Synthesis and electrochemical applications of gold nanoparticles

This review covers recent advances in synthesis and electrochemical applications of gold nanoparticles (AuNPs). Described approaches include the synthesis of AuNPs via designing and choosing new protecting ligands; and applications in electrochemistry of AuNPs including AuNPs-based bioelectrochemical sensors, such as direct electrochemistry of redox-proteins, genosensors and immunosensors, and AuNPs as enhancing platform for electrocatalysis and electrochemical sensors.

Adaptive recognition of small molecules by nucleic acid aptamers through a label-free approach

We report a novel label-free method for the investigation of the adaptive recognition of small molecules by nucleic acid aptamers using capillary electrophoresis analysis. Cocaine and argininamide were chosen as model molecules, and the two corresponding DNA aptamers were used. These single-strand DNAs folded into their specific secondary structures, which were mainly responsible for the binding of the target molecules with high affinity and specificity. For molecular recognition, the nucleic acid structures then underwent additional conformational changes, while keeping the target molecules stabilized by intermolecular hydrogen bonds. The intrinsic chemical and physical properties of the target molecules enabled them to act as indicators for adaptive binding. Thus any labeling or modification of the aptamers or target molecules were made obsolete. This label-free method for aptamer-based molecular recognition was also successfully applied to biological fluids and therefore indicates that this approach is a promising tool for bioanalysis.

An effective hydrothermal route for the synthesis of multiple PDDA-protected noble-metal nanostructures

In this Article, we demonstrate an effective hydrothermal route for the synthesis of multiple PDDA-protected (PDDA = poly(diallyl dimethylammonium) chloride) noble-metal (including silver, platinum, palladium, and gold) nanostructures in the absence of any seeds and surfactants, in which PDDA, an ordinary and water-soluble polyelectrolyte, acts as both a reducing and a stabilizing agent. Under optimal experimental conditions, Ag nanocubes, Pt and Pd nanopolyhedrons, and Au nanoplates can be obtained, which were characterized by transmission electron microscopy, scanning electron microscopy, energy-dispersive spectroscopy, and X-ray diffraction. More importantly, the nanostrucfures synthesized show potential applications in surface-enhanced Raman scattering and electrocatalysis, in which Ag nanocubes and Pt nanopolyhedrons were chosen as the examples, respectively.

Direct electrochemistry and electrocatalysis of horseradish peroxidase immobilized in Nafion-RTIL composite film

The composite film based on Nafion and hydrophobic room-temperature ionic liquid (RTIL) 1-butyl-3-methyl-imidazolium hexafluorophosphate ([bmim] PF6) was explored. Here, Nafion was used as a binder to form Nafion-ionic liquids composite film and help [bmim] PF6 effectively adhered on glassy carbon (GC) electrode. X-ray photoelectron spectroscopy (XPS), cyclic voltammtery (CV) and electrochemical impedance spectroscopy (EIS) were used to characterize this composite film, showing that the composite film can effectively adhere on the GC electrode surface through Nafion interacting with [bmim] PF6 and GC electrode. Meanwhile, doping [bmim] PF6 in Nafion can also effectively reduce the electron transfer resistance of Nafion. The composite film can be readily used as an immobilization matrix to entrap horseradish peroxidase (HRP). A pair of well-defined redox peaks of HRP was obtained at the HRP/Nafion[bmim] PF6 composite film-modified GC electrode through direct electron transfer between the protein and the underlying electrode. HRP can still retain its biological activity and enhance electrochemical reduction towards O-2 and H2O2. It is expected that this composite film may find more potential applications in biosensors and biocatalysis.

Guanidine/Pd(OAc)(2)-catalyzed room temperature Suzuki cross-coupling reaction in aqueous media under aerobic conditions

A highly efficient Pd(OAc)(2)/guanidine aqueous system for the room temperature Suzuki cross-coupling reaction has been developed. The new water-soluble and air-stable catalyst Pd(OAc)(2)(.)(1f)(2) from Pd(OAc)(2) and 1,1,3,3-tetramethyl-2-n-butylguanidine (1f) was synthesized and characterized by X-ray crystallography. In the presence of Pd(OAc)(2)(.)(1f)(2), coupling of arylboronic acids with a wide range of aryl halides, including aryl iodides, aryl bromides, even activated aryl chlorides, was carried out smoothly in aqueous solvent to afford the cross-coupling products in good to excellent yields and high turnover numbers (TONs) (TONs up to 850 000 for the reaction of 1-iodo-4-nitrobenzene and phenylboronic acid). Furthermore, this mild protocol could tolerate a broad range of functional groups.

