Jie Xu

Surfactant-free microemulsion composed of oleic acid, n-propanol, and H2O.

Generally, a microemulsion consists of oil, water, surfactant, and sometimes cosurfactant. Herein, we report a surfactant-free microemulsion (denoted as SFME), consisting of oleic acid (oil phase), water, and n-propanol without the amphiphilic molecular structure of a traditional surfactant. The phase behavior of the ternary system was investigated, showing that there were a single-phase microemulsion region and a multiphase region in the ternary phase diagram. The electrical conductivity measurement was employed to investigate the microregions of the single-phase microemulsion region, and three different microregions, that is, water-in-oleic acid (W/O), a bicontinuous (B.C.) region, and oleic acid-in-water (O/W), were identified, which were further confirmed by freeze-fracture and cryogenic transmission electron microscopy (FF-TEM and Cryo-TEM) observations. The polarity and the salt solubility of water domains in the W/O SFME were investigated by UV-visible spectroscopy using methyl orange and potassium ferricyanide as probes, respectively. Experimental results showed that the water domains in the W/O microemulsion had a lower polarity than bulk water and a normal solubility for salt species, indicating that the SFMEs have much significance in the preparation of various nanomaterials.

Nonaqueous ionic liquid microemulsions of 1-butyl-3-methylimidazolium tetrafluoroborate, toluene and ethanol

The phase behavior of the ternary system consisting of the hydrophilic ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4), toluene and ethanol was investigated. Single-phase microemulsion and multiphase regions were observed in the ternary phase diagram. To the best of our knowledge, this is the first report on nonaqueous IL microemulsions prepared in the absence of traditional surfactants. The microstructures and structural transitions of the microemulsion system were investigated by cyclic voltammetry, pulse field gradient spin-echo nuclear magnetic resonance and electrical conductivity measurements. The microemulsions exhibit IL-in-toluene (IL/O), bicontinuous (BC) and toluene-in-IL (O/IL) microstructures, similarly to traditional surfactant-based microemulsions. The three kinds of microstructures were confirmed from freeze-fracture electron microscopy observations. A pearl necklace-like structure was observed in the BC microemulsion. The polarity of bmimBF4 domains in the IL/O microemulsion was investigated by UV-visible absorption spectroscopy using methyl orange as a probe. It was found that the polarity was lower than that of the bulk bmimBF4, and it increased with increasing bmimBF4 content at a constant toluene–ethanol ratio.

Synthesis of Mg2Al-Cl layered double hydroxide nanosheets in a surfactant-free reverse microemulsion

The synthesis of Mg2Al-Cl layered double hydroxide (LDH) nanosheets in a surfactant-free reverse microemulsion is described. The microemulsion was composed of toluene, isopropanol, and an aqueous solution as the dispersed phase. An aqueous LDH nanosheet dispersion was obtained by a double-microemulsion technique. LDH nanosheets were characterized by X-ray powder diffraction, transmission electron microscopy, scanning electron microscopy, atomic force microscopy, Fourier transform infrared spectroscopy, and thermogravimetric and elemental analyses. The LDH nanosheets consisted of a single brucite layer without any loading of organic molecules. To the best of our knowledge, this is the first report of a naked LDH monolayer aqueous dispersion being directly obtained. The LDH monolayers can be used as building blocks for LDH-based functional materials.

Structural characterization and electrocatalytic application of hemoglobin immobilized in layered double hydroxides modified with hydroxyl functionalized ionic liquid

Hemoglobin (Hb) was immobilized in Zn2Al-Layered Double Hydroxides (LDH) modified with Hydroxyl Functionalized Ionic Liquid (HFIL) through adsorption and coprecipitation method, respectively. Adsorption experiments showed that the presence of HFIL could enhance the maximum protein loading. However, the Hb loading through coprecipitation technique was far higher than that for adsorption. The role of HFIL on the interaction between Hb and LDH was investigated by XRD, FTIR, UV-vis and fluorescence spectroscopies. Although the quaternary structure of Hb entrapped in HFIL-LDH through coprecipitation technique (denoted as HFIL-LDH-Hbcop) might be altered slightly more than that in LDH (LDH-Hbcop), its secondary structure and redox-active heme groups kept intact. Morphologies of LDH-Hbcop and HFIL-LDH-Hbcop biohybrids were analyzed through SEM and TEM images. The direct electrochemistry of the immobilized Hb indicated that the coprecipitation bioelectrode performed better than that of the corresponding adsorption one. Regardless of adsorption and coprecipitation, the introduction of HFIL could distinctly promote the electron transport. Among all bioelectrodes, HFIL-LDH-Hbcop/GCE displayed the best electrocatalytic activity for H2O2 determination with a larger electroactive Hb percentage (6.76%), higher sensitivity (40.63A/Mcm(2)) and lower detection limit (0.0054μmol/L). So HFIL-LDH could effectively immobilize enzymes via coprecipitation technique, which had potential applications in the fabrication of electrochemical biosensors.

