Crowding in the Eye Lens: Modeling the Multisubunit Protein β-Crystallin with a Colloidal Approach.

We present a multiscale characterization of aqueous solutions of the bovine eye lens protein β crystallin from dilute conditions up to dynamical arrest, combining dynamic light scattering, small-angle x-ray scattering, tracer-based microrheology, and neutron spin echo spectroscopy. We obtain a comprehensive explanation of the observed experimental signatures from a model of polydisperse hard spheres with additional weak attraction. In particular, the model predictions quantitatively describe the multiscale dynamical results from microscopic nanometer cage diffusion over mesoscopic micrometer gradient diffusion up to macroscopic viscosity.

Soft particles in an electric field - a zero average contrast study.

We report on the structural properties of ionic microgel particles subjected to alternating electric fields, using small-angle neutron scattering. The experiments were performed under so-called zero average contrast conditions, which cancel the structure factor contribution to the scattered intensity, allowing us to obtain direct information on the single particle size and structure as particles align in field-induced strings. Our results reveal only a marginal compression of the particles as they align in strings, and indicate considerable particle overlap at higher field strengths.

A new look at effective interactions between microgel particles.

Thermoresponsive microgels find widespread use as colloidal model systems, because their temperature-dependent size allows facile tuning of their volume fraction in situ. However, an interaction potential unifying their behavior across the entire phase diagram is sorely lacking. Here we investigate microgel suspensions in the fluid regime at different volume fractions and temperatures, and in the presence of another population of small microgels, combining confocal microscopy experiments and numerical simulations.

Deswelling behaviour of ionic microgel particles from low to ultra-high densities.

The swelling of ionic microgel particles is investigated at a wide range of concentrations using a combination of light, X-ray and neutron scattering techniques. We employ a zero-average contrast approach for small-angle neutron scattering experiments, which enables a direct determination of the form factor at high concentrations. The observed particle size initially decreases strongly with the particle concentration in the dilute regime but approaches a constant value at intermediate concentrations.

Interpenetration of polymeric microgels at ultrahigh densities.

Soft particles such as polymeric microgels can form ultra-dense phases, where the average center-to-center distance a can be smaller than the initial unperturbed particle diameter σ , due to their ability to interpenetrate and compress. However, despite of the effort devoted to microgels at ultrahigh densities, we know surprisingly little about their response to their environment at effective volume fractions ϕ above close packing (ϕ ), and the existing information is often contradictory. Here we report direct measurements of the size and shape of poly(N-isopropylacrylamide) microgels at concentrations below and above ϕ using the zero average contrast method in small-angle neutron scattering.

Cubosomes for in vivo fluorescence lifetime imaging.

Herein we provided the first proof of principle for in vivo fluorescence optical imaging application using monoolein-based cubosomes in a healthy mouse animal model. This formulation, administered at a non-cytotoxic concentration, was capable of providing both exogenous contrast for NIR fluorescence imaging with very high efficiency and chemospecific information upon lifetime analysis. Time-resolved measurements of fluorescence after the intravenous injection of cubosomes revealed that the dye rapidly accumulated mainly in the liver, while lifetimes profiles obtained in vivo allowed for discriminating between free dye or dye embedded within the cubosome nanostructure after injection.

Docetaxel-Loaded Fluorescent Liquid-Crystalline Nanoparticles for Cancer Theranostics.

Here, we describe a novel monoolein-based cubosome formulation engineered for possible theranostic applications in oncology. The Docetaxel-loaded nanoparticles were stabilized in water by a mixture of commercial Pluronic (poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer) F108 (PF108) and rhodamine- and folate-conjugated PF108 so that the nanoparticles possess targeting, therapeutic, and imaging properties. Nanoparticles were investigated by DLS, cryo-TEM, and SAXS to confirm their structural features.

Water-Insoluble Surface Coatings of Polyion-Surfactant Ion Complex Salts Respond to Additives in a Surrounding Aqueous Solution.

Hydrated, but water-insoluble, "complex salts" (CS) composed of alkyltrimethylammonium surfactant ions with polyacrylate counterions are known to exhibit a rich phase behavior in bulk mixtures with water and have recently been shown to act as water-responsive surface coatings. Here it is shown, by SAXS measurements, that surface coatings of CS also respond to various added solutes in a surrounding aqueous solution, by altering their liquid crystalline structure. The obtained results provide new information on the phase behavior of CS in contact with water and aqueous solutions.

Thermo-Resistant Soft Glassy Suspensions of Polymeric Micellar Nanoparticles in Ionic Liquid.

We report the rheological and structural properties of a suspension comprising poly(ethylene oxide)-polystyrene-poly(ethylene oxide) core-shell micellar nanoparticles dispersed in 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid. A liquid to soft solid transition was observed at a copolymer concentration of 10 wt % above which an elastic soft material was formed, which was composed of non-ordered jammed core-shell micellar nanoparticles. In the soft solid state, a significant reduction in the size of the nanoparticles, approaching hard sphere behavior, was observed by small-angle X-ray scattering which is attributed to compression of the soft poly(ethylene oxide) coronas.

Interactions of small dendrimers with sodium dodecyl sulfate at the air-water interface.

