Synthesis of gold nanoparticles modified with ionic liquid based on the imidazolium cation

The synthesis and processing of nanoparticles consisting of metallic nanocrystal cores and organic monolayer shells promise interesting technological applications. Here, we report the synthesis of gold nanoparticles modified with ionic liquids based on the imidazolium cation. Aggregation-induced color changes of the gold nanoparticles in an aqueous solution were used as an optical sensor for anions via anion exchange of ionic liquid moiety. We also demonstrated the phase transfer of the gold nanoparticles from aqueous media to ionic liquid.     

Water-dispersible nanoparticles via interdigitation of sodium dodecylsulphate molecules in octadecylamine-capped gold nanoparticles at a liquid-liquid interface

This paper describes the formation of water-dispersible gold nano-particles capped with a bilayer of sodium dodecylsulphate (SDS) and octadecylamine (ODA) molecules. Vigorous shaking of abiphasic mixture consisting of ODA-capped gold nanoparticles in chloroform and SDS in water results in the rapid phase transfer of ODA-capped gold nanoparticles from the organic to the aqueous phase, the latter acquiring a pink, foam-like appearance in the process. Drying of the coloured aqueous phase results in the formation of a highly stable, reddish powder of gold nanoparticles that may be readily redispersed in water. The water-dispersible gold nanoparticles have been investigated by UV-Vis spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and Fourier transform infrared spectroscopy (FTIR). These studies indicate the presence of interdigitated bilayers consisting of an ODA primary monolayer directly coordinated to the gold nanoparticle surface and a secondary monolayer of SDS, this secondary monolayer providing sufficient hydrophilicity to facilitate gold nanoparticle transfer into water and rendering them water-dispersible. Dedicated to Professor C N R Rao on his 70th birthday     

Phase transfer of large gold nanoparticles to organic solvents with increased stability

In this paper, we describe a new procedure to phase transfer large gold nanoparticles (diameters > 45 nm) from aqueous solution to organic solvents. This is accomplished using a covalent amide coupling reaction that incorporates dicyclohexylamine (DCHA) headgroups on the surface of mercaptoacetic acid (MAA) functionalized gold nanoparticles. Gold nanoparticles are first synthesized in aqueous solution by the citrate-reduction method, and nanoparticle size is controlled by the molar ratio of the reducing agent (sodium citrate) and the gold precursor (KAuCl4). MAA is then adsorbed to the surface of the gold nanoparticles followed by an amide-coupling reaction to covalently attach DCHA to the surface-immobilized MAA. The bulky dicyclohexyl groups entropically stabilize gold nanoparticles in organic solvents. This procedure was used to reliably transfer gold nanoparticles with diameters between 45 and 100 nm from aqueous solution to organic solvents such as dimethyl sulfoxide and chloroform.     

Photofragmentation of phase-transferred gold nanoparticles by intense pulsed laser light

Gold nanoparticles with an average diameter of approximately 20 nm were prepared in an aqueous solution by a wet chemistry method. The parent gold nanoparticles were then capped with a 4-aminothiophenol protecting layer and transferred into toluene by tuning the surface charge of the modified nanoparticles. Gold nanoparticles before and after phase transfer were subjected to photofragmentation by a pulsed 532 nm laser. The effects of solvent properties and surface chemistry on the photofragmentation of the gold nanoparticles have been investigated. Fast photofragmentation has been observed in the organic solvent in which the dielectric constant, heat capacity, and thermal conductivity are lower. The results suggest new approaches for the preparation of very small gold clusters from gold nanoparticles.     

Facile synthesis of gold nanoparticles capped with an ammonium-based chiral ionic liquid crystal

Herein, we describe a facile synthesis of stable chiral ionic liquid crystal (ILC)-capped gold nanoparticles. A new ILC containing a chiral cholesterol moiety having a terminal triethylammonium group was synthesised which exhibited an enantiotropic lamellar mesophase. Stable, monodisperse citrate-stabilised gold nanoparticles having a size of ~60 nm were prepared and the citrate ligands on the gold nanoparticles were replaced with chiral ILC through a two-phase ligand exchange process. The resulting chiral ILC-stabilised particles were characterised using UV–visible (UV–Vis) and transmission electron microscopy (TEM) studies. Different from the citrate-stabilised nanoparticles, the ligand exchanged gold nanoparticles were dispersible in organic solvent and resulting dispersion was stable for more than observed period of 3 months. Furthermore, the chiral ILC-decorated gold nanoparticles were found to be well dispersible in a nematic host without any aggregation and induced a vertical alignment of the nematic director.     

