One-pot synthesis of dendritic gold nanostructures in aqueous solutions of quaternary ammonium cationic surfactants: effects of the head group and hydrocarbon chain length.

Hierarchical, three-fold symmetrical dendritic gold was prepared in an aqueous solution of the quaternary ammonium cationic surfactant dodecyltrimethylammonium bromide (DTAB). Similar surfactants with different head groups and hydrocarbon chain lengths were also used for comparison. Two-fold and one-fold symmetrical dendritic gold nanostructures were obtained in N-dodecyl-N-methylpyrrolidinium bromide (C(12)-MPB) and dodecyltriethylammonium bromide (DTEAB) aqueous solutions, respectively. Longer hydrocarbon chain lengths were unfavorable for the formation of dendritic nanostructures. The interaction energies between the individual surfactants and Au (111) plane were calculated using molecular dynamics simulations. Based on a series of contrast experiments and molecular dynamics simulations, the possible growth mechanism and fabrication process of the dendritic structures were proposed. The DTAB-capped, three-fold gold dendrites exhibited good surface-enhanced Raman scattering (SERS) sensitivity toward rhodamine 6G (R6G), indicating their potential for use in SERS-based detections and analysis. This work provides a simple and effective strategy for fabricating dendritic gold nanostructures in aqueous solutions.

The effects of the π-π stacking interactions on the patterns of gold nanoparticles formed at the air-water interface.

Benzyl-n-hexadecyl dimethylammonium chloride (BHDC) monolayer-stabilized gold nanoparticles were synthesized in a two-phase liquid-liquid system and found to self-assemble into varied structures under the control of temperature at the air-water interface. It has been demonstrated that the π-π stacking interactions between the capping agent molecules significantly affect the formation of the unique patterns. A possible mechanism based on Marangoni-Bénard convection in the evaporating droplets and π-π stacking interactions was proposed. Four surfactants with similar structures: N-hexadecyl-N-methylpyrrolidinium bromide (C(16)MPB), 1-hexadecyl-3-methylimidazolium bromide (C(16)mimBr), 1-(2,4,6-trimethylphenyl)-3-hexadecylimidazolium bromide (C(16)pimBr) and hexadecyltrimethylammonium bromide (CTAB) were also used to further verify the formation mechanism mentioned above.

Patterns of gold nanoparticles formed at the air/water interface: effects of capping agents.

Gold nanoparticles stabilized with different capping agents were synthesized in a two-phase liquid-liquid system and found to self-assemble into various patterns at the air/water interface. The shapes of the patterns are closely related to the molecule structures of the capping agents. Systems with mixed capping agents were also investigated, and honeycomb patterns can be obtained in this way. T-shape and H-shape patterns were also observed. A possible mechanism based on Marangoni-Benard convection in evaporating droplets is proposed.

C12mimBr ionic liquid/SDS vesicle formation and use as template for the synthesis of hollow silica spheres.

The phase behavior of an aqueous catanionic surfactant system, composed of a long-chain imidazolium ionic liquid 1-dodecyl-3-methylimidazolium bromide (C(12)mimBr) and sodium dodecyl sulfate (SDS), is described. The phase diagram of the catanionic system was determined by electrical conductivity measurements and the formation of vesicles in a birefringent L(alpha) phase characterized by transmission electron microscopy (TEM) and freeze-fracture transmission electron microscopy (FF-TEM). Rheological measurements were used to characterize the macroscopic properties of the birefringent L(alpha) phase. Both electrostatic and hydrophobic interactions contribute to the vesicle formation in the catanionic system. Compared to the DTAB/SDS aqueous solution, differences between the imidazolium and trimethylammonium headgroups geometric packing and charge density induce the different phase behavior in each system. Silica hollow spheres, with diameters 30-60 nm and a wall thickness of 8-10 nm, were prepared by using the vesicles as the templates. The hollow silica spheres were characterized by TEM, scanning electron microscopy (SEM), and nitrogen adsorption-desorption. The results suggest additional application for ionic liquid based vesicles to be used as templates for the synthesis of hollow inorganic materials.

Chiral ionic liquid monolayer-stabilized gold nanoparticles: synthesis, self-assembly, and application to SERS.

