Effect of silica particles on stability of highly concentrated water-in-oil emulsions with non-ionic surfactant

Water-in-oil, high internal phase emulsion made of super-cooled aqueous solution containing a mixture of inorganic salts and stabilized with non-ionic surfactant (sorbitan monooleate) alone was investigated. It was not possible to produce a highly concentrated emulsion (with aqueous phase fraction = 94 wt %), stabilized with surface-treated silica, solely: we were able to form an emulsion with a maximal aqueous phase mass fraction of 85 wt % (emulsion inverts/breaks above this concentration). The inversion point is dependent on the silica particle concentration, presence of salt in the aqueous phase, and does not depend on the pH of the dispersed phase. All emulsions stabilized by the nanoparticles solely were unstable to shear. So, the rheological properties and stability of the emulsions containing super-cooled dispersed phase, with regards to crystallization, were determined for an emulsion stabilized by non-ionic surfactant only. The results were compared to the properties obtained for emulsions stabilized by surface treated (relatively hydrophobic) silica nanoparticles as a co-surfactant to sorbitan monooleate. The influence of the particle concentration, type of silica surface treatment, particle/surfactant ratio on emulsification and emulsion rheological properties was studied. The presence of the particles as a co-stabilizer increases the stability of all emulsions. Also, it was found that the particle/surfactant ratio is important since the most stable emulsions are those where particles dominate over the surfactant, when the surfactant’s role is to create bridging flocculation of the particles. The combination of the two types of hydrophobic silica particles as co-surfactants is: one that resides at the water/oil interface and provides a steric boundary and another that remains in the oil phase creating a 3D-network throughout the oil phase, which is even more beneficiary in terms of the emulsion stability.     

Synthesis of nanocrystalline calcium phosphate in microemulsion--effect of nature of surfactants

Nanosized calcium phosphate (CP) powders have been synthesized by an inverse microemulsion system using kerosene as the oil phase, a cationic surfactant Aliquat 336, a non-ionic surfactant Tween 20 and their mixture and aqueous solutions of calcium nitrate tetrahydrate and biammonium hydrogen phosphate as the water phase. It has been found that the nature of surfactants played an important role to regulate the size and morphologies of the calcium phosphate nanoparticles. The cationic surfactant Aliquat 336 has been found to regulate the nucleation and crystal growth. The synthesized powders have been comprehensively characterized using transmission electron microscopy (TEM), scanning electron microscopy (SEM), powder X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). Our results show that the brushite (DCPD) is the major phase comprising the calcium phosphate nanoparticles. In mixed surfactants mediated system a morphological controlled highly crystalline particles have been synthesized. Further, the role of Aliquat 336 has been established and a plausible synthetic mechanism has been proposed.     

Non-ionic surfactant catalyzed synthesis of Betti base in water

We have developed an efficient non-ionic surfactant (Triton X-100) catalyzed multicomponent synthesis of Betti base from secondary amine, aromatic aldehydes, and β-naphthol using Mannich-type reaction in water. Lewis and Brønsted acid catalysts, ionic and non-ionic surfactant have been screened for the reaction. Non-ionic surfactant (Triton X-100) gave the best results and the reaction proceeds through the imine formation, which is stabilized by colloidal dispersion and undergoes nucleophilic addition to afford the corresponding N,N-dialkylated Betti base in excellent yields.     

Synthesis and characterization of PbS nanorods in W/O microemulsion system

PbS nanorods have been successfully synthesized in water-in-oil (W/O) microemulsion containing non-ionic surfactant OP, n-pentanol, cyclohexane, and aqueous solution. The effects of the molar ratio of water to surfactant (ω₀), the concentration of reactants and the ageing time on the morphologies of PbS nanoparticles were investigated. The microstructures, morphologies and properties of the synthesized products were characterized by means of X-ray diffraction, transmission electron microscopy, and ultraviolet-visible (UV-VIS) absorption spectroscopy, respectively. The results showed that the synthesized rod-like products are composed of cubic phase PbS. These nanorods have an average diameter of about 100 nm, and an average length of about 500 nm. In the UV-VIS absorption spectrum, the absorption edge of PbS nanorods exhibit a blue shift compared with that of bulk PbS, indicating the quantum confinement effect of PbS nano-particles     

The preparation by true liquid crystal templating of mesoporous silicates containing nanoparticulate metals

Mesostructured silicates containing metal nanoparticles have been synthesised via templating around a pre-formed, metal-containing mesophase using a non-ionic surfactant.     