Lamellar multilayer hexadecylaniline-modified gold nanoparticle films deposited by the Langmuir-Blodgett technique

Organization of hexadecylaniline (HDA)-modified colloidal gold particles at the air-water interface and the formation thereafter of lamellar, multilayer films of gold nanoparticles by the Langmuir-Blodgett technique is described in this paper. Formation of HDA-capped gold nanoparticles is accomplished by a simple biphasic mixture experiment wherein the molecule hexadecylaniline present in the organic phase leads to electrostatic complexation and reduction of aqueous chloroaurate ions, capping of the gold nanoparticles thus formed and phase transfer of the now hydrophobic particles into the organic phase. Organization of gold nanoparticles at the air-water interface is followed by surface pressure—area isotherm measurements while the formation of multilayer films of the nanoparticles by the Langmuir-Blodgett technique is monitored by quartz crystal microgravimetry, UV-Vis spectroscopy, Fourier transform infrared spectroscopy and transmission electron microscopy.     

Growth of sputter-deposited gold nanoparticles in ionic liquids

The growth of gold nanoparticles (NPs) synthesized by sputter deposition on an ionic liquid surface is studied in situ in the bulk phase of the ionic liquids (ILs) 1-butyl-3-methylimidazolium dicyanamide [C(1)C(4)Im][N(CN)(2)], 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide [C(1)C(4)Im][Tf(2)N], 1-butyl-3-methylimidazolium tetrafluoroborate [C(1)C(4)Im][BF(4)], 1-butyl-3-methylimidazolium hexafluorophosphate [C(1)C(4)Im][PF(6)] and 1-butyl-3-methylimidazolium triflate [C(1)C(4)Im][TfO]. It is found that primary nanoparticles with a diameter smaller than 2.5 nm are present in the sample immediately after sputtering. Growth of these primary particles proceeds after the end of the sputtering process and stops when the nanoparticles reach a certain size. Depending on the viscosity of the ionic liquid this growth process can proceed several hours to several days. The growth speed is fastest for the least viscous ionic liquid and follows the trend [C(1)C(4)Im][N(CN)(2)] > [C(1)C(4)Im][Tf(2)N] > [C(1)C(4)Im][TfO] > [C(1)C(4)Im][BF(4)] > [C(1)C(4)Im][PF(6)]. It is also found that a higher concentration of sputtered gold results in faster growth of the gold nanoparticles. A discussion on the growth mechanism of sputtered gold NPs is included.     

Electrochemical nucleation of gold nanoparticles in a polymer film at a liquid-liquid interface

Simultaneous nucleation of gold nanoparticles and polymerization of tyramine has been carried out at an immiscible electrolyte interface. By transferring the gold ion of tetraoctylammoniumtetracloroaurate (TOAAuCl(4)) from the organic to the aqueous phase, a fast homogeneous electron transfer from the tyramine monomer reduces the gold ion. Electropolymerization then proceeds, and gold nanoparticles form. The newly formed nanoparticles act as nucleation sites for the deposition of the oligomers/polymer (and possibly vice versa). This results in gold nanoparticles stabilized in a polytyramine matrix. The size of the nanoparticles is controlled by the concentration of oligomers/polymer in solution. The polymer nanoparticle composite film was analyzed with TEM, XPS, and AFM.     

Organic phase stabilization of rhodium nanoparticle catalyst by direct phase transfer from aqueous solution to room temperature ionic liquid based on surfactant counter anion exchange

We describe the organic phase transfer of surfactant-stabilized rhodium nanoparticles previously synthesized in an aqueous solution of N,N-dimethyl-N-dodecyl-N-(2-hydroxyethyl)ammonium chloride (HEA12Cl); the addition of LiN(Tf)2 to the aqueous suspension of Rh-HEA12Cl transferred the hydrosol nanoparticles to an ionic liquid phase.     

