Laser-induced cavitation in nanoemulsion with gold nanospheres for blood clot disruption: in vitro results.

Optically activated cavitation in a nanoemulsion contrast agent is proposed for therapeutic applications. With a 56°C boiling point perfluorohexane core and highly absorptive gold nanospheres at the oil-water interface, cavitation nuclei in the core can be efficiently induced with a laser fluence below medical safety limits (70 mJ/cm2 at 1064 nm). This agent is also sensitive to ultrasound (US) exposure and can induce inertial cavitation at a pressure within the medical diagnostic range. Images from a high-speed camera demonstrate bubble formation in these nanoemulsions. The potential of using this contrast agent for blood clot disruption is demonstrated in an in vitro study. The possibility of simultaneous laser and US excitation to reduce the cavitation threshold for therapeutic applications is also discussed.

Pickering emulsions stabilized by nanoparticle surfactants.

Amphiphilic gold nanoparticles are demonstrated to effectively stabilize emulsions of hexadecane in water. Nanoparticle surfactants are synthesized using a simple and scalable one-pot method that involves the sequential functionalization of particle surfaces with thiol-terminated polyethylene glycol (PEG) chains and short alkane-thiol molecules. The resulting nanoparticles are shown to be highly effective emulsifying agents due to their strong adsorption at oil-water and air-water interfaces. The original nonfunctionalized gold nanoparticles are unable to effectively stabilize oil-water emulsions due to their small size and low adsorption energy. Small-angle X-ray scattering and electron microscopy are used to demonstrate the formation of nanoparticle-stabilized colloidosomes that are stable against coalescence and show significant shifts in plasmon resonance enhancing the near-infrared optical absorption.

Competitive adsorption of thiolated poly(ethylene glycol) and alkane-thiols on gold nanoparticles and its effect on cluster formation.

The surface concentration and conformation of thiol-terminated poly(ethylene glycol) (PEG) on gold nanoparticles are studied before and after coadsorption of alkane-thiols. Thermogravimetric analysis (TGA) indicates alkane-thiol ligands will competitively adsorb on gold surfaces of nanoparticles and that the extent of PEG-thiol replacement depends on the specific length of the alkane-thiol molecule. The conformation of the polymer is also affected by the length and packing density of the alkane-thiol. Dynamic light scattering (DLS) shows that the hydrodynamic size of coated particles has an intermediate maximum for the adsorption of octane-thiol, which also forms the most densely packed alkane-thiol monolayers. These two factors greatly impact the formation of clusters by nanoparticle surfactants. Small angle X-ray scattering (SAXS) shows that the largest clusters are formed when particles have a low PEG-thiol surface concentration and an extended PEG conformation.

SANS and SAXS analysis of charged nanoparticle adsorption at oil-water interfaces.

A systematic study of the adsorption of charged nanoparticles at dispersed oil-in-water emulsion interfaces is presented. The interaction potentials for negatively charged hexadecane droplets with anionic polystyrene latex particles or cationic gold particles are calculated using DLVO theory. Calculations demonstrate that increased ionic strength decreases the decay length of the electrostatic repulsion leading to enhanced particle adsorption. For the case of anionic PS latex particles, the energy barrier for particle adsorption is also reduced when the surface charge is neutralized through changes in pH. Complementary small-angle scattering experiments show that the highest particle adsorption for PS latex occurs at moderate ionic strength and low pH. For cationic gold particles, simple DLVO calculations also explain scattering results showing that the highest particle adsorption occurs at neutral pH due to the electrostatic attraction between oppositely charged surfaces. This work demonstrates that surface charges of particles and oil droplets are critical parameters to consider when engineering particle-stabilized emulsions.

Highly transparent multifunctional bilayer coatings on polymers using low-temperature atmospheric plasma deposition.

We report on the synthesis of hard, adhesive, and highly transparent bilayer organosilicate thin films on large poly(methyl methacrylate) substrates by atmospheric plasma, in ambient air, at room temperature, in a one-step process, using a single precursor. The method overcomes the challenge of fabricating coatings with high mechanical and interfacial properties in a one-step process. The bottom layer is a carbon-bridged hybrid silica with excellent adhesion with the poly(methyl methacrylate) substrate, and the top layer is a dense silica with high Young's modulus, hardness, and scratch resistance. The bilayer structure exhibited ~100% transmittance in the visible wavelength range, twice the adhesion energy and three times the Young's modulus of commercial polysiloxane sol­gel coatings.

Nonlinear contrast enhancement in photoacoustic molecular imaging with gold nanosphere encapsulated nanoemulsions.

A composite contrast agent, a nanoemulsion bead with assembled gold nanospheres at the interface, is proposed to improve the specific contrast of photoacoustic molecular imaging. A phase transition in the bead's core is induced by absorption of a nanosecond laser pulse with a fairly low laser fluence (∼3.5 mJ/cm2), creating a transient microbubble through dramatically enhanced thermal expansion. This generates nonlinear photoacoustic signals with more than 10 times larger amplitude compared to that of a linear agent with the same optical absorption. By applying a differential scheme similar to ultrasound pulse inversion, more than 40 dB contrast enhancement is demonstrated with suppression of background signals.

Small angle scattering model for Pickering emulsions and raspberry particles.

Pickering emulsions, raspberry particles and other colloidal particle complexes are often characterized using small angle scattering techniques. The present work derives an analytical scattering model that accounts for the self-correlation of a spherical core and surface adsorbed particles as well as the particle-particle and core-particle correlation terms characteristic of Pickering emulsions and raspberry particles. It is shown that contrast matching of the scattering length density is not essential to obtain meaningful information as long as the scattering contrasts of all phases are precisely known. The derived equations are useful for analyzing data and planning experiments for Small Angle Neutron Scattering (SANS) and Small Angle X-ray Scattering (SAXS) involving these colloidal systems.