EFFECT OF CHAIN LENGTH OF OXYETHYLENE GROUP ON PARTICLE SIZE AND ABSORPTION SPECTRA OF SILVER NANOPARTICLES PREPARED IN NON-IONIC WATER-IN-OIL MICRO EMULSIONS

The formation of silver nanoparticles by the method of reduction of silver ions by sodium borohydride in non-ionic water-in-oil microemulsion was investigated as a function of structure of the surfactant. Three types of non-ionic surfactants were selected differing in the chain length of the oxyethylene groups for example: NP-5, NP-9 and NP-11. The silver nanoparticles were characterized by UV-Visible Absorption Spectroscopy and Transmission Electron Microscopy. TEM. The results of this study showed that the panicle size is relatively smaller incase of NP-9 while for NP-5 and NP-11 the sizes are comparable. This obsevation is explained on the basis of structure of the droplets and the influence of Intermicellar exchange on nucleation and growth of particles.     

Influences of surfactant and nanoparticle assembly on effective interfacial tensions

We have studied assembly at air-water and liquid-liquid interfaces with an emphasis on systems containing both surfactants and nanoparticles. Anionic surfactants, sodium dodecyl sulfate (SDS) and non-ionic surfactants, Triton X-100 and tetraethylene glycol alkyl ethers (C(8)E(4), C(12)E(4) and C(14)E(4)), effectively decrease the surface tension of air-water interfaces. The inclusion of negatively charged hydrophilic silica nanoparticles (diameters of approximately 13 nm) increases the efficiency of the SDS molecules but does not alter the performance of the non-ionic surfactants. The former is likely due to the repulsive Coulomb interactions between the SDS molecules and nanoparticles which promote the surfactant adsorption at air-water interfaces. For systems involving trichloroethylene (TCE)-water interfaces, the SDS and Triton X-100 surfactants effectively decrease the interfacial tensions and the nanoparticle effects are similar compared to those involving air-water interfaces. Interestingly, the C(12)E(4) and C(14)E(4) molecules, with or without the presence of nanoparticles, fail to decrease the TCE-water interfacial tensions. Our molecular dynamics simulations have suggested that the tetraethylene glycol alkyl ether molecules tend to disperse in the TCE phase rather than adsorb at the TCE-water interfaces.     

Investigation on the locus of solubilization of polycyclic aromatic hydrocarbons in non-ionic surfactant micelles with H NMR spectroscopy

This research investigates the locus of solubilization of two significant compounds, the polycyclic aromatic hydrocarbons (PAHs) naphthalene and phenanthrene from a synthesized organic liquid phase comprised of the two PAHs and hexadecane in micelles of five polyoxyethylene non-ionic surfactants. The locus was inferred by the examination of the nuclear magnetic resonance (NMR) spectra. In this method, the ring current shifts on the ¹H resonance of the surfactant chain protons are monitored. ¹H NMR spectra were recorded for the five surfactant solutions in absence and presence of PAHs. The presence of the PAH induced the ¹H to shift along the surfactant chain. The proton shift changes were obtained by comparing the NMR spectra for the pure surfactant solutions with those for surfactant solution contacted with various non-aqueous phase liquids. It was demonstrated that the distribution of PAHs between the shell and the core of the micelles changed with the concentration of PAHs in the micelles and in the NAPL phase. The ¹H NMR analysis identified the presence of both PAHs in the shell region of the non-ionic micelles. This is an important observation because it is commonly assumed that in multi-component systems the solutes with relatively greater hydrophobicity are partitioned only in core of the non-ionic micelles. The results demonstrated the potential of the ¹H NMR analysis for the identification of the locus of solubilization of PAHs in micelles of non-ionic surfactant.     