Surface plasmon modes of gold nanospheres, nanorods, and nanoplates in an organic solvent: phase-transfer from aqueous to organic media

We present a process for the phase-transfer of gold nanoparticles from an aqueous to an organic medium with normal alkanethiols. This method can be applied not only to large nanospheres (d~100 nm) but also to anisotropic nanoparticles like nanorods and nanoplates. It allows the comparison of the nanoparticle optical properties when they are dispersed in both aqueous and organic media.     

A combination of dispersive liquid–liquid microextraction and surface plasmon resonance sensing of gold nanoparticles for the determination of ziram pesticide

We have developed a reliable, fast, and highly sensitive analytical method utilizing dispersive liquid–liquid microextraction and gold nanoparticles probes for ziram (zinc bis(dimethyldithiocarbamate)) determination. The method is based on the in situ formation of gold nanoparticles in carbon tetrachloride as an organic phase. It was found that the trace levels of ziram influenced the formation of gold nanoparticles, leading to absorbance change of a sedimented phase. The results of the colorimetric ziram determination were in the concentration range of 0.12–2.52 ng/mL with a limit of detection of 0.06 ng/mL. The formation of the stable and dispersed gold nanoparticles in the organic phase provides a good precision for dispersive liquid–liquid microextraction method, resulting in the relative standard deviation of 3.8 and 1.2% for 0.56 and 1.58 ng/mL of ziram, respectively. This method has been successfully used for the ziram determination in samples of well and river water, soil, potato, carrot, wheat, and paddy soil.     

Transfer of biosynthesized gold nanoparticles from water into an ionic liquid using alkyltrimethyl ammonium bromide: an anion-exchange process

Biosynthesized gold nanoparticles (GNPs) were transferred from water to a hydrophobic ionic liquid (IL), [Bmim]PF(6), with the assistance of alkyl trimethyl ammonium bromide. The phase transfer mechanism was illustrated through the exemplification of cetyltrimethyl ammonium bromide (CTAB). Interaction between GNPs and CTAB was demonstrated through zeta potential analysis. Moreover, an anion-exchange process was discovered between CTAB and IL. During the process, the hydrophobic CTAPF(6) formed in situ on the GNPs led to the hydrophobization and thus phase transfer of the GNPs. The phase transfer efficiency was found to be size-dependent.     

Inhibited and enhanced nucleation of gold nanoparticles at the water|1,2-dichloroethane interface

The deposition of gold at the interface between immiscible electrolyte solutions has been investigated using reduction of tetrachloroaurate or tetrabromoaurate in 1,2-dichloroethane, with aqueous phase hexacyanoferrate as reducing agent. In a clean environment without defects present at the interface, the Au(III) complex was reduced to the Au(I) complex, but no solid phase formation could be observed. A deposition process could only be observed through the addition of artificial nucleation sites in the form of palladium nanoparticles at the interface. This process could be associated with the reduction of the Au(I) halide complex to metallic gold, by determining the gold reduction potentials in 1,2-dichloroethane. XANES measurements indicate that tetrachloroaurate ion transfers intact into the organic phase, with the central Au atom retaining its oxidation state of +3 and the overall anion remaining charged at -1.     

Stabilizer-free nanosized gold sols

The paper describes a convenient, rapid, and reproducible method for the synthesis of stable dispersions of uniform gold nanoparticles at ambient temperatures by mixing aqueous solutions of tetrachloroauric acid and iso-ascorbic acid. The influence of the experimental conditions on the size of the gold particles and the stability of the final sols was monitored by dynamic light scattering and UV-vis spectrophotometry. It was found that the size of the resulting nanoparticles is affected by the concentration and the pH of gold solution, while the stability of the electrostatically stabilized final sols is strongly dependent on the excess of reductant in the system, the ionic strength, and the temperature of the precipitation. Since the preparation process does not require the addition of a dispersing agent, the surface of the resulting gold nanoparticles can be easily functionalized to make them suitable for applications in medicine, biology, and catalysis.     

