Microemulsion Droplets Research Articles

Microemulsions with the ionic liquid ethylammonium nitrate: phase behavior, composition, and microstructure.

In this study, we investigate properties of microemulsions which consist of the ionic liquid (IL) ethylammonium nitrate (EAN), the nonionic surfactant C12E3 and an n-alkane, namely n-dodecane or n-octane. The compositions of the coexisting phases are calculated from the densities and volumes of the respective phases. Since the interfacial tension between the water-rich and the oil-rich phase in traditional microemulsions (containing water and oil) relates to the microstructure, spinning drop tensiometry is used to measure the interfacial tension σab and to estimate the domain sizes. Finally, measuring the self-diffusion coefficients of all components via the Fourier Transform Pulsed Gradient Spin Echo (FTPGSE) NMR technique allowed distinguishing between continuous and discrete structures. Our results indicate that the general principles underlying water-n-alkane-CiEj microemulsions can indeed be transferred to oil-in-EAN droplet and the respective bicontinuous microemulsions, while differences are observed for EAN-in-oil droplet microemulsions.

In vivo evaluation of an oral self-microemulsifying drug delivery system (SMEDDS) for leuprorelin

The objective of this study was to develop a self-microemulsifying drug delivery system (SMEDDS) for the model peptide drug leuprorelin to prove a protective effect against luminal enzymatic metabolism. In order to incorporate leuprorelin into microemulsion droplets (o/w), the commercially available hydrophilic leuprolide acetate was modified by hydrophobic ion paring with sodium oleate. The obtained hydrophobic leuprolide oleate was dissolved in the SMEDDS formulation (30% (m/m) Cremophor EL, 30% (m/m) Capmul MCM, 10% (m/m) propylene glycol and 30% (m/m) Captex 355) in a concentration of 4mg/g showing a mean droplet size of 50.1nm when dispersed in a concentration of 1% (m/v) in phosphate buffer pH 6.8. The microemulsion was able to shield leuprolide oleate from enzymatic degradation by trypsin and α-chymotrypsin, so that after 120min 52.9% and 58.4%, respectively, of leuprolide oleate were still intact. Leuprolide acetate dissolved in an aqueous control solution was completely metabolized by trypsin within 60min and by α-chymotrypsin within 5min. Moreover, an in vivo study in rats showed a 17.2-fold improved oral bioavailability of leuprolide oleate SMEDDS compared to a leuprolide acetate control solution. This is the first time, to our knowledge, that hydrophobic ion pairing is utilized in order to incorporate a peptide drug in SMEDDS and evidence of a protective effect of oil-in-water (o/w) microemulsion droplets against enzymatic degradation of a peptide drug was provided. According to these results, the system could be likely a novel platform technology to improve the oral bioavailability of peptide drugs.

Effect of biopolymer addition on the formulation and properties of an oil-in-water microemulsion

In this study stable microemulsions with very low interfacial tension (IFT) were developed. This type of microemulsion has very low viscosity (very similar to that of water). For application of these systems for solubilization and enhanced oil recovery, we studied the effect on the properties of such microemulsions of adding biopolymer to increase viscosity while maintaining IFT as low as possible. Hydroxyethylcellulose and hydrophobically modified hydroxyethylcellulose were selected; their mode of addition to the formulation is discussed. Microemulsion zones were determined by phase diagram investigation in accordance with Winsor’s classification. In addition to spontaneous formation, transparency, and stability, other properties were measured and others calculated to better define the formulated systems and to confirm the presence of microemulsions. Microemulsion droplet number and size both decrease with increasing salt concentration. Depending on emulsion size, rheological measurements confirm that both polysaccharides have a favourable effect on the viscosity of microemulsion without important modification of IFT.