Pressurized liquid extraction of active ingredients (ginsenosides) from medicinal plants using non-ionic surfactant solutions

The feasibility of employing aqueous non-ionic surfactant solutions as an alternative solvent system in pressurized liquid extraction (PLE) is demonstrated for the first time using the roots of American ginseng as model solid samples. When compared to the use of pure water or methanol, the presence of a common non-ionic surfactant (Triton X-100) in water at a concentration above its critical micelle concentration was shown to enhance the amount of pharmacologically active ingredients (ginsenosides) extracted from ginseng roots. The advantages of using aqueous non-surfactant solutions were also demonstrated by comparing extraction performances between ultrasonic-assisted extraction and PLE methods. Furthermore, the combination of PLE and cloud point extraction was shown to be a new and effective approach for the rapid sample preconcentration of herbal materials prior to analysis by high-performance liquid chromatography.     

A novel method for the preparation of Bi4Ti3O12 nanoparticles in w/o microemulsion

Nanometer-sized Bi₄Ti₃O₁₂ particles have been prepared by chemical reaction of bismuth nitrate pentahydrate, titanium sulfate and ammonia solution in a reverse microemulsion system consisting of water, OP (P-octyl polyethylene glycol phenylether, non-ionic surfactant), n-butanol (co-surfactant), and cyclohexane (oil). Precursor hydroxides precipitated in the droplets of water-in-oil (w/o) microemulsion were calcined at 800 °C for 4 h to form Bi₄Ti₃O₁₂ nanoparticles. The samples were investigated with X-ray diffraction (XRD), transmission electron microscopy (TEM), fourier transform infrared spectrophotometer (FT-IR) and ultraviolet visible spectrophotometer (UV–vis). It was found that the as-prepared Bi₄Ti₃O₁₂ nanoparticles had small particle sizes (35 nm), high crystallinity, narrow size distributions and strong light absorption properties not only in the ultraviolet light but also in the visible light region.     

A triptycene-based approach to solubilising carbon nanotubes and C60

We describe herein the synthesis of a triptycene-based surfactant designed with the ability to solubilise single-walled carbon nanotubes (SWNTs) and C(60) in water through non-covalent interactions. Furthermore, an amphiphilic naphthalene-based surfactant with the same ability to solubilise SWNTs and C(60) has also been prepared. The compounds synthesised were designed with either two ionic or non-ionic tails to ensure a large number of supramolecular interactions with the solvent, thereby promoting strong solubilisation. The surfactants produced stable suspensions in which the SWNTs are dispersed and the surfactant/SWNT complexes formed are stable for more than one year. UV/Vis/NIR absorption spectroscopy, TEM and AFM were employed to probe the solubilisation properties of the dispersion of surfactants and SWNTs in water.     

Spectrophotometric study of interaction and solubilization of procaine hydrochloride in micellar systems

The interaction of Procaine hydrochloride (PC) with cationic, anionic and non-ionic surfactants; cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS) and triton X-100, were investigated. The effect of ionic and non-ionic micelles on solubilization of Procaine in aqueous micellar solution of SDS, CTAB and triton X-100 were studied at pH 6.8 and 29°C using absorption spectrophotometry. By using pseudo-phase model, the partition coefficient between the bulk water and micelles, K_x, was calculated. The results showed that the micelles of CTAB enhanced the solubility of Procaine higher than SDS micelles (K_x = 96 and 166 for SDS and CTAB micelles, respectively) but triton X-100 did not enhanced the solubility of drug because of weak interaction with Procaine. From the resulting binding constant for Procaine-ionic surfactants interactions (K_b = 175 and 128 for SDS and CTAB surfactants, respectively), it was concluded that both electrostatic and hydrophobic interactions affect the interaction of surfactants with cationic procaine. Electrostatic interactions have a great role in the binding and consequently distribution of Procaine in micelle/water phases. These interactions for anionic surfactant (SDS) are higher than for cationic surfactant (CTAB). Gibbs free energy of binding and distribution of procaine between the bulk water and studied surfactant micelles were calculated.      