Hydrophilic gold nanoparticles adaptable for hydrophobic solvents

Surface ligand molecules enabling gold nanoparticles to disperse in both polar and nonpolar solvents through changes in conformation are presented. Gold nanoparticles coated with alkyl-head-capped PEG derivatives were initially well dispersed in water through exposure of the PEG residue (bent form). When chloroform was added to the aqueous solution of gold nanoparticles, the gold nanoparticles were transferred from an aqueous to a chloroform phase through exposure of the alkyl-head residue (straight form). The conformational change (bent to straight form) of immobilized ligands in response to the polarity of the solvents was supported by NMR analyses and water contact angles.     

Versatile phase transfer of gold nanoparticles from aqueous media to different organic media

A novel, simple, and very efficient method to prepare hydrophobically modified gold particles is presented. Gold nanoparticles of different sizes and polydispersities were prepared. The diameter of the gold particles ranges from 5 to 37 nm. All systems were prepared in aqueous solution stabilized by citrate and afterwards transferred into an organic phase by using amphiphilic alkylamine ligands with different alkyl chain lengths. The chain length was varied between 8 and 18 alkyl groups. Depending on the particle size and the alkylamine, different transfer efficiencies were obtained. In some cases, the phase transfer has a yield of about 100%. After drying, the particles can be redispersed in different organic solvents. Characterization of the particles before and after transfer was performed by using UV/Vis spectroscopy, transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS) techniques. The effect of organic solvents with various refractive indices on the plasmon band position was investigated.     

Electrodeposition of gold nanoparticles at a solid|ionic liquid|aqueous electrolyte three-phase junction

Gold nanoparticles have been electrodeposited on an electrode through electrogeneration at an ITO|AuCl₄^? solution in an ionic liquid|aqueous electrolyte three-phase junction. The electrodeposition was carried out by inverted double-pulse potential chronoamperometry. The direct reduction of AuCl₄^? ions at the electrode is followed by a counterion transfer through the liquid|liquid interface. Contrary to the electrodeposition from a single ionic liquid phase, scanning electron microscopy reveals that the shape of the resulting nanoparticles is highly angular and well-developed with a diameter of 110 ± 30 nm. Catalytic oxidation of glucose on the modified electrode is demonstrated.     

Single laser pulse induced aggregation of gold nanoparticles

Gold nanoparticles with an average diameter of 11 nm (Au(39000)) were prepared in an SDS aqueous solution. A 80-microm liquid droplet (microdroplet) of the solution was ejected into the atmosphere from a microdroplet nozzle. Structural changes of the gold nanoparticles in the microdroplet, after they were irradiated with a focused single-nanosecond laser pulse at the wavelength of 532 nm, were studied by transmission electron microscopy (TEM) and optical absorption spectroscopy. It was revealed that the gold nanoparticles are fragmented into small particles and then the small fragments aggregate with each other. The aggregation was found to be terminated 100 micros after the laser-pulse excitation.     

Two-dimensional self-organization of polystyrene-capped gold nanoparticles

Thiol end-functionalized polystyrene chains have been introduced onto the surface of gold nanoparticles via a two-step grafting-to method. This simple grafting procedure is demonstrated to be efficient for gold nanoparticles of different sizes and for particles initially dispersed in either aqueous or organic media. The method has been applied successfully for a relatively large range of polystyrene chain lengths. Grafting densities, as determined by thermogravimetric analysis, are found to decrease with increasing chain length. In all cases, the grafting density indicates a dense brush conformation for the tethered chains. The resulting functionalized nanoparticles self-organize into hexagonally ordered monolayers when cast onto solid substrates from chloroform solution. Furthermore, the distance between the gold cores in the dried monolayer is controlled by the molecular weight of the grafted polystyrene. Optical absorption spectra recorded for the organized monolayers show the characteristic plasmon absorption of the gold particles. Importantly, the plasmon resonance frequency exhibits a distinct dependence on interparticle separation that can be attributed to plasmon coupling between neighboring gold cores.     

Organic-soluble fluorescent Au8 clusters generated from heterophase ligand-exchange induced etching of gold nanoparticles and their electrochemiluminescence

A unique heterophase ligand exchange induced etching process was used to transform gold nanoparticles into organic-soluble fluorescent gold clusters which were assigned to Au(8) by optical spectroscopy and MALDI-TOF mass spectrometry. Both the annihilation electrochemiluminescence of fluorescent Au(8) clusters in organic solution and the coreactant electrochemiluminescence of Au(8) cluster film in aqueous solution were studied.