We have determined how the bulk behavior of mixtures of small cationic poly(amidoamine) dendrimers (generation 2, PAMAM-G2) and sodium dodecyl sulfate (SDS) affects the structure and composition of the adsorbed layers at the air-water interface. The aim is to reveal how the size of a well-defined hyperbranched polyelectrolyte affects the interfacial and bulk solution behavior of mixtures with oppositely charged surfactants, when the size of the polyelectrolyte approaches that of the surfactant. A combination of electrophoretic mobility, UV-vis spectroscopy, dynamic light scattering, and small-angle X-ray scattering measurements have been employed to characterize the interactions in the bulk solution.

The effect of protein PEGylation on physical stability in liquid formulation.

The presence of micron aggregates in protein formulations has recently attracted increased interest from regulatory authorities, industry, and academia because of the potential undesired side effects of their presence. In this study, we characterized the micron aggregate formation of hen egg-white lysozyme (Lyz) and its diPEGylated (5 kDa) analog as a result of typical handling stress conditions. Both proteins were subjected to mechanical stress in the absence and presence of silicone oil (SO), elevated temperatures, and freeze-thaw cycles.

On the self-assembly of a tryptophan labeled deoxycholic acid.

Self-assembly of peptides and bile acids has been widely investigated because of their biological role and their potential as a tool for the preparation of nanostructured biomaterials. We herein report both the synthesis and the self-association behavior of a compound that combines the aggregation properties of bile acid- and amino acid-based molecules. The derivative has been prepared by introducing a L-tryptophan residue into the C-3 position of the deoxycholic acid skeleton and resulted in an amphoteric fluorescent labeled bile acid that shows a pH-dependent self-assembly.

Sugar-bile acid-based bolaamphiphiles: from scrolls to monodisperse single-walled tubules.

The introduction of a mannose residue on carbon 3 of lithocholic acid gives rise to an asymmetric and rigid bolaamphiphilic molecule, which self-assembles in water to form elongated tubular aggregates with an outer diameter of about 20 nm. These tubular structures display a temporal evolution, where the average tube diameter decreases with time, which can be followed by time-resolved small-angle X-ray scattering experiments. Cryogenic transmission electron microscopy images collected as a function of time show that at short times after preparation tubular scrolls are formed via the rolling of layers, after which a complex transformation of the scrolls into single-walled tubules takes place.

Sterically stabilized colloids with tunable repulsions.

When studying tunable electrostatic repulsions in aqueous suspensions of charged colloids, irreversible colloid aggregation or gelation may occur at high salt concentrations. For many commonly used synthetic colloids, such as polystyrene and silica particles, the reason for coagulation is the presence of unbalanced, strongly attractive, and short-ranged van der Waals (VDW) forces. Here, we present an aqueous polystyrene model colloid that is sterically stabilized against VDW attractions.

Structure and dynamics of soft repulsive colloidal suspensions in the vicinity of the glass transition.

We use a combination of different scattering techniques and rheology to highlight the link between structure and dynamics of dense aqueous suspensions of soft repulsive colloids in the vicinity of a glass transition. Three different latex formulations with an increasing amount of the hydrophilic component resulting in either purely electrostatically or electrosterically stabilized suspensions are investigated. From the analysis of the static structure factor measured by small-angle X-ray scattering, we derive an effective volume fraction that includes contributions from interparticle interactions.

Aggregation behavior of bovine κ- and β-casein studied with small angle neutron scattering, light scattering, and cryogenic transmission electron microscopy.

In the native bovine casein micelle the calcium sensitive caseins (α(S1)-, α(S2)- and β-casein) sequester amorphous calcium phosphate in nanometer-sized clusters, whereas the calcium-insensitive κ-casein limits the growth of the micelle. In this paper, we further investigate the self-association of κ- and β-casein, which are two of the key proteins that control the substructure of the milk casein micelle, using neutron and light scattering techniques and cryogenic transmission electron microscopy. Results demonstrate that κ-casein can, apart from the known self-assembly, form amyloid-like fibrils already at temperatures of 25 °C when subject to agitation.

Light and neutron scattering study of PEG-oleate and its use in emulsion polymerization.

Steric stabilization of colloids forms a robust mechanism to obtain colloids that are stable in a variety of environments, and that can be used to study the phase behavior of hard or soft spheres. We report the synthesis of sterically stabilized colloids in an aqueous environment using readily dissolvable surfactants, with an unsaturated hydrophobic tail. We synthesized a new surfactant by esterification of a poly(ethylene glycol) (PEG) chain of 4.

Viscoelastic properties of polystyrene and poly(methyl methacrylate) dispersions sterically stabilized by hydrophobically modified inulin (polyfructose) polymeric surfactant.

Recently, steric repulsive forces induced by a new graft copolymer surfactant, which is based in inulin (polyfructose), have been described. Previous investigations by atomic force microscopy between solid surfaces covered with adsorbed surfactant indicated strong repulsive forces even at high electrolyte concentration, due to the steric repulsion produced by the surfactant hydration. In the present paper, the colloidal stabilization provided by this surfactant is studied by rheology.