Induced Optical Chirality of Porphyrin J-Aggregates with 2-Alkyl Alcohol in a Microemulsion System

Abstract The J-aggregates of the diprotonated tetraphenylporphin formed in the o/w microemulsions including 2-alkyl alcohol, Triton X-100, toluene, and sulfuric acid, exhibited an induced circular dichroism (ICD) spectra corresponding to the chirality of the alcohol. The ICD intensity remarkably depended on the concentrations of Triton X-100 and sulfuric acid as well as 2-alkyl alcohol. The results suggested the nonstoichiometric formation of the chiral conformation of the nano-J-aggregates in the microemulsion droplets.

Ethanol-in-palm oil/diesel microemulsion-based biofuel: Phase behavior, viscosity, and droplet size

Increased environmental awareness and depletion of resources are driving industry to develop viable fuels from renewable resources. Vegetable oils are one alternative being considered for the production of renewable fuels. Surfactant reverse micelle microemulsions can be used as an alternative method for reducing high viscosities of vegetable oil without chemical wastes generated from the transesterification reaction. The objective of this research is to study the effects of surfactant saturation, unsaturation, and ethylene oxide groups on the phase behavior, kinematic viscosity, and microemulsion-droplet size with the goal of formulating optimized surfactant based biofuel. Four nonionic surfactants, stearyl alcohol (saturated), oleyl alcohol (unsaturated), methyl oleate (unsaturated with ester group), and Brij-010 (EO groups), were investigated in this research. It was found that the presence of methyl oleate unsaturated surfactant can greatly reduce the bulk viscosity and produce uniformly size of microemulsion droplets while use the least amount of surfactant for solubilizing ethanol-in-oil in the system. Thus, these results show that reverse micelle microemulsion can produce biofuels with desirable viscosity and fuel properties as compared to diesel.

Spherical-to-Cylindrical Transformation of Reverse Micelles and Their Templating Effect on the Growth of Nanostructures

We discuss a complete mechanistic study on the anisotropic growth of zinc oxalate nanostructures within reverse micelles. We have employed small-angle X-ray scattering (SAXS), dynamic light scattering (DLS), and transmission electron microscopy (TEM) to understand the detailed growth of the nanostructures. We have been able to observe the generation of nuclei and their aggregation to a critical size beyond which they form nanostructures of higher dimensions in self-assembled templates. One of our aims was to find a correlation between size and shape of microemulsion droplets (MDs) and that of the resulting nanostructures of zinc oxalate (ZO) which grow within the MDs. Combination of SAXS and DLS show in situ growth of nanoparticles in the individual droplets which consume the water-insoluble product formed and undergo exchange coalescence with other droplets. The structural transition of the MDs is captured by observing the change in shape anisotropy, together with a detailed structural analysis of micelles in which the nanostructures grow as a function of time. Importantly, once the reaction is triggered, the nucleation of the droplets start instantly, and a very short period is noticed where MDs become cylindrical with approximate aspect ratio of 4:1 in which nanostructures grow anisotropically and achieve an average critical size of 55 nm (elongated nanoparticles) signifying the existence of short nucleation-dominant particle growth period, beyond which a transition from elongated nanostructures to small rods is observed. The critical size for the elongated droplets is 80 nm in length and 18 nm in diameter, and these critical dimensions at the point of transition are a new finding about an asymmetric particle before the rods begin to start self-assembling. Once the shape of microemulsions turns cylindrical, the dynamical exchange with other microemulsions is very fast at both ends, resulting in the formation of nanorods of zinc oxalate and an increase in the aspect ratio of these rods. This growth process can be viewed as a morphologically templated nucleation process, and the droplets act as shaping vesicles for the formation of ZO nanorods. This study is significant since it attempts to correlate the size and shape of the reverse micellar (microemulsion) droplets with the newborn product nanoparticles inside the droplets and the subsequent growth of the nanoparticles within the droplets.