Chiral ionic liquid monolayer-stabilized gold nanoparticles were synthesized in a two-phase liquid-liquid system and found to self-assemble into ringlike structures at the air/water interface. Control experiments with long-chain ILs revealed that the molecular structure of the CIL significantly affects the formation of the gold nanoparticle ring structures. A possible mechanism based on Marangoni-Bénard convection in evaporating droplets was proposed. These gold nanoparticle structures were shown to yield a large SERS enhancement for Rhodamine 6G.

Microstructures of micellar aggregations formed within 1-butyl-3-methylimidazolium type ionic liquids.

Nonionic surfactant Triton X-100 was shown to aggregate and form micellar aggregation in ionic liquids (ILs), 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF(4)) and 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF(6)). The surface tension measurements revealed that the dissolution of Triton X-100 in ILs depressed the surface tension in a manner analogous to aqueous solutions, and a relatively higher critical micellar concentration (CMC) was obtained compared to that of water. Freeze-fracture transmission electron microscopy (FFTEM) shows that the micelles have an irregular droplet shape, which is larger than that formed in water. The micellar droplets preferred to assemble into larger clusters. (1)H NMR and two-dimensional rotating frame nuclear Overhauser effect (NOE) experiments (2D ROESY) show that the addition of Triton X-100 destroyed the ion pairs of pure ILs due to the electrostatic interaction between the positively charged imidazolium cation of ILs and the electronegative oxygen atoms of oxyethylene (OE) units of Triton X-100. The electrostatic interaction behaves similar to hydrogen bond that occurred between the OE units of nonionic surfactants and water molecules in aqueous micelles and cooperates with solvatophobicity, leading to the formation of IL micelles. The 2D ROESY analysis reveals that the microstructures of Triton X-100-based micelles in ILs are not regular spherical, which accords with the FFTEM image. Similar to the aqueous micellar systems, the hydrophobic interaction or solvatophobicity was found to drive the formation of micelles.

States of water located in the continuous organic phase of 1-butyl-3-methylimidazolium tetrafluoroborate/Triton X-100/triethylamine reverse microemulsions.

We demonstrate a novel ionic liquid (IL) microemulsion, consisting of 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4) and nonionic surfactant Triton X-100 prepared in triethylamine which is used either as an organic solvent or a Lewis base. The effects of small amounts of added water on the microstructure of the IL microemulsion are investigated by various techniques. UV/Vis spectroscopic analysis and FTIR spectra indicate that these water molecules are not solubilized into the IL pools of the microemulsions. 1H NMR spectra further show that the added water binds with triethylamine to form a surrounding OH- base environment. Some of OH- ions enter the palisade layers of the IL microemulsions and a continuous base interface is created. The unique solubilization behavior of water reveals that it is possible to use the triethylamine microemulsions as a template to prepare metal hydroxides as well as metal oxides in the microemulsions, which is not possible when using traditional microemulsions.

Role of solubilized water in the reverse ionic liquid microemulsion of 1-butyl-3-methylimidazolium tetrafluoroborate/TX-100/benzene.

The ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4) can form nonaqueous microemulsions with benzene by the aid of nonionic surfactant TX-100. The effect of water on ionic liquid-in-oil (IL/O) microemulsions was studied, and it was shown that the addition of small amount of water to the IL microemulsion contributed to the stability of microemulsion and thus increased the amount of solubilized bmimBF4 in the microemulsion. The conductivity measurements also showed that the attractive interactions between IL microdroplets were weakened, that is, the IL/O microemulsion becomes more stable in the present of some water. Fourier transform IR was carried out to analyze the states of the added water, and the result showed that these water molecules mainly behaved as bound water and trapped water, indicating that the water molecules are located in the palisade layers of the IL/O microemulsion. Furthermore, 1H NMR and 19F NMR spectra suggested that the added water molecules built the hydrogen binding network of imidazolium cations and H2O, BF4- anion and H2O, and at the same time the electronegative oxygen atoms of the oxyethylene units of TX-100 and water in the palisade layers, which made the palisade layers more firm and thus increased the stability of the microemulsion. The study can help in further understanding the formation mechanism of microemulsions. In addition, the characteristic solubilization behavior of the added water can provide an aqueous interface film for hydrolysis reactions and therefore may be used as an ideal medium to prepare porous or hollow nanomaterials.