We present an approach to fabricate solid capsules with precise control of size, permeability, mechanical strength, and compatibility. The capsules are fabricated by the self-assembly of colloidal particles onto the interface of emulsion droplets. After the particles are locked together to form elastic shells, the emulsion droplets are transferred to a fresh continuous-phase fluid that is the same as that inside the droplets. The resultant structures, which we call "colloidosomes", are hollow, elastic shells whose permeability and elasticity can be precisely controlled. The generality and robustness of these structures and their potential for cellular immunoisolation are demonstrated by the use of a variety of solvents, particles, and contents.
We present novel measurements of the structure of colloidal gels. Using confocal microscopy, we obtain the precise three-dimensional positions of a large number of particles. We develop quantitative descriptions of the topology of the gel, including the number of bonds per particle, the chemical or bond fractal dimension, the number of flexible pivot points and other topological parameters that describe the chainlike structure. We investigate the dependence of these parameters on the particle volume fraction and the strength of the attraction that holds the particles together. While all samples have approximately the same fractal and chemical dimensions, we find that gels formed with stronger attraction or larger volume fraction have fewer bonds per particle, more filamentous chains and a greater number of flexible pivot points. Finally, we discuss the topological results in the context of the gel's elasticity. Measurements of the elastic constants of individual chainlike segments are explained with a simple model. The distribution of elastic constants, however, has a general form that is not understood.
We have developed a technique in ultrasonic correlation spectroscopy called diffusing acoustic wave spectroscopy (DAWS). In this technique, the motion of the scatterers (e.g., particles or inclusions) is determined from the temporal fluctuations of multiply scattered sound. In DAWS, the propagation of multiply scattered sound is described using the diffusion approximation, which allows the autocorrelation function of the temporal field fluctuations to be related to the dynamics of the multiply scattering medium. The expressions relating the temporal field autocorrelation function to the motion of the scatterers are derived, focusing on the types of correlated motions that are most likely to be encountered in acoustic measurements. The power of this technique is illustrated with ultrasonic data on fluidized suspensions of particles, where DAWS provides a sensitive measure of the local relative velocity and strain rate of the suspended particles over a wide range of time and length scales. In addition, when combined with the measurements of the rms velocity of the particles using dynamic sound scattering, we show that DAWS can be used to determine the spatial extent of the correlations in the particle velocities, thus indirectly measuring the particle velocity correlation function. Potential applications of diffusing acoustic wave spectroscopy are quite far reaching, ranging from the ultrasonic nondestructive evaluation of the dynamics of inhomogeneous materials to geophysical studies of mesoscopic phenomena in seismology.
Experiments investigating the local viscoelastic properties of a simple uncross-linked flexible polymer are performed on polyethylene oxide solutions in the semidilute regime using polystyrene beads of varying sizes and surface chemistry as probes. We measure the thermal motions of the beads to obtain the elastic and viscous moduli of our sample. Two different dynamic light scattering techniques, diffusing wave spectroscopy and quasielastic light scattering (QELS), are used to determine the dynamics of the probe particles. Diffusing wave spectroscopy probes the short time dynamics of the scatterers while QELS or single scattering measures the dynamics at larger times. This results in a larger frequency overlap of the data obtained from the microrheological techniques with the data obtained from the conventional bulk measurements. The moduli are estimated using a modified algebraic form of the generalized Stokes-Einstein equation. Comparison of microrheology with,bulk measurements shows excellent similarity confirming the applicability of this method for simple, uncross-linked polymeric systems.
Using particle tracking routines the location of single point light sources can be determined with an accuracy of a few nanometers. By using quantum dots (QDs) emitting at different wavelengths, the measurement of the distance between these point light sources, which are closer than the optical resolution of 200 nm, was achieved. The nanocrystals have major advantages over conventional chromophores in higher quantum yield, more photostability, and the possibility of different emission wavelengths by an excitation with a single wavelength. The colocalization of two single QDs at the least distance of 40 nm can be measured with a standard deviation of 5 nm and a time resolution of 117 ms using one excitation wavelength.
We describe a new design for a microscope-based static light-scattering instrument that provides simultaneous high-resolution images and static light-scattering data. By correlating real space images with scattering patterns, we can interpret measurements from heterogeneous samples, which we illustrate by using biological tissue. (C) 2001 Optical Society of America.
We develop a multiple particle tracking technique for making precise., localized measurements of the mechanical microenvironments of inhomogeneous materials. Using video microscopy, we simultaneously measure the Brownian dynamics of roughly one hundred fluorescent tracer particles embedded in a complex medium and interpret their motions in terms of local viscoelastic response. To help overcome the inherent statistical limitations due to the finite imaging volume and limited imaging times, we develop statistical techniques and analyze the distribution of particle displacements in order to make meaningful comparisons of individual particles and thus characterize the diversity and properties of the microenvironments. The ability to per-form many local measurements simultaneously allows more precise measurements even in systems that evolve in time. We show several examples of inhomogeneous materials to demonstrate the flexibility of the technique and learn new details of the mechanics of the microenvironments that small particles explore. This technique extends other microrheological methods to allow simultaneous measurements of large numbers of probe particles, enabling heterogeneous samples to be studied more effectively.
