerged in liquid, using a home-built AFM instrument. The micelles were immobilized via carbodiimide chemistry to a self-assembled monolayer supported on gold-coated slides. Off-line data analysis allowed the extraction of both surface topography and elastic properties. Relative Young moduli (E*) were derived from force-vs-indentation curves, using the Hertz theory. The obtained E* values were found to increase with CM diameter, following a straight line dependence. The data showed that temperature, via its influence on both the protein-protein interactions and the composition of the micelle, has a clear effect on the mechanical properties of the CMs: higher temperatures and lower serum casein concentrations result in stiffer micelles. For pH < or = 5.6, effecting calcium phosphate release from the micelles by decreasing the pH does not have a large effect on CM stiffness. On decrease of the pH below 5.0, particulate gels and multilayers were obtained. Their measured elasticity (expressed by an equivalent G'AFM) agrees remarkably well with the storage moduli as measured with a conventional rheometer. Compared to single micelles, gels from nonheated CM suspensions are about 3 orders of magnitude softer. The "softness" of these gels (measured under compression or shear) therefore must come from the microscopic and/or mesoscopic links rather than the micelles themselves.

We used video microscopy to study the behavior of aggregating suspensions in shear flow. Suspensions consisted of 920 nm diameter silica spheres, dispersed in a methanol/bromoform solvent, to which poly(ethylene glycol) (M = 35.000 g) was added to effect weak particle aggregation. With our solvent mixture, the refractive index of the particles could be closely matched, to allow microscopic observations up to 80 microm deep into the suspension. Also the mass density is nearly equal to that of the particles, thus allowing long observation times without problems due to aggregate sedimentation. Particles were visualized via fluorescent molecules incorporated into their cores. Using a fast confocal scanning laser microscope made it possible to characterize the (flowing) aggregates via their contour-area distributions as observed in the focal plane. The aggregation process was monitored from the initial state (just after adding the polymer), until a steady state was reached. The particle volume fraction was chosen at 0.001, to obtain a characteristic aggregation time of a few hundred seconds. On variation of polymer concentration, cP (2.2-12.0 g/L), and shear rate, gamma (3-6/s), it was observed that the volume-averaged size, Dv, in the steady state became larger with polymer concentration and smaller with shear rate. This demonstrates that the aggregate size is set by a competition between cohesive forces caused by the polymer and rupture forces caused by the flow. Also aggregate size distributions were be measured (semiquantitatively). Together with a description for the internal aggregate structure they allowed a modeling of the complete aggregation curve, from t = 0 up to the steady state. A satisfactory description could be obtained by describing the aggregates as fractal objects, with Df = 2.0, as measured from CSLM images after stopping the flow. In this modeling, the fitted characteristic breakup time was found to increase with cP.