A novel volatile microemulsion formed by the catanionic surfactant hexadecyltrimethylammonium octylsulfonate (TA(16)So(8)), heptane and water has been explored as a template for producing nanoparticles of hydrophobic organic materials. Butylated hydroxytoluene (BHT) was employed as the model hydrophobic substance. First, the oil-in-water microemulsion was formed, containing TA16So8 as the single emulsifier and BHT dispersed in the volatile microphase. Microstructure characterization by self-diffusion NMR revealed that BHT was indeed incorporated into the oil droplets and that the mean diameter of the main droplet population was 30 nm, larger than in the BHT-free microemulsion. Next, a rapid solvent and water removal by freeze drying allowed converting the microemulsion droplets into nanoparticles in the form of a dry, fine powder. This powder was freely dispersible in water to yield a stable suspension of amorphous BHT particles with a mean size of 19 nm and zeta-potential of +37 mV. The solid nanoparticles in the aqueous dispersion were thus smaller than the initial microemulsion droplets. For comparison, a conventional o/w microemulsion composed of CTAB and sec-butanol was also tested as a template for BHT particle formation by the same process, and it was found that it yielded crystalline particles of micrometre size. On the basis of our results, we anticipate the catanionic microemulsion method to be an efficient one for producing size-controlled, water-dispersible nanoparticles of other hydrophobic organic materials.
The inhibitory effect of ammonium glycyrrhizinate (AG) on crystallization of celecoxib (CXB) nanoparticles in aqueous medium was studied. CXB nanoparticles in powder form were prepared by rapid evaporation of all solvents from a volatile oil-in-water microemulsion. A powder containing 13 wt % CXB was obtained by immediate conversion of microemulsion droplets into nanoparticles by spray drying. CXB was amorphous in this powder, which could be easily dispersed 1 wt % in water as nanoparticles. However, these particles crystallized rapidly upon dispersion, and a significant particle growth was observed. The natural surfactant, AG, which is US Food and Drug Administration approved for oral administration, inhibited crystallization of CXB, enabling a stable dispersion of nanoparticles with average size of 14 nm. Molecular dynamics simulations revealed rapid attachment of glycyrrhizinate to the growing CXB crystal and suggested that crystallization inhibition is due to interactions between the hydrophobic part of glycyrrhizinate and the phenyl moieties of CXB. (C) 2011 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 100:4390-4400, 2011
We describe here a new and simple method for preparation of polyurea nanocapsules from nanodroplets that were obtained by the phase inversion temperature (PIT) method. In the first stage, a nano-emulsion was prepared, by a heating-cooling cycle, in which the oil phase contained an oil soluble monomer (toluene 2,4-diisocyanate (TDI)). In the second stage, a water-soluble monomer and crosslinker (diethylenetriamine (DETA)) was added, leading to formation of a polymeric shell by an interfacial polycondensation reaction. The new method was demonstrated for obtaining nanocapsules of about 100 nm, in which hexadecane, dodecane, or decane were the core materials, without using any special equipment. The morphology and structure of the nanocapsules were evaluated by attenuated total reflection Fourier transform infrared (ATR-FTIR) measurements and electron microscopy. The thermal behavior of the nanocapsules containing hexadecane was studied by Differential Scanning Calorimetry (DSC) measurements, indicating that such nanocapsules can be utilized in thermal energy storage. Copyright (C) 2010 John Wiley & Sons, Ltd.
In the past few years, the synthesis of Cu nanoparticles has attracted much attention because of its huge potential for replacing expensive nano silver inks utilized in conductive printing. A major problem in utilizing these copper nanoparticles is their inherent tendency to oxidize in ambient conditions. Recently, there have been several reports presenting various approaches which demonstrate that copper nanoparticles can resist oxidation under ambient conditions, if they are coated by a proper protective layer. This layer may consist of an organic polymer, alkene chains, amorphous carbon or graphenes, or inorganic materials such as silica, or an inert metal. Such coated copper nanoparticles enable achieving high conductivities by direct printing of conductive patterns. These approaches open new possibilities in printed electronics, for example by using copper based inkjet inks to form various devices such as solar cells, Radio Frequency Identification (RFID) tags, and electroluminescence devices. This paper provides a review on the synthesis of copper nanoparticles, mainly by wet chemistry routes, and their utilization in printed electronics.
A new composition of a fully water-dilutable microemulsion system stabilized by natural surfactants is presented as a template for preparation of celecoxib nanoparticles. Nanoparticles are obtained as a dry powder upon rapid conversion of microemulsion droplets with dissolved celecoxib into nanoparticles, followed by evaporation of all the liquid in a spray dryer. The resultant powder is easily re-dispersible in water to form a clear, transparent dispersion. The celecoxib nanoparticles are amorphous and their average size in the dispersion is 17 nm, in agreement with cryo-TEM results and concentration measurements after filtration. As a result of the nanometric size and amorphous state, about 10-fold increase in dissolution of the powder was obtained, compared to that for particulate celecoxib in the presence of surfactants. (C) 2010 Elsevier B.V. All rights reserved.
A method for preparation of silica nanocapsules is described, by interfacial polymerisation of nanoemulsions which are prepared by the phase inversion temperature (PIT) method. This is a low-energy emulsification technique which does not require any special equipment, such as high-pressure homogenisers. The nanoemulsions were prepared with decane as the oil phase, in which tetraethoxysilane (TEOS) was dissolved with an ethoxylated alcohol as the surfactant. The hydrolysis and polymerisation of the TEOS was performed under acidic and basic conditions using HCl and ammonia, respectively. The obtained nanocapsules with an average size between 100 and 300 nm, which were comprised of an oil core (decane) and silica shell, were characterised using dynamic light scattering, fourier transform infrared spectroscopy (FTIR), high-resolution scanning electron microscopy (HR-SEM) and by fluorescence of an encapsulated solvatochromic dye. The capsules could be positively or negatively charged by adsorption of ionic surfactants after they were formed.
Polyelectrolyte protected beta-carotene nanoparticles (nanosuspensions) with average diameter of <100 nm were achieved by turbulent mixing and flash nanoprecipitation (FNP). Three types of multi-amine functional polyelectrolytes, epsilon-polylysine (epsilon-PL), poly(ethylene imine) (PEI), and chitosan, were investigated to electrosterically protect the nanoparticles. Particle size and distribution were measured by dynamic light scattering (DLS); particles were imaged via scanning electron microscopy (SEM) and cryogenic transmission electron microscopy (cryo-TEM). Low pH and high polyelectrolyte molecular weight gave the smallest and most stable particles. High drug loading capacity, >80 wt%, was achieved by using either PEI or chitosan. X-ray diffraction (XRD) patterns showed that beta-carotene nanoparticles were amorphous. These findings open the way for utilization of FNP for preparation of nanoparticles with enhanced bioavailability for highly water insoluble drugs. (C) 2010 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 99:4295-4306, 2010
A new approach to achieve coalescence and sintering of metallic nanoparticles at room temperature is presented. It was discovered that silver nanoparticles behave as soft particles when they come into contact with oppositely charged polyelectrolytes and undergo a spontaneous coalescence process, even without heating. Utilizing this finding in printing conductive patterns, which are composed of silver nanoparticles, enables achieving high conductivities even at room temperature. Due to the sintering of nanoparticles at room temperature, the formation of conductive patterns on plastic substrates and even on paper is made possible. The resulting high conductivity, 20% of that for bulk silver, enabled fabrication of various devices as demonstrated by inkjet printing of a plastic electroluminescent device.