Ionic liquid microemulsions of 1-butyl-3-methylimidazolium hexafluorophosphate, N,N-dimethylformamide, and water

The phase behavior of a ternary system consisting of the hydrophobic ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF6), N,N-dimethylformamide, and water was investigated. Single-phase microemulsion and multiphase regions were observed in the ternary phase diagram. To the best of our knowledge, this is the first report of aqueous IL microemulsions prepared in the absence of traditional surfactants, i.e., surfactant-free microemulsions (SFMEs) containing IL. The microstructures and structural transitions of the aqueous IL SFMEs were investigated using cyclic voltammetry, electrical conductivity, and dynamic laser light scattering techniques. The results showed that the aqueous IL SFMEs exhibit IL-in-water, bicontinuous, and water-in-IL microstructures, similar to the case of traditional surfactant-based microemulsions. The three kinds of microstructures were confirmed from freeze-fracture electron microscopy observations. Ultraviolet-visible and fluorescence spectroscopies were used to examine the polarities of microdomains in the microemulsions, using methyl orange and pyrene, respectively, as probes. It was found that these two techniques can be used to identify the microstructures and microstructural transitions of the aqueous IL microemulsions.

Synthesis of Hierarchical Flower-Like Mg2Al-Cl Layered Double Hydroxide in a Surfactant-Free Reverse Microemulsion

Hierarchical flower-like Mg2Al-Cl LDH microspheres were synthesized using a reverse surfactant-free microemulsion (SFME) route at a low temperature (∼25°C), and characterized by XRD, TEM, SEM, FT-IR, TG, N2 adsorption/desorption, and elemental analyses. The SFME used consists of n-hexane, isopropanol, and water. The so-obtained flower-like microspheres are constructed with LDH nanosheets with ∼10nm thickness. After destroyed by calcination, their crystal structure and flower-like morphology can be reconstructed by rehydration. The flower-like LDH and its calcined product (CLDH) have large specific surface areas being ∼84.3 and 163.9m2g-1, respectively. The sorption of methyl orange (MO) on the LDH and CLDH were determined, showing high MO sorption capacities of ∼559 and 1112gg-1, respectively, which are obviously higher than those reported for conventional LDHs and CLDHs. Possible mechanisms for the flower-like microsphere formation and the MO sorption are discussed. Our results demonstrate that, like traditional surfactant-based microemulsions, SFMEs as microreactors or templates can be used to synthesize nanomaterials. The hierarchical flower-like LDH microspheres and their calcined product have potential applications such as in the treatment of organic waste water.

A surfactant-free microemulsion composed of isopentyl acetate, n-propanol, and water

It has been demonstrated that in the absence of traditional surfactants, microemulsions can form from a ternary mixture of oil, water, and an amphi-solvent. These microemulsions are called surfactant-free microemulsions (SFMEs). To date, only a small number of SFME systems have been reported, and the current understanding of SFMEs is very limited. Herein, we report an SFME consisting of isopentyl acetate (IA), n-propanol, and water, in which IA (a simple ester compound) and n-propanol are used as the oil phase and amphi-solvent, respectively. The microstructures and structural transition of the SFME were investigated by cyclic voltammetry, fluorescence spectroscopy, and UV-visible spectroscopy techniques. Moreover, three kinds of microstructures, namely, oil-in-water (O/W), bicontinuous (BC), and water-in-oil (W/O), have been identified in the SFME, which are directly verified by cryo-TEM observations. A change in the composition of the SFME may lead to a structural transition from O/W through BC to W/O or vice versa, which is similar to the case of traditional surfactant-based microemulsions (SBMEs). To the best of our knowledge, this is the first time that the microstructures and structural transition of an SFME obtained using a simple ester compound as the oil phase have been identified.

Surfactant-Free Microemulsions of 1-Butyl-3-methylimidazolium Hexafluorophosphate, Diethylammonium Formate, and Water

Surfactant-free microemulsions (SFMEs) are a unique kind of microemulsion, which form from immiscible fluids (i.e., oil and water phases) in the presence of amphi-solvents rather than traditional surfactants. In comparison with traditional surfactant-based microemulsions (SBMEs), SFMEs have received much less attention, and the current understanding of the unique system is very limited. Herein, we report a SFME consisting of the hydrophobic ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF6), the protic IL diethylammonium formate (DEAF), and water, in which the bmimPF6 and DEAF are used as the oil phase and amphi-solvent, respectively. Three kinds of microstructures, namely, water-in-bmimPF6 (W/IL), bicontinuous (BC), and bmimPF6-in-water (IL/W), are identified for the SFME, using cyclic voltammetry, cryo-TEM, and DLS techniques. Especially, the volumetric and surface free energy properties of the SFME are investigated by excess molar volume ( VmE) and surface tension (γ) measurements, and they are found to be similar to those of SBMEs. Discontinuous changes in VmE and γ with the system compositions are observed as the system microstructures change, which can be used to identify the structural transition of SFMEs. We think this study provides a better understanding of SFME features.