An atomic absorption spectrometric method for the determination of non-ionic surfactants

A method is described for the determination of non-ionic surfactants in the concentration range 0.05–2 mg l^-1.Surfactant molecules are extracted into 1,2-dichlorobenzene as a neutral adduct with potassium tetrathiocyanatozincate(II) and the determination is completed by atomic absorption spectrometry. With a 150-ml water sample, the limit of detection is 0.03 mg l^-1(as Triton X-100).The method requires a single phase separation step, is applicable, without modification, to fresh, estuarine and sea-water samples and is relatively free from interference by anionic surfactants; the presence of up to 5 mg l^-1 of anionic surfactant (as LAS) introduces an error of no more than 0.07 mg l^-1 (as Triton X-100) in the apparent non-ionic surfactant concentration.     

Preconcentration and determination of lead(II) by microextraction based on suspended cadion covered zirconia nanoparticles in a surfactant media

We have developed a method for the microextraction of lead(II) ion. It is based on the use of suspended zirconia nanoparticles modified with the reagent cadion. Pb(II) ions in the sample are adsorbed onto the modified zirconia nanoparticles suspended in the solution of a non-ionic surfactant. After cloud formation and phase separation by sedimentation, the surfactant rich phase was acidified and diluted to 100 μL with 3.0 mol L^?1 nitric acid and ultrasonicated for a few seconds to desorb the analyte from the sorbent. The mixture was centrifuged and 10 μL of the supernatant liquid phase along with 10 μL of the Pd/Mg modifier were submitted to the electrothermal atomic absorption spectrometer. The parameters affecting the extraction efficiency were optimized by the univariable method. Under the optimized conditions, a sample volume of 40 mL resulted in an enhancement factor of 384 and a detection limit (defined as 3S_b/m) of 2.2 ng L^?1. The method was successfully applied to the determination of Pb(II) in water, tea and rice samples. Accuracy was determined by the recovery experiments and the analysis of two certified reference materials.

Fine tuning of gadolinium doped ceria electrolyte nanoparticles via reverse microemulsion process

Gadolinium doped ceria (Gd–CeO₂) nanoparticles have been synthesized by an reverse microemulsion system using cyclohexane as the oil phase, a non-ionic surfactant Igepal CO 520 and their mixed aqueous solutions of gadolinium III nitrate hexahydrate and cerium III nitrate hexahydrate as the water phase. The control of particle size was achieved by varying the water to surfactant molar ratio. The synthesized and calcined powders were characterized by thermogravimetry-differential thermal analysis (TGA-DTA), X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy. The XRD results show that all the samples calcined at 700 °C were single phase cubic fluorite structure. The average size of the particle was found to increase with increase in water to surfactant molar ratio (R). The mean diameter of the particle for various value of R varies between 8–15 nm (SEM) and 7.5–11 nm (TEM), respectively. EDS confirm the presence of gadolinia and ceria phase in the nanopowder calcined at 700 °C. FTIR analysis was carried to monitor the elimination of residual oil and surfactant phases from the microemulsion-derived precursor and calcined powder. Raman spectroscopy and DTA evidenced the formation of a solid solution of gadolinium doped ceria at room temperature.     

Mixed surfactant enabled EVA emulsion for PPD applications

PPD emulsion product is advantageous for use in sub-ambient temperature as it improve the physical handling characteristic compared to traditional product. However, existing PPD emulsion system is solely implementing a single anionic surfactant system which leads instability towards a series of temperature changes. Therefore, mixed surfactant (anionic and non-ionic) surfactant was introduced to overcome this problem. Through this research, sodium dodecyl sulfate (SDS) act as anionic surfactant and Tween 80 used as non-ionic surfactant in this study. The stability of an emulsion was identified through particle size and zeta potential. For the mixed surfactant composition, the result show the presence of SDS content contributes in reduction on particle size. Furthermore, the study on effectiveness of surfactant on EVA emulsion was evaluated. The result indicates with present of surfactant, interfacial surface tension was reduced. The freezing point and pour point depressant test of the EVA emulsion was evaluated. Present of non-ionic surfactant help in stability and flow-respond at low temperature. Mixed surfactant system provides sufficient protection from droplet size growth caused by the temperature changes which eventually leads to instability.     

