Structure of concentrated nanoemulsions

We use extreme shear to create a dispersion of nanoscale droplets of silicone oil in an immiscible water phase containing an anionic surfactant sodium dodecylsulfate. Using centrifugal size fractionation, we obtain nanoemulsions having a well-defined average radius of a=75 nm. We measure the structure of concentrated nanoemulsions over a wide range of volume fractions, 0相似文献   

Oil-in-water nanoemulsions for pesticide formulations

A two-step process for formation of nanoemulsions in the system water/poly(oxyethylene) nonionic surfactant/methyl decanoate at 25 degrees C is described. First, all the components were mixed at a certain composition to prepare a microemulsion concentrate, which was rapidly subjected into a large dilution into water to generate an emulsion. Bluish transparent oil-in-water (O/W) nanoemulsions were formed only when the concentrate was located in the bicontinuous microemulsion (BC) or oil-in-water microemulsion (Wm) region. The existence of an optimum oil-to-surfactant ratio (R(os)) in the BC or Wm region indicates that both the phase behavior and the composition of the concentrate are important factors in nanoemulsion formation. To demonstrate potential applications of these systems, they were employed to formulate a water-insoluble pesticide, beta-cypermethrin (beta-CP). The nanoemulsion was compared with a commercial beta-CP microemulsion in terms of the stability of sprayed formulations.     

PTFE nanoemulsions as ultralow-k dielectric materials

Modern integrated circuits require insulating materials with a dielectric constant as low as possible in order to obtain device speed improvements through lower RC delay. We have investigated the electrical and structural properties of PTFE thin films obtained from Algoflon^®-PTFE nanoemulsions, via spin coating deposition, followed by sintering. Films as thin as 160 nm with dielectric strength better than 4 MV/cm have been obtained.     

Effective structure factor of osmotically deformed nanoemulsions

Extreme osmotic compression of nanoemulsion droplets, achieved by ultracentrifugation, can create solidlike biliquid foams without causing significant droplet coalescence. Using small-angle neutron scattering (SANS), we probe the structure of a uniform silicone oil-in-water nanoemulsion stabilized by sodium dodecyl sulfate over a wide range of volume fractions, phi, up to and beyond the limit associated with maximal random jamming of spheres, phiMRJ = 0.64. Although some features in the structure can be understood at lower phi using simple predictions for hard spheres, the anionic repulsion and deformability of the droplet interfaces creates departures from these predictions at higher phi. For phi near and beyond phiMRJ, the effective structure factor, Seff, as a function of wavenumber, q, exhibits a primary peak that is subunity. We speculate that this striking feature is due to the deformation of the droplets into nonspherical shapes as the system begins to approach the limit of a random array of nanoscopic thin films, Plateau borders, and vertexes characteristic of a polyhedral foam.     

Aging of quenched polypropylene

Structural changes occurring during the aging of polypropylene quenched from the melt have been investigated by measurements of gas transport parameters and mechanical properties. Major changes in diffusion and sorption behavior during the first 30 hr of aging at room temperature were found to be strongly dependent on the atomic size of the inert gas penetrants. Tensile mechanical properties increased with aging time, while resilience and mechanical damping showed more complex behavior. The interpretation of the combined results suggests that the aging process may involve molecular rearrangements generally comparable to those for secondary crystallization processes, but within domains comparable in size to that of the smaller penetrant species. The relaxation of a residual stress distribution related to nonuniform plastic flow during quenching may be superimposed on the rearrangement phenomena.     

Diffuse polymer interfaces in lobed nanoemulsions preserved in aqueous media

Using valence electron energy loss spectroscopy (EELS) in the cryo-scanning transmission electron microscopy (STEM), we found that the polymer-polymer interface in two-phase nanocolloids of polydimethyl siloxane (PDMS) and copolymer (methyl acrylate (MA)-methyl methacrylate (MMA)-vinyl acetate (VA)) preserved in water was diffuse despite the fact that equilibrium thermodynamics indicates it should only be on the order of a few nanometers. The diffuse interface is a result of the kinetic trapping of the copolymer within the PDMS phase, and this finding suggests new nonequilibrium pathways to control interfaces during the synthesis of multicomponent polymeric nanostructures.     

Electron capture posteffects in quenched molten salts

Chemical consequences of electron capture in the ⁵⁷Co nucleus in quenched eutectic melts of salts (nitrates, thiocyanates, and carbamides) have been investigated using nuclear gamma resonance spectroscopy. The posteffects of the nuclear transformation are interpreted in terms of the scavenger competition model.     

Estimation of crystallization temperatures in quenched polyethylene

A numerical method has been employed to calculate crystallization temperature as a function of position in slabs or films of polyethylene quenched to various temperatures. The method is iterative, and combines a recent theoretical fit to empirical data for rate of crystal growth as a function of temperature with a solution to the thermal diffusion equation which takes latent heat into account. Results apply strictly only to transcrystalline regions near external surfaces but also provide lower limits to crystallization temperatures throughout the interiors of samples where spherulites nucleate ahead of the general crystallization front. Emphasis is given to assessing the relative importance of various physical parameters in determining crystallization temperatures.     

How to prepare and stabilize very small nanoemulsions

Practical and theoretical considerations that apply when aiming to formulate by ultrasonication very small nanoemulsions (particle diameter up to 150 nm) with very high stability are presented and discussed. The droplet size evolution during sonication can be described by a monoexponential function of the sonication time, the characteristic time scale depending essentially on the applied power. A unique master curve is obtained when plotting the mean diameter size evolution as a function of sonication energy. We then show that Ostwald ripening remains the main destabilization mechanism whereas coalescence can be easily prevented due to the nanometric size of droplets. The incorporation of "trapped species" within the droplet interior is able to counteract Ostwald ripening, and this concept can be extended to the membrane compartment. We finally clarify that nanoemulsions are not thermodynamically stable systems, even in the case where their composition lies very close to the demixing line of a thermodynamically stable microemulsion domain. However, as exemplified in the present work, nanoemulsion systems can present very long-term kinetic stability.     

Laser-induced quenched phosphorescence detection in capillary electrophoresis.

The feasibility of laser-based excitation for quenched phosphorescence detection in capillary electrophoresis (CE) was explored for the first time by using a small-size, quadrupled Nd-YAG laser emitting 266 nm pulses (duration, 0.4 ns) at a repetition rate of 7.8 kHz. To provide a continuous phosphorescence background, the phosphorophore 1-bromo-4-naphthalene sulfonic acid (BrNS) was added to the separation buffer. Both experiments and theory show that in laser-induced phosphorescence (LIP) - in contrast with lamp-excited phosphorescence - one normally deals with such high triplet-state phosphorophore concentrations that triplet-triplet annihilation is the major deactivation pathway. This results in a lower quantum yield of the analyte-induced bimolecular quenching interaction and, thus, the observed quenching signal. The situation can be improved by using a cylindrical lens for excitation in order to reduce the irradiance. In this case limits of detection (LODs) similar to those obtained using lamp excitation (1x10(-8) M) were achieved, while the width of the detection window was reduced from about 4 mm to 1 mm. Even under exclusion of triplet-triplet annihilation, i.e., under conditions of low irradiance, for our setup the quenching yields in LIP were smaller than in lamp-based phosphorescence detection. This is due to the repetition rate of the laser (7.8 kHz), which is too high in view of the phosphorescence lifetime (ca. 300 micros at low irradiance). Theory shows that this disadvantageous effect will be fully eliminated if the repetition rate is decreased to 1 kHz.     

Modeling arrested cluster growth in quenched nanoparticle solutions

We have carried out numerical simulations on a model of phase separation in a binary mixture in the presence of a third, surface-active component. Based on this model we study phase separation in a quenched solution of gold nanoparticles with dodecane thiol ligands in a mixed solvent of butanone and toluene. In our model gold nanoparticles-butanone correspond to the generic binary mixture, while toluene is modeled as a surface-active third component. Our results show that the surface-active component acts as an inhibitor for the phase separation process but its effect decreases with the increase in quench temperature. Simulation results are consistent with two major findings in recent experiments: (a) growth of gold nanoparticle clusters gets arrested at late times and (b) the saturation value of the cluster size is smaller at lower temperatures of quench.     

Crystallisation behaviour of palm oil nanoemulsions carrying vitamin E

Four emulsions were prepared using high pressure homogenisation at 300 or 1200 bar and aqueous phases containing 4.5 wt% whey proteins in mixture with 20 wt% palm oil (PO), alone (E300 and E1200), or in which 20 wt% PO was replaced by vitamin (EV300, EV1200). Thermal behaviour of bulk fat and emulsions in the absence or presence of vitamin, as monitored by differential scanning calorimetry (DSC), indicated that fat crystallisation in supercooled melt was delayed in bulk fat in the presence of vitamin and more delayed in emulsions with lower droplet sizes and containing vitamin. These results were supported by (i) isothermal DSC experiments where exothermic peaks occurred at higher holding times and (ii) dynamic DSC experiments which showed lower melting reactions in emulsions with lower droplet sizes and containing vitamin. Synchrotron X-ray scattering measurements performed simultaneously at small and wide angles on fat samples stored at 4 °C for 12 h showed co-existence of 2L and 3L longitudinal stacking in bulk fat without vitamin, and only 2L organisation of TAGs in the presence of vitamin. Trends in the proportions of α, β′, β lateral packing in lipid droplets were also observed to be more affected by the presence of vitamin rather than their size, indicating a higher rate of α → β′ → β polymorphic transformations in the presence of vitamin. Combining data obtained from DSC and X-Ray signals showed that lipid droplets with lower solid fat content, of which a higher proportion of β polymporphs, were those presenting lower size and lower ability for vitamin protection against chemical degradation, which is of great interest for formulation of lipid nanoparticles as bioactive matrix carriers.     

Cationic nanoemulsions as non-viral vectors for plasmid DNA delivery

Non-viral gene carriers have been extensively investigated as alternatives to viral vectors for therapeutic gene delivery. Many cationic lipid carriers including liposomes, emulsions, and solid lipid nanoparticles are used to transfer plasmid DNA. Stable nanoemulsions were prepared and modified by conjugating fatty acids with cationic amino acids including lysine, arginine, and histidine with the help of carbodiimide. Concentrations of crosslinker and amino acids were optimized to obtain the maximal surface potential. The zeta potential and size distribution of the cationic nanoemulsions were measured using photon correlation spectroscopy. The morphology of nanoemulsion-DNA complexes was examined by transmission electron microscopy. The transfection efficiencies and cytotoxicity of three cationic nanoemulsions were evaluated using 3T3 fibroblast cells. The maximal zeta potentials of lysine-, arginine-, and histidine-modified nanoemulsions were 50, 43, and 7 mV, respectively. The transfection efficiencies of amino acid-modified nanoemulsions were in the order of lysine > arginine > histidine. Low cytotoxicities of these three amino acid-modified nanoemulsions were observed. A facile and inexpensive in situ modification for producing cationic nanoemulsions was developed. The results show the potential of amino acid-modified cationic nanoemulsions as non-viral vectors for gene delivery.     

Characteristics of spontaneously formed nanoemulsions in octane/AOT/brine systems

Nanoemulsions were formed spontaneously by diluting water-in-oil (W/O) or brine-in-oil (B/O) microemulsions of a hydrocarbon (octane), anionic surfactant (Aerosol-OT or AOT) and water or NaCl brine in varying levels of excess brine. The water-continuous nanoemulsions were characterized by interfacial tension, dynamic light scattering, electrophoresis, optical microscopy and phase-behavior studies. The mechanism of emulsification was local supersaturation and resulting nucleation of oil during inversion. For nanoemulsions formed at low salinities with Winsor I phase behavior, octane drops grew from initial diameters of 150-250nm to 480-1000nm over 24h, depending on salinity. Growth was caused by mass transfer but seemed to approach the asymptotic stage of Ostwald ripening described by the Lifshitz-Slyozov-Wagner (LSW) theory only for dilution with salt-free water. Near the higher cross-over salinity (Winsor III), the nanoemulsions showed much slower growth with droplet size consistently remaining below 200nm over 24h and reaching 250nm after 1week. Birefringence indicated the presence of liquid crystal for these conditions, which could have contributed to the slow growth rate. At even higher salinity levels in the Winsor II domain, W/O/W multiple emulsions having drops greater than 1μm in diameter were consistently recorded for the first 5-7h, after which size decreased to values below 1μm. The number and size of internal water droplets in multiple emulsion drops was found to decrease over time, suggesting coalescence of internal droplets with the continuous water phase and mass transfer of water from internal droplets to continuous phase as possible mechanisms of the observed drop shrinkage. Electrophoresis studies showed the nanoemulsions to be highly negatively charged (zeta potentials of -60mV to -120mV). The high charge on octane droplets helped assure stability to flocculation and coalescence, thereby allowing mass transfer to control growth in the Winsor I and III regions.     

Structural changes in solvent-induced crystallization of quenched isotactic polypropylene

Solvent-induced crystallization of quenched isotactic polypropylene (iPP) films in dichloromethane, cyclohexane, carbon tetrachloride, and chloroform has been investigated.WAXD, density, and DSC measurements indicate that smectic iPP films undergo a complex rearrangement of the structure in these liquids, leading to a process of crystallization.Transport properties of the dried samples, after the solvent treatment, show that the first stage of crystallization involves, in addition to the smectic phase, a fraction of amorphous phase, while further crystallization regards only the smectic phase.The morphology of the crystallized samples has been investigated by transmission electron microscopy following permanganic etching. No change in the basic morphology is found, although local organization showing splaying and branching appears clearer in the solvent crystallized samples than in the starting smectic sample.     

Space charge distribution and crystalline structure in quenched polytetrafluoroethylene

Three polytetrafluoroethylene (PTFE) specimens were prepared under different cooling rates after sintering. The space charge distribution in PTFE specimens under direct current electrical field was measured by the pulsed electro-acoustic method (PEA). It was found that the amount of space charges decreased and field distribution tended to be uniform in the quenched specimen. Differential scanning calorimeter (DSC) and wide-angle X-ray diffraction (WAXD) showed that crystallinity and crystalline size of PTFE decreased after quenching whereas the crystalline form of PTFE remained the same. The structure of crystallites became disorderly and imperfect. All the changes in crystalline structure after quenching might decrease the number of space charges trapped in specimens and enhance the transmission of the charge-carriers in amorphous regions, which probably resulted in a decrease of the accumulation of space charges.     

Dynamics of water-in-oil nanoemulsions revealed by fluorescence lifetime correlation spectroscopy

The size, diffusional properties, and dynamics of reverse water-in-oil nanoemulsions, or reverse micelles (RMs), have been widely investigated because of interest in this system as a model for biological compartmentalization. Here, we have employed fluorescence lifetime correlation spectroscopy (FLCS) to reveal the dynamics and sizes of aerosol-OT (AOT)/isooctane RMs using a fluorescent xanthene derivative called Tokyo Green II (TG-II). The dye undergoes a partition and a shift in its tautomeric equilibrium such that the TG-II anion remains in the inner micellar aqueous core, and the neutral quinoid form lies in the interfacial region. By applying FLCS, we specifically obtained the lifetime filtered autocorrelation curves of the anionic TG-II, which shows a characteristic lifetime of approximately 4 ns. Analysis of the FLCS curves provides the diffusion coefficient and hydrodynamic radius of the RMs as well as micelle dynamics in the same experiment. The FLCS curves show dynamics in the microsecond time range, which represents an interconversion rate that changes the distribution of the TG-II neutral and anionic forms in the hydrophobic interface and the water core.