How a Viscoelastic Solution of Wormlike Micelles Transforms into a Microemulsion upon Absorption of Hydrocarbon: New Insight

In this article, we investigate the effect of hydrocarbon addition on the rheological properties and structure of wormlike micellar solutions of potassium oleate. We show that a viscoelastic solution of entangled micellar chains is extremely responsive to hydrocarbons-the addition of only 0.5 wt % n-dodecane results in a drastic drop in viscosity by up to 5 orders of magnitude, which is due to the complete disruption of micelles and the formation of microemulsion droplets. We study the whole range of the transition of wormlike micelles into microemulsion droplets and discover that it can be divided into three regions: (i) in the first region, the solutions retain a high viscosity (∼10-350 Pa·s), the micelles are entangled but their length is reduced by the solubilization of hydrocarbons; (ii) in the second region, the system transitions to the unentangled regime and the viscosity sharply decreases as a result of further micelle shortening and the appearance of microemulsion droplets; (iii) in the third region, the viscosity is low (∼0.001 Pa·s) and only microemulsion droplets remain in the solution. The experimental studies were accompanied by theoretical considerations, which allowed us to reveal for the first time that (i) one of the leading mechanisms of micelle shortening is the preferential accumulation of the solubilized hydrocarbon in the spherical end caps of wormlike micelles, which makes the end caps thermodynamically more favorable; (ii) the onset of the sharp drop in viscosity is correlated with the crossover from the entangled to unentangled regime of the wormlike micellar solution taking place upon the shortening of micellar chains; and (iii) in the unentangled regime short cylindrical micelles coexist with microemulsion droplets.

Isothermal Behavior of the Soret Effect in Nonionic Microemulsions: Size Variation by Using Different n-Alkanes

In this work we investigate the thermodiffusion behavior of microemulsion droplets of the type H2O/n-alkane/C12E5 (pentaethylene glycol monododecyl ether) using the n-alkanes: n-octane, n-decane, n-dodecane, and n-tetradecane. In order to determine the thermodiffusion behavior of these microemulsion droplets, we apply the infrared thermal diffusion forced Rayleigh scattering (IR-TDFRS) technique. We measure the Soret coefficient (ST) as function of the structure upon approaching the emulsification failure boundary (efb) and as a function of the radius of the spherical o/w microemulsion droplets close to the efb. By varying the chain length of the n-alkanes, we are able to study the thermodiffusion behavior of spherical o/w microemulsion droplets of different sizes at the same temperature. In the investigated range a linear dependence of the Soret coefficient as function of the radius was found. By use of a proposed relationship between the Soret coefficient and the temperature dependence of the interfacial tension, the transition layer l could be determined for the first time. Additionally, small angle neutron scattering (SANS) experiments are performed to determine the size and to prove that the shape of the microemulsion droplets is spherical close to the efb. Accordingly, the scattering curves could be quantitatively described by a combination of a spherical core-shell form factor and sticky hard sphere structure factor.

Diversity in the dynamical behaviour of a compartmentalized programmable biochemical oscillator

In vitro compartmentalization of biochemical reaction networks is a crucial step towards engineering artificial cell-scale devices and systems. At this scale the dynamics of molecular systems becomes stochastic, which introduces several engineering challenges and opportunities. Here we study a programmable transcriptional oscillator system that is compartmentalized into microemulsion droplets with volumes between 33 fl and 16 pl. Simultaneous measurement of large populations of droplets reveals major variations in the amplitude, frequency and damping of the oscillations. Variability increases for smaller droplets and depends on the operating point of the oscillator. Rather than reflecting the stochastic kinetics of the chemical reaction network itself, the variability can be attributed to the statistical variation of reactant concentrations created during their partitioning into droplets. We anticipate that robustness to partitioning variability will be a critical challenge for engineering cell-scale systems, and that highly parallel time-series acquisition from microemulsion droplets will become a key tool for characterization of stochastic circuit function.

Synthesis and modeling of calcium alginate nanoparticles in quaternary water-in-oil microemulsions

Calcium alginate nanoparticles were prepared using the water-in-oil microemulsion route. Sodium alginate and CaCl2 were solubilised in the aqueous phase of two microemulsions, and their mixing induced the crosslinking of the alginate polymer by the calcium ions. The microemulsions were based on the nonionic ethoxylated surfactant Brij30 and the nonionic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock-copolymer L64. Dynamic light scattering analysis revealed that the microemulsion droplet size was not affected by the species in the aqueous phase and that the alginate polymer was strongly confined in the microemulsion water pool. Atomic force microscopy of the collected alginate nanoparticles indicated a polydisperse population with an average size of 54nm and hinted at an active template role of the microemulsion droplets. A detailed description of the conformation adopted by the alginate polymer in the water droplet in the presence of mono- and divalent counterions was provided by Monte Carlo simulations. The binding of both counterions was nonspecific, with the chain configuration allowing the carboxylic, hydroxylic, and ether groups to coordinate the small ions. Addition of divalent counterions did not modify the radial extension of the alginate chain, yet it mediated the transient bridging between strands.

Dynamics of microemulsions bridged with hydrophobically end-capped star polymers studied by neutron spin-echo.

The mesoscopic dynamical properties of oil-in-water microemulsions (MEs) bridged with telechelic polymers of different number of arms and with different lengths of hydrophobic stickers were studied with neutron spin-echo (NSE) probing the dynamics in the size range of individual ME droplets. These results then were compared to those of dynamicic light scattering (DLS) which allow to investigate the dynamics on a much larger length scale. Studies were performed as a function of the polymer concentration, number of polymer arms, and length of the hydrophobic end-group. In general it is observed that the polymer bridging has a rather small influence on the local dynamics, despite the fact that the polymer addition leads to an increase of viscosity by several orders of magnitude. In contrast to results from rheology and DLS, where the dynamics on much larger length and time scales are observed, NSE shows that the linear polymer is more efficient in arresting the motion of individual ME droplets. This finding can be explained by a simple simulation, merely by the fact that the interconnection of droplets becomes more efficient with a decreasing number of arms. This means that the dynamics observed on the short and on the longer length scale depend in an opposite way on the number of arms and hydrophobic stickers.

Striped, bioactive Ce-TiO2 materials with peroxynitrite-scavenging activity.

Controlling aligned fiber micro-architectures to simulate the extracellular matrix for inducing important biological functions is a key challenge with regard to successful tissue regeneration. Here we present a bottom-up microemulsion-mediated strategy to obtain highly bioactive and biocompatible, striped Ce-TiO2 nano-crystalline superstructures with ONOO- scavenging activity. The employment of a bulkier organic ceria precursor in the material synthesis has several concurrent effects: (I) influencing the interfacial microemulsion droplet elasticity to create an aligned distribution of prismatic anatase nanoparticles causing the final lined morphology, (II) stabilizing the anatase active phase in a fine dispersed state and improving its resistance to the thermal anatase-rutile conversion, (III) indirectly favoring the rapid formation on the material surface of a hydroxyapatite layer composed of sphere-like globules of 3-5 μm in diameter essential for bone-bonding, and finally (IV) accelerating the ONOO- degradation into less harmful species NO2 - and O2.

Combined phase behavior, dynamic light scattering, viscosity and spectroscopic investigations of a pyridinium-based ionic liquid-in-oil microemulsion

Proposed model, phase diagram and variation in size (d), viscosity (η) and fluorescence intensity (FI) for 1-butyl-4-methyl pyridinium tetrafluoroborate ([b4mpy][BF4])–(Tween 20 + n-pentanol)–n-heptane ionic liquid-in-oil-microemulsion system.

Solvent dependent interactions between droplets in water-in-oil microemulsions.

In this paper, we investigated the dilution enthalpies of the droplets in water/AOT/oil microemulsions with oil being isooctane, decane, or cyclohexane by isothermal titration microcalorimetry (ITC). Combining with the results obtained from the study of the water/AOT/toluene system in our previous work, it was found that the enthalpy interactions between droplets for isooctane and decane systems were repulsive, while the enthalpy interactions were attractive for cyclohexane and toluene systems. The repulsive droplet interaction for the isooctane system was also confirmed by static light scattering. The solvents appear to play important roles in varying the droplet enthalpy interactions from positive to negative, and the entropy contribution seems to be dominant for the stability of these microemulsion droplet systems.

