Modulated 3D cross-correlation light scattering: improving turbid sample characterization

Accurate characterization using static light scattering (SLS) and dynamic light scattering (DLS) methods mandates the measurement and analysis of singly-scattered light. In turbid samples, the suppression of multiple scattering is therefore required to obtain meaningful results. One powerful technique for achieving this, known as 3D cross-correlation, uses two simultaneous light scattering experiments performed at the same scattering vector on the same sample volume in order to extract only the single scattering information common to both. Here we present a significant improvement to this method in which the two scattering experiments are temporally separated by modulating the incident laser beams and gating the detector outputs at frequencies exceeding the timescale of the system dynamics. This robust modulation scheme eliminates cross-talk between the two beam- detector pairs and leads to a four-fold improvement in the cross-correlation intercept. We measure the dynamic and angular-dependent scattering intensity of turbid colloidal suspensions and exploit the improved signal quality of the modulated 3D cross-correlation DLS and SLS techniques.Comment: Review of Scientific Instruments, accepted for publicatio

Charactrisation of particle assemblies by 3D cross correlation light scattering and diffusing wave spectroscopy

To characterize the structural and dynamic properties of soft materials and small particles, information on the relevant mesoscopic length scales is required. Such information is often obtained from traditional static and dynamic light scattering (SLS/DLS) experiments in the single scattering regime. In many dense systems, however, these powerful techniques frequently fail due to strong multiple scattering of light. Here I will discuss some experimental innovations that have emerged over the last decade. New methods such as 3D static and dynamic light scattering (3D LS) as well as diffusing wave spectroscopy (DWS) can cover a much extended range of experimental parameters ranging from dilute polymer solutions, colloidal suspensions to extremely opaque viscoelastic emulsions

Lifetime of fluorescent dye molecules in dense aqueous suspensions of polystyrene nanoparticles

We study the lifetime of two common fluorescent dye molecules from the Alexa Fluor NHS Ester family dissolved in water in an opaque aqueous dispersion of dielectric polystyrene nanoparticles. We investigate the role of the dispersion composition by varying the particle concentration and adding SDS (sodium dodecyl sulfate) surfactant molecules. The observed strong changes in lifetime of Alexa 430 can be attributed to the relative contribution of radiative and non-radiative decay channels while the lifetime of the Alexa 488 dye depends only weakly on the sample composition. For Alexa 430, a dye with a rather low quantum yield in aqueous solution, the addition of polystyrene nanoparticles leads to a significant enhancement in quantum yield and an associated increase of the fluorescent lifetime by up to 55 %. We speculate that the increased quantum yield can be attributed to the hydrophobic effect on the structure of water in the boundary layer around the polystyrene particles in suspension. Adding SDS acts as a quencher. Over a range of particle concentrations the particle induced increase of the lifetime can be completely compensated by adding SDS

Rapid high resolution imaging of diffusive properties in turbid media

We propose a laser speckle based scheme that allows the analysis of local scattering properties of light diffusely reflected from turbid media. This turbid medium can be a soft material such as a colloidal or polymeric material but can also be biological tissue. The method provides a 2D map of the scattering properties of a complex, multiple scattering medium by recording a single image. We demonstrate that the measured speckle contrast can be directly related to the local transport mean free path l* or the reduced scattering coefficient μt = 1/l* of the medium. In comparison to some other approaches, the method does not require scanning (of a laser beam, detector or the sample itself) in order to generate a spatial map. It can conveniently be applied in a reflection geometry and provides a single characteristic value at any given position with an intrinsic resolution typically on the order of 5–50 μm. The actual resolution is however limited by the transport mean free path itself and can thus range from microns to millimeter

Crossover between entropic and interfacial elasticity and osmotic pressure in uniform disordered emulsions

We develop a simple predictive model of the osmotic pressure Π and linear shear elastic modulus G′p of uniform disordered emulsions that includes energetic contributions from entropy and interfacial deformation. This model yields a smooth crossover between an entropically dominated G′p ∼ kBT/a³ for droplet volume fractions ϕ below a jamming threshold for spheres, ϕc, and an interfacially dominated G′p ∼ σ/a for ϕ above ϕc, where a and σ are the undeformed radius and interfacial tension, respectively, of a droplet and T is the temperature. We show that this model reduces to the known ϕ-dependent jamming behavior G′p(ϕ) ∼ (σ/a)ϕ(ϕ − ϕc) as T → 0 for ϕ > ϕc of disordered uniform emulsions, and it also produces the known divergence for disordered hard spheres G′p(ϕ) ∼ (kBT/a³)ϕ/(ϕc − ϕ) for ϕ ϕc when σ → ∞. We compare predictions of this model to data for disordered uniform microscale emulsion droplets, corrected for electrostatic repulsions. The smooth crossover captures the observed trends in G′p and Π below ϕc better than existing analytic models of disordered emulsions, which do not make predictions below ϕc. Moreover, the model predicts that entropic contributions to the shear modulus can become more significant for nanoemulsions as compared to microscale emulsions.LaMnO

Superresolution Microscopy of the Volume Phase Transition of pNIPAM Microgels

Hierarchical polymer structures such as pNIPAM microgels have been extensively studied for their ability to undergo significant structural and physical transformations that can be controlled by external stimuli such as temperature, pH or solvent composition. However, direct three-dimensional visualization of individual particles in situ have so far been hindered by insufficient resolution, with optical microscopy, or contrast, with electron microscopy. In recent years superresolution microscopy techniques have emerged that in principle can provide nanoscopic optical resolution. Here we report on the in-situ superresolution microscopy of dye-labeled submicron sized pNIPAM microgels revealing the internal microstructure during swelling and collapse of individual particles. Using direct STochastic Optical Reconstruction Microscopy (dSTORM) we demonstrate a lateral optical resolution of 30nm and an axial resolution of 60nm.Comment: 7 pages, 5 figure