A wide variety of systems, including granular media, colloidal suspensions and molecular systems, exhibit non-equilibrium transitions from a fluid-like to a solid-like state, characterized solely by the sudden arrest of their dynamics. Crowding or jamming of the constituent particles traps them kinetically, precluding further exploration of the phase space(1). The disordered fluid-like structure remains essentially unchanged at the transition. The jammed solid can be refluidized by thermalization, through temperature or vibration, or by an applied stress. The generality of the jamming transition led to the proposal(2) of a unifying description, based on a jamming phase diagram. It was further postulated that attractive interactions might have the same effect in jamming the system as a confining pressure, and thus could be incorporated into the generalized description. Here we study experimentally the fluid-to-solid transition of weakly attractive colloidal particles, which undergo markedly similar gelation behaviour with increasing concentration and decreasing thermalization or stress. Our results support the concept of a jamming phase diagram for attractive colloidal particles, providing a unifying link between the glass transition(3), gelation(4,5) and aggregation(6-8).
We show that gelation of weakly attractive colloids is remarkably similar to the colloidal glass transition. Like the glass transition, dynamic light scattering functions near gelation scale with scattering vector, and exhibits a two-step decay with a power-law divergence of the final decay time. Like the glass transition, static light scattering does not change upon gelation. These results suggest that, like the glass transition, gelation results from kinetic arrest due to crowding of clusters, and that both gelation and the glass transition are manifestations of a more general jamming transition.
The slow sedimentation of suspensions of solid particles in a fluid results in complex phenomena that are poorly understood. For a low volume fraction (phi) of particles, long-range hydrodynamic interactions result in surprising spatial correlations(1) in the velocity fluctuations; these are reminiscent of turbulence, even though the Reynolds number is very low(2-4). At higher values of phi, the behaviour of sedimentation remains unclear; the upward backflow of fluid becomes increasingly important, while collisions and crowding further complicate inter-particle interactions(5-8). Concepts from equilibrium statistical mechanics could in principle be used to describe the fluctuations and thereby provide a unified picture of sedimentation, but one essential ingredient-an effective temperature that provides a mechanism for thermalization-is missing. Here we show that the gravitational energy of fluctuations in particle number can act as an effective temperature. Moreover, we demonstrate that the high-phi behaviour is in fact identical to that at low phi, provided that the suspension viscosity and sedimentation velocity are scaled appropriately, and that the effects of particle packing are included.
In order to provide depth resolution for bulk tissue imaging experiments using fluorescence or absorption signals, we have designed an internal laser point spread technique. A laser light source has been imbedded in different depths into cardiac tissue and tissue phantoms, the signal on the tissue surface detected by a CCD detector. These measurements in combination with an analytic solution of the diffusion equation allow us to estimate optical properties of the investigated tissue. We show how this information provides the core of depth quantification of fluorescence and absorption measurements in bulk tissue and investigate experimentally the transition from single scattering to diffuse photon transport in cardiac tissue and suspensions of microscopic spherical particles that serve as model systems. (C) 2001 Optical Society of America.
Times Cited: 0 Conference on Photon Migration, Optical Coherence Tomography, and Microscopy Jun 18-21, 2001 Munich, germany Opt Soc Amer; SPIE; Deutsch Gesell Lasermed eV; European Opt Soc; IEEE
We study the effect of isopropyl alcohol (IPA) and various salts (sodium chloride, sodium thiocyanate, sodium carbonate, and urea) on the rheological behavior and the conformation of aqueous guar solutions. Ultralow angle light scattering, conventional light scattering, and neutron scattering are used to probe the structure of guar over length scales spanning 5 decades, from a few angstroms to several tens of microns. Although both IPA and salts worsen solvent conditions, their effect is very different. Isopropyl alcohol promotes the formation of a network of large-scale structures via intermolecular associations, thus increasing dramatically the elastic response of guar solutions. Salts. on the contrary, affects guar on a local scale, leading to a more collapsed chain configuration, thus to a lower effective volume fraction and to reduced viscosity.
Crystallization of concentrated colloidal suspensions was studied in real space with laser scanning confocal microscopy. Direct imaging in three dimensions allowed identification and observation of both nucleation and growth of crystalline regions, providing an experimental measure of properties of the nucleating crystallites. By following their evolution, we identified critical nuclei, determined nucleation rates, and measured the average surface tension of the crystal-liquid interface. The structure of the nuclei was the same as the bulk solid phase, random hexagonal close-packed, and their average shape was rather nonspherical, with rough rather than faceted surfaces.
Confocal microscopy is used in the study of colloidal gels, glasses, and binary fluids. We measure the three-dimensional positions of colloidal particles with a precision of approximately 50 nm (a small fraction of each particle's radius) and with a time resolution sufficient for tracking the thermal motions of several thousand particles at once. This information allows us to characterize the structure and the dynamics of these materials in qualitatively new ways, for example, by quantifying the topology of chains and clusters of particles as well as by measuring the spatial correlations between particles with high mobilities. We describe our experimental technique and describe measurements that complement the results of light scattering. (C) 2001 Optical Society of America.