Communication and Computation by Bacteria Compartmentalized within Microemulsion Droplets

Amphiphilic inducer molecules such as N-acyl-L-homoserine lactones (AHLs) or isopropyl-β-D-thio-galactopyranoside (IPTG) can be utilized for the implementation of an artificial communication system between groups of E. coli bacteria encapsulated within water-in-oil microemulsion droplets. Using spatially extended arrays of microdroplets, we study the diffusion of both AHL and IPTG from inducer-filled reservoirs into bacteria-containing droplets, and also from droplets with AHL producing sender bacteria into neighboring droplets containing receiver cells. Computational modeling of gene expression dynamics within the droplets suggests a strongly reduced effective diffusion coefficient of the inducers, which markedly affects the spatial communication pattern in the neighborhood of the senders. Engineered bacteria that integrate AHL and IPTG signals with a synthetic AND gate gene circuit are shown to respond only in the presence of both types of sender droplets, which demonstrates the potential of the system for genetically programmed pattern formation and distributed computing.

Depletion-induced sphere-cylinder transition in C12E5 microemulsion: a small-angle X-ray scattering study

Small-angle X-ray scattering was used to study the mixture of C12E5 (pentaethylene glycol monododecyl ether)/H2O/n-decane microemulsion and polyethylene glycol (PEG). The size, shape and the structure factor of the microemulsion were investigated by adding the polymer (PEG) to the mixture. Attractive depletion potential was induced between the microemulsion droplets by the non-adsorb polymer. The range and strength of the attractive potential were changed by varying the molecular weight and concentration of PEG. The forward scattering, S(0), of the spherical microemulsion, declined gradually as the polymer concentration decreased. For PEG with the molecular weight of Mn = 285−315, the microemulsion morphology remained spherical, but the main peak of the structure factor moved towards a bigger q. When PEG with molecular weights of Mn = 2200 and Mn = 6000 were used, a shape transition from spherical to cylindrical was induced in line with increasing polymer concentration.

Micellar interactions in water-AOT based droplet microemulsions containing hydrophilic and amphiphilic polymers

We investigate the influence of addition of hydrophilic and amphiphilic polymer on percolation behavior and micellar interactions in AOT-based water-in-oil droplet microemulsions. We focus on two series of samples having constant molar water to surfactant ratio W = 20 and constant droplet volume fraction Φ = 30%, respectively. From dielectric spectroscopy experiments, we extract the bending rigidity of the surfactant shell by percolation temperature measurements. Depending on droplet size, we find stabilization and destabilization of the surfactant shell upon addition of hydrophilic poly(ethylene glycol) (PEG) (Mn = 3100 g mol(-1)) and amphiphilic poly(styrene)-b-poly(ethylene glycol) copolymer with comparable length of the hydrophilic block. Complementary small angle X-ray scattering experiments corroborate the finding of stabilization for smaller droplets and destabilization of larger droplets. Subsequent analysis of dielectric spectra enables us to extract detailed information about micellar interactions and clustering by evaluating the dielectric high frequency shell relaxation. We interpret the observed results as a possible modification of the inter-droplet charge transfer efficiency by addition of PEG polymer, while the amphiphilic polymer shows a comparable, but dampened effect.