Comparison of the performance of non-ionic and anionic surfactants as mobile phase additives in the RPLC analysis of basic drugs

Surfactants added to the mobile phases in reversed-phase liquid chromatography (RPLC) give rise to a modified stationary phase, due to the adsorption of surfactant monomers. Depending on the surfactant nature (ionic or non-ionic), the coated stationary phase can exhibit a positive net charge, or just change its polarity remaining neutral. Also, micelles in the mobile phase introduce new sites for solute interaction. This affects the chromatographic behavior, especially in the case of basic compounds. Two surfactants of different nature, the non-ionic Brij-35 and the anionic sodium dodecyl sulfate (SDS) added to water or aqueous-organic mixtures, are here compared in the separation of basic compounds (β-blockers and tricyclic antidepressants). The reversible/irreversible adsorption of the monomers of both surfactants on the stationary phase was examined. The changes in the nature of the chromatographic system using different columns and chromatographic conditions were followed based on the changes in retention and peak shape. The study revealed that Brij-35 is suitable for analyzing basic compounds of intermediate polarity, using "green chemistry", since the addition of an organic solvent is not needed and Brij-35 is a biodegradable surfactant. In contrast, RPLC with hydro-organic mixtures or mobile phases containing SDS required high concentrations of organic solvents.     

Novel Oil‐in‐Water Emulsions Stabilised by Ionic Surfactant and Similarly Charged Nanoparticles at Very Low Concentrations

Novel oil‐in‐water (O/W) emulsions are prepared which are stabilised by a cationic surfactant in combination with similarly charged alumina nanoparticles at concentrations as low as 10^?5 m and 10^?4 wt %, respectively. The surfactant molecules adsorb at the oil‐water interface to reduce the interfacial tension and endow droplets with charge ensuring electrical repulsion between them, whereas the charged particles are dispersed in the aqueous films between droplets retaining thick lamellae, reducing water drainage and hindering flocculation and coalescence of droplets. This stabilization mechanism is universal as it occurs with different oils (alkanes, aromatic hydrocarbons and triglycerides) and in mixtures of anionic surfactant and negatively charged nanoparticles. Further, such emulsions can be switched between stable and unstable by addition of an equimolar amount of oppositely charged surfactant which forms ion pairs with the original surfactant destroying the repulsion between droplets.     

Optimization of dye-doped silica nanoparticles prepared using a reverse microemulsion method

Fluorescent labeling based on silica nanoparticles facilitates unique applications in bioanalysis and bioseparation. Dye-doped silica nanoparticles have significant advantages over single-dye labeling in signal amplification, photostability and surface modification for various biological applications. We have studied the formation of tris(2,2'-bipyridyl)dichlororuthenium(II) (Ru(bpy)) dye-doped silica nanoparticles by ammonia-catalyzed hydrolysis of tetraethyl orthosilicate (TEOS) in water-in-oil microemulsion. The fluorescence spectra, particle size, and size distribution of Ru(bpy) dye-doped silica nanoparticles were examined as a function of reactant concentrations (TEOS and ammonium hydroxide), nature of surfactant molecules, and molar ratios of water to surfactant (R) and cosurfactant to surfactant (p). The particle size and fluorescence spectra were dependent upon the type of microemulsion system chosen. The particle size was found to decrease with an increase in concentration of ammonium hydroxide and increase in water to surfactant molar ratio (R) and cosurfactant to surfactant molar ratio (p). This optimization study of the preparation of dye-doped silica nanoparticles provides a fundamental knowledge of the synthesis and optical properties of Ru(bpy) dye-doped silica nanoparticles. With this information, these nanoparticles can be easily manipulated, with regard to particle size and size distribution, and bioconjugated as needed for bioanalysis and bioseparation applications.