PEG-supported dipyridyl ligand for palladium-catalyzed Suzuki and Suzuki-type reactions in PEG and aqueous media

An air- and water-stable PEG-supported bidentate nitrogen ligand is prepared and its applications in the palladium-catalyzed Suzuki reaction of aryl halides with arylboronic acids in PEG and Suzuki-type reaction of aryl halides with sodium tetraphenylborate in aqueous media are reported. The homogeneous catalyst system is environmentally friendly and offers the advantages of high activity, reusability and easy separation.

Local and semilocal density functional computations for crystals of 1-alkyl-3-methyl-imidazolium salts

The accuracy and reliability of popular density functional approximations for the compounds giving origin to room temperature ionic liquids have been assessed by computing the T=0 K crystal structure of several 1-alkyl-3-methyl-imidazolium salts. Two prototypical exchange-correlation approximations have been considered, i.e., the local density approximation (LDA) and one gradient corrected scheme [PBE-GGA, Phys. Rev. Lett. 77, 3865 (1996)]. Comparison with low-temperature x-ray diffraction data shows that the equilibrium volume predicted by either approximations is affected by large errors, nearly equal in magnitude (~10%), and of opposite sign. In both cases the error can be traced to a poor description of the intermolecular interactions, while the intramolecular structure is fairly well reproduced by LDA and PBE-GGA. The PBE-GGA optimization of atomic positions within the experimental unit cell provides results in good agreement with the x-ray structure. The correct system volume can also be restored by supplementing PBE-GGA with empirical dispersion terms reproducing the r-6 attractive tail of the van der Waals interactions.

Ion Association in [bmim][PF6]/Naphthalene Mixtures: An Experimental and Computational Study

Mixtures of room temperature ionic liquids (IL) with neutral organic molecules provide a valuable testing ground to investigate the interplay of the ionic and molecular-dipolar state in dense Coulomb systems at near ambient conditions. In the present study, the viscosity eta and the ionic conductivity a of 1-n-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6])/naphthalene mixtures at T = 80 degrees C have been measured at 10 stoichiometries spanning the composition range from pure naphthalene to pure [bmim][PF6]. The viscosity grows nearly monotonically with increasing IL mole fraction (x), whereas the conductivity per ion displays a clear peak at x approximate to 15%. The origin of this maximum has been investigated using molecular dynamics simulations based on a classical force field. Snapshots of the simulated samples show that the conductivity maximum is due to the gradual transition in the IL component from an ionic state at high x to a dipolar fluid made of neutral ion pairs at low x. At concentrations x <0.20 the ion pairs condense into molecular-thin filaments bound by dipolar forces and extending in between nanometric droplets of IL. These results are confirmed and complemented by the computation of dynamic and transport properties in [bmim][PF6]/naphthalene mixtures at low IL concentration.

Voltammetric characterization of the ferrocene vertical bar ferrocenium and cobaltocenium vertical bar cobaltocene redox couples in RTILs

Ferrocene, Fc, and cobaltocenium hexafluorophosphate, CcPF(6), have been recommended for use as internal reference redox couples in room-temperature ionic liquids (RTILs), as well as in more conventional aprotic solvents. In this study, the electrochemical behavior of Fc and CcPF(6) is reported in eight commonly used RTILs; [C(2)mim][NTf2], [C(4)mim][NTf2], [C(4)mim][BF4], [C(4)mim][PF6], [C(4)mim][OTf], [C(4)mim][NO3], [C(4)mpyrr][NTf2], and [P-14,P-6.6,P-6][FAP], where [C(n)mim](+) = 1-butyl-3-methylimidazolium, [NTf2](-) = bis(trifluoromethylsulfonyl)imide, [BF4](-) = tetrafluoroborate, [PF6](-) = hexafluorophosphate, [OTf](-) = trifluoromethylsulfonate, [NO3](-) = nitrate, [C(4)mpyrr](+) = N-butyl-N-methylpyrrolidinium, [P-14,P-6,P-6,P-6](+) = tris(ri-hexyl)-tetradecylphosphonium and [FAP](-) = trifluorotris(pentafluoroethyl)phosphate, over a range of concentrations and temperatures. Solubilities and diffusion coefficients, D, of both the charged and neutral species were determined using double potential-step chronoamperometry, and CcPF(6) (36.5-450.0 mM) was found to be Much more Soluble than Fc (27.5-101.8 mM). It was observed that classical Stokes-Einstein diffusional behavior applies for Fc and CcPF(6) in all eight RTILs. Diffusion coefficients of Fc and CcPF(6) were calculated at a range of temperatures, and activation energies calculated. It was also determined that D for Fc and CcPF(6) does not change significantly with concentration. This supports the use of both Fe and CcPF(6) to provide a well-characterized and model redox couple for use as a voltammetric internal potential reference in RTILs contrary to previous literature reports in the former case.

Lewis acid platinum complexes of conformationally flexible NUPHOS diphosphines: Highly efficient catalysts for the carbonyl-ene reaction

Enantiopure Lewis acid complexes of conformationally flexible acyclic and monocyclic NUPHOS diphosphines, delta- and lambda-[(NUPHOS)Pt(OTf)(2)], are efficient catalysts for the carbonyl-ene reaction between various unsymmetrical 1,1'-disubstituted alkenes and phenylglyoxal or ethyl glyoxylate. While catalyst performance was substrate dependent, ee values as high as 95% and yields up to 90% have been obtained. In a number of cases catalysts generated from delta- and lambda-[(NUPHOS)Pt{(S)-BINOL}] showed marked enhancements in enantioselectivity in ionic liquids compared with organic media. Although an enhancement in enantioselectivity was not obtained for all substrate combinations in such cases, the enantioselectivities were comparable to those obtained in dichloromethane. Furthermore, although the ee's are initially comparable in both the ionic liquid and dichloromethane, a gradual erosion of ee with time was found in the organic solvent, whereas the ee remained constant in the ionic liquid. Preliminary kinetic investigations suggest that the decrease in ee may be due to a faster racemization of the catalyst in dichloromethane compared with the ionic liquid.

A structural and electrochemical investigation of 1-alkyl-3-methylimidazollum salts of the nitratodioxouranate(VI) anions [{UO2(NO3)(2)}(2)(mu(4)-C2O4)](2-), [UO2(NO3)(3)](-), and [UO2(NO3)(4)](2-)

The properties of the 1-butyl-3-methylimidazolium salt of the dinuclear mu(4)-(O,O,O',O'-ethane-1,2-dioato)bis[bis-(nitrato-O,O)dioxouranate(VI)] anion have been investigated using electrochemistry, single-crystal X-ray crystallography, and extended X-ray absorbance fine structure spectroscopy: the anion structures from these last two techniques are in excellent agreement with each other. Electrochemical reduction of the complex leads to the a two-electron metal-centered reduction of U(VI) to U(IV), and the production Of UO2, or a complex containing UO2. Under normal conditions, this leads to the coating of the electrode with a passivating film. The presence of volatile organic compounds in the ionic liquids 1-alkyl-3-methylimidazolium nitrate (where the 1-alkyl chain was methyl, ethyl, propyl, butyl, pentyl, hexyl, dodecyl, hexadecyl, or octadecyl) during the oxidative dissolution of uranium(IV) oxide led to the formation of a yellow precipitate. To understand the effect of the cation upon the composition and structure of the precipitates, 1-alkyl-3-methylimidazolium salts of a number of nitratodioxouranate(VI) complexes were synthesized and then analyzed using X-ray crystallography. It was demonstrated that the length of the 1-alkyl chain played an important role, not only in the composition of the complex salt, but also in the synthesis of dinuclear anions containing the bridging mu(4)-(O,O,O',O'-ethane-1,2-dioato), or oxalato, ligand, by protecting it from further oxidation.

Liquid and solid-state structures of 1,3-dimethylimidazolium salts

Using neutron and single crystal X-ray diffraction the structures of 1,3-dimethylimidazolim chloride and hexafluorophosphate salts have been determined in the liquid and the solid-state. The relative hydrogen bonding characteristics and sizes of the two anions force the ions to pack differently. In each case, a strong correlation between the crystal structure and liquid structure is found.

An EXAFS, X-ray diffraction, and electrochemical investigation of 1-alkyl-3-methylimidazolium salts of [{UO2(NO3)(2)}(2)(mu(4)-C2O4)](2-)

The structure of the 1-alkyl-3-methylimidazolium salts of the dinuclear mu(4)-(O,O,O',O'-ethane-1,2-dioato)-bis[bis(nitrato-O,O)dioxouranate(VI)] anion have been investigated using single crystal X-ray crystallography. In addition, EXAFS and electrochemical studