Understanding the Droplet Diffusion in Ionic Liquid Microemulsions.

Ionic liquids (ILs) as polar components in nonaqueous microemulsions are complex formulations that have interesting transport and structural properties, and offer broader applicability of ILs in areas such as drug delivery and cleaning technology. The phase behavior, electrical conductivity, and nanostructures of these formulations have been investigated for quite some time, but the characteristics of the diffusion of nanodroplets were rarely explored─ and hence little understood. This work investigates the droplet diffusion processes in a series of IL-microemulsions containing 1-butyl-3-methylimidazolium tetrafluoroborate ([C4mim]BF4) by means of viscosity and depolarized dynamic light scattering (DDLS) measurements. The intensity correlation functions are strikingly similar to polymeric solutions in nonaqueous media and aqueous microemulsions containing block copolymers─having bimodal relaxations that are separated by three to four decades of correlation delay times. The "faster" diffusion process is likely a collective process characterizing the correlated motions of droplets in droplet clusters. The collective diffusion coefficient Dcol values are quite comparable to aqueous microemulsions. The "slower" diffusion is likely due to the "caging" effect caused by nearby clusters and/or bulk solvent─this mode may be linked to the microemulsion bulk viscosity. Interestingly, the Dcol variations on increasing [C4mim]BF4 concentration are strongly correlated to the microemulsion viscosity changes as well as locations of these compositions on the microemulsion phase diagram.

Tailored Engineering of Bimetallic Plasmonic Au@Ag Core@Shell Nanoparticles.

A distinctive synthetic method for the efficient synthesis of multifunctional bimetallic plasmonic Au@Ag core@shell nanoparticles (NPs) with tunable size, morphology, and localized surface plasmon resonance (LSPR) using Triton X-100/hexanol-1/deionized water/cyclohexane-based water-in-oil (W/O) microemulsion (ME) is described. The W/O ME acted as a "true nanoreactor" for the synthesis of Au@Ag core@shell NPs by providing a confined and controlled environment and suppressing the nucleation, growth, agglomeration, and aggregation of the NPs. High-resolution transmission electron microscopic analysis of the synthesized Au@Ag core@shell NPs revealed an "unusual core@shell" contrast, and the selected area electron diffraction and Moiré patterns showed that Au layers are paralleled to Ag layers, thus indicating the formation of Au@Ag core@shell NPs. Interestingly, the UV-visible spectrum of the Au@Ag core@shell NPs exhibited enthralling plasmonic properties by introducing a high-frequency quadrupolar LSPR mode originated from the isolated Au@Ag NPs along with a low-frequency dipolar LSPR mode originated from the coupled Au@Ag NPs. The effective plasmonic enhancement of the Au@Ag core@shell NPs is attributed to the extreme enhancement of the localized electromagnetic field by coupling of the localized surface plasmons of the Au core and Ag shell. The mechanisms for the nucleation and growth of Au@Ag core@shell NPs in W/O ME have been proposed. A unique electron transfer phenomenon between the Au core and Ag shell is elucidated for better understanding and manipulation of the electronic properties, which evinced the development of Au@Ag core@shell NPs through suppression of the galvanic replacement reaction.

Silver/poly(vinyl alcohol) nanocomposite film prepared using water in oil microemulsion for antibacterial applications.

HYPOTHESIS: Water in oil microemulsion (w/o) is a simple preparative route for nanoparticles where water droplets (dispersed in continuous oil medium and stabilized by surfactants and cosurfactants) act as nanoreactors to carry out chemical reactions. If polymeric matrix is incorporated inside the core of the microemulsions, it should prevent the agglomeration of nanoparticles after separation from microemulsions. Thus polymer nanocomposite films prepared from w/o microemulsions are expected to give narrow and homogeneous size distribution of nanoparticles throughout the polymer host. EXPERIMENTS: Silver/poly(vinyl alcohol) (Ag/PVA) nanocomposite film was successfully prepared, for the first time, using Triton X-100 (TX-100)/1-butanol/cyclohexane/water microemulsion. Reduction of the metal salt was carried out in the core of w/o microemulsion droplets containing PVA polymeric matrix. After separation from the microemulsion, Ag/PVA nanocomposite film was then prepared by solution casting method. The antibacterial activity of the nanocomposites was tested against Gram-negative, Escherichia coli and Gram-positive, Staphylococcus aureus by agar diffusion method. FINDINGS: Ag nanoparticles with an average diameter of 105 nm could be synthesized using PVA, whereas in the absence of PVA the nanoparticles agglomerated. The distribution of Ag nanoparticles on PVA surface of the nanocomposite film prepared using microemulsion was uniform, whereas the film prepared through in situ generation of Ag nanoparticles by chemical reduction process on PVA host showed non-uniform, coagulated, bunches of Ag nanoparticles. The film synthesized using microemulsion exhibited enhanced antibacterial efficacy compared to that prepared through in situ synthesis under the same test condition.

Dynamic Percolation and Swollen Behavior of Nanodroplets in 1-Ethyl-3-methylimidazolium Trifluoromethanesulfonate/Triton X-100/Cyclohexane Microemulsions.

Microemulsions comprising an ionic liquid (IL), 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([emim][OTf]), as the polar component, Triton X-100 as a surfactant, and cyclohexane as the nonpolar medium were prepared and characterized. Conductivity and dynamic viscosity data were critically analyzed to confirm dynamic percolation among the droplets that are in continuous motion, aggregation, and fission. The transition from oil-continuous phase to bicontinuous phase was observed at the conductance and viscosity percolation thresholds and sharp changes in the values of conductivity and dynamic viscosity could be identified. Dynamic light scattering measurements revealed swelling of the droplets, which varied within the hydrodynamic diameter range of 10-100 nm. Diffusivity of the droplets suggested less Brownian movement with increased amount of the IL. Moreover, changes in the droplet sizes and diffusivity with increase in IL content supported dynamic percolation within the systems.

Electrochemical treatment of Orange II dye solution--use of aluminum sacrificial electrodes and floc characterization.

Electrocoagulation (EC) of Orange II dye in a flow through cell with aluminum as sacrificial electrodes was carried out under varying conditions of dye concentration, current density, flow rate, conductivity, and the initial pH of the solution in order to optimize the operating parameters for maximum benefits. Maximum removal efficiency of 94.5% was obtained at the following conditions: dye concentration=10 ppm, current density=160 A/m(2), initial pH 6.5, conductance=7.1 mS/cm, flow rate=350 mL/min, and concentration of added NaCl=4.0 g/L of dye solution. The EC-floc was characterized using Fourier transform infrared spectroscopy, scanning electron microscopy/energy dispersive X-ray spectroscopy, and powder X-ray diffraction techniques. The removal mechanism has been proposed that is in compliance with the Pourbaix diagram, solubility curve of aluminum oxides/hydroxides, and physico-chemical properties of the EC-floc.