Colloidal HgTe nanocrystals with widely tunable narrow band gap energies: from telecommunications to molecular vibrations

A convenient, aqueous-based synthesis of stable HgTe nanocrystals with widely size-tunable room temperature emission between wavelengths of 1.2 to 3.7 mum is demonstrated. By the choice of the thiols, applied as stabilizers, we optimized the growth dynamics, the luminescence quantum yields (up to 40%), and a ligand-exchange procedure, required to transfer the nanocrystals from water to nonpolar organic solvents. The latter is greatly improved and facilitated by the use of mercaptoethylamine as initial stabilizer. The possibility to tune the HgTe nanocrystal sizes from 3 to 12 nm and to control their surface functionalities (hydrophobic and hydrophilic) makes them very promising for the development of infrared optical devices, emitting in the wavelength region between the telecommunications and the molecular vibrations.     

Photoinduced phase separation

A novel approach of photoinduced phase separation has been demonstrated with a photolabile anionic surfactant, mixed with an inert nonionic surfactant in the presence of salting-out electrolyte. Breakdown of the photolyzable surfactant results in hydrophobic photoproducts, which are emulsified by the remaining inert surfactant; added electrolyte resolves the emulsion into macroscopic oily and aqueous phases. The initial micellar systems can disperse an insoluble additive marker dye (shown), which may be spatially segregated from the aqueous environment by the action of UV light.     

Effect of emulsifier type on droplet disruption in repeated shirasu porous glass membrane homogenization

The influence of various emulsifier types (anionic, nonionic, and zwitterionic) on the mean particle size, transmembrane flux, and membrane fouling in repeated membrane homogenization using a Shirasu porous glass (SPG) membrane has been investigated. Oil-in-water (O/W) emulsions (40 wt % corn oil stabilized by 0.06-2 wt % sodium dodecyl sulfate (SDS) or 0.1-2 wt % Tween 20 at pH 3 or 0.5-2 wt % beta-lactoglobulin (beta-Lg) at pH 7) were prepared by passing coarsely emulsified feed mixtures five times through the membrane with a mean pore size of 8.0 microm under the transmembrane pressure of 100 kPa. The flux increased as the number of passes increased, tending to a maximum limiting value. The maximum flux for the Tween 20-stabilized emulsions (5-47 m3.m(-2).h(-1)) was smaller than that for the SDS-stabilized emulsions (29-60 m3.m(-2).h(-1)) because less energy was needed for the disruption of a SDS-stabilized droplet due to the lower interfacial tension. The mean particle size after five passes was 4.1-6.8 and 6.4-8.7 mum for 0.1-2 wt % SDS and Tween 20, respectively. The flux in the presence of beta-Lg was much smaller than that in the presence of SDS and Tween 20, which was a consequence of more pronounced membrane fouling, due to the protein adsorption to the membrane surface. After five passes through the membrane, the fouling resistance in the presence of 2 wt % beta-Lg (1.1 x 10(10) 1/m) was 2 orders of magnitude higher than that for 0.5 wt % Tween 20 and an order of magnitude higher than the membrane resistance. If a clean membrane was used in the fifth pass, a 2-fold reduction of the fouling resistance was observed.     

Influence of interfacial characteristics on Ostwald ripening in hydrocarbon oil-in-water emulsions

The influence of the nature of the interfacial membrane on the kinetics of droplet growth in hydrocarbon oil-in-water emulsions was investigated. Droplet growth rates were determined by measuring changes in the droplet size distribution of 1 wt % n-tetradecane or n-octadecane oil-in-water emulsions using laser diffraction. The interfacial properties of the droplets were manipulated by coating them with either an SDS layer or with an SDS-chitosan layer using an electrostatic deposition method. The emulsion containing SDS-coated octadecane droplets did not exhibit droplet growth during storage for 400 h, which showed that it was stable to Ostwald ripening because of this oils extremely low water-solubility. The emulsion containing SDS-coated n-tetradecane droplets showed a considerable increase in mean droplet size with time, which was attributed to Ostwald ripening associated with this oils appreciable water-solubility. On the other hand, an emulsion containing SDS-chitosan coated n-tetradecane droplets was stable to droplet growth, which was attributed to the ability of the interfacial membrane to resist deformation because of its elastic modulus and thickness. This study shows that the stability of emulsion droplets to Ostwald ripening can be improved by using an electrostatic deposition method to form thick elastic membranes around the droplets.     

Unexpected adsorption behavior of nonionic surfactants from glycol solvents

Adsorption and interfacial properties of model methyl-capped nonionic surfactants C8E4OMe [C8H17O(C2H4O)4CH3] and C10E4OMe [C10H21O(C2H4O)4CH3] were studied in water and water/ethylene glycol mixtures as well as pure ethylene glycol. Critical micellar concentrations (cmc's), surface tensions, and surface excess were determined using surface tension (ST) and neutron reflection (NR) as a function of solvent type and surfactant tail length. The ST results show a strong dependence on solvent type in terms of cmc. The NR data were analyzed using a single-layer model for the adsorbed surfactant films. Surprisingly, the adsorption parameters obtained in both water and pure ethylene glycol were very similar, and variations in film thickness or area per molecule are negligible in respect of the uncertainties. Similarly, for C10E4OMe, estimates for the free energies of adsorption and micellization show only a weak solvent dependence. These results suggest that for such model nonionic surfactants dilute solution properties are dictated by solvophobicity, which is quite similar for this class of water, glycol, and water-glycol mixtures. More specifically, the nature of the adsorption layer appears to be hardly affected by the type of solvent subphase. The findings highlight the significance of solvophobicity and show that model nonionic surfactants can behave very similarly in hydrogen-bonding glycol solvents and water.     

Design and optimization of a new self-nanoemulsifying drug delivery system

To improve the dissolution rate of ibuprofen, a model poorly water soluble drug, self-nanoemulsifying drug delivery systems (SNEDDS) were developed. Various surfactants and oils were screened as candidates for SNEDDS on the basis of droplet size of the resulting emulsions. The influence of the constituent structure, concentration and the composition of SNEDDS formulations, and the emulsifier HLB value, on the properties of the resulting emulsions was systematically investigated. Several SNEDDS formulations were employed to study the relationship between the emulsion droplet size and the dissolution rate of ibuprofen. The dissolution rate was accelerated by decreasing the nanoemulsion droplet size, and was significantly faster than that from a conventional tablet. The optimal SNEDDS formulation had a mean nanoemulsion droplet diameters of 58 nm in phosphate buffer, pH 6.8 (simulated intestinal fluid), and released ibuprofen more than 95% within 30 min. Therefore, these novel SNEDDS carriers appear to be useful for controlling the release rate of poorly water soluble drugs.