Synthesis of Ni-Ag Core-shell Nanoparticles by Polyol process and Microemulsion Process

Ni-Ag core-shell nanoparticles were synthesized by polyol process and microemulsion technique successfully. In the polyol process, a chemical reduction method for preparing highly dispersed pure nickel and Ag shell formation have been reported. The approach involved the control of reaction temperature and reaction time in presence of organic solvent (ethylene glycol) as a reducing agent for Ag cation with poly(vinyl-pyrrolidone) (PVP. Mw = 40000) as a capping agent. In microemulsion method, the emulsion was prepared by water/cetyltrimetylammonium bromide (CTAB)/cyclohexane. The size of microemulsion droplet was determined by the molar ratio of water to surfactant (). The core-shell formation along with the change in structural phase and stability against oxidation at high temperature heat treatments of nanoparticles were investigated by X-ray diffraction and TEM analysis. Under optimum conditions the polyol process gives the Ni-Ag core-shell structures with 13 nm Ni core covered with 3 nm Ag shell, while the microemulsion method gives Ni core diameter of 8 nm with Ag shell of thickness 6 nm. The synthesized Ni-Ag core-shell nanoparticles were stable against oxidation up to .

Electrospun Hierarchical TiO2 Nanorods with High Porosity for Efficient Dye-Sensitized Solar Cells

Ultraporous anatase TiO2 nanorods with a composite structure of mesopores and macropores fabricated via a simple microemulsion electrospinning approach were first used as photoanode materials for high-efficiency dye-sensitized solar cells (DSSCs). The special multiscale porous structure was formed by using low-cost paraffin oil microemulsion droplets as the soft template, which can not only provide enhanced adsorption sites for dye molecules but also facilitate the electrolyte diffusion. The morphology, porosity, and photovoltaic and electron dynamic characteristics of the porous TiO2 nanorod based DSSCs were investigated in detail by scanning electron microscopy (SEM), N2 sorption measurements, current density-voltage (J-V) curves, UV-vis diffuse reflectance spectra, electrochemical impedance spectroscopy (EIS), intensity modulated photocurrent/photovoltage spectroscopy (IMPS/IMVS), and open-circuit voltage decay (OCVD) measurements. The results revealed that, although fewer amounts of dyes were anchored on the porous TiO2 nanorod films, they exhibited stronger light scattering ability, fast electrolyte diffusion, and extended electron lifetime compared to the commercial P25 nanoparticles. A power conversion efficiency of 6.07% was obtained for the porous TiO2 nanorod based DSSCs. Moreover, this value can be further improved to 8.53% when bilayer structured photoanode with porous TiO2 nanorods acting as the light scattering layer was constructed. This study demonstrated that the porous TiO2 nanorods can work as promising photoanode materials for DSSCs.

Microstructure of microemulsion modified with ionic liquids in microemulsion electrokinetic chromatography and analysis of seven corticosteroids

In this work, the influences of ionic liquid (IL) as a modifier on microemulsion microstructure and separation performance in MEEKC were investigated. Experimental results showed that synergetic effect between IL 1-butyl-3-methylimidazolium tetrafluoro-borate (BmimBF4 ) and surfactant SDS gave a decreased CMC. With increment of IL in microemulsion, negative ζ potential of the microdroplets reduced gradually. The influence of IL on the dimensions of microdroplet was complicated. At BmimBF4 less than 8 mM, IL made microemulsion droplet smaller in size. While at BmimBF4 more than 10 mM, the size increased and reached to a maximum value at 12 mM, where the microdroplets were larger than that without IL. After that, the micreodroplet size decreased again. Relative fluorescence intensity of the first vibration band of pyrene to the third one (I1 /I3 ) enhanced as IL was added to microemulsion, which indicated that this addition increased environmental polarity in the inner core of microdroplets. Prednisone, hydrocortisone, prednisolone, hydrocortisone acetate, cortisone acetate, prednisolone acetate, and triamcinolone acetonide were analyzed with MEEKC modified with IL to evaluate the separation performance. Cortisone acetate and prednisolone acetate could not be separated at all in typical microemulsion. The seven analytes could be separated by the addition of 10 mM BmimBF4 into the microemulsion system. The method has been used for analysis of corticosteroids in cosmetic samples with simple extraction; the recoveries for seven analytes were between 86 and 114%. This method provides accuracy, reproducibility, pretreatment simplicity, and could be applied to the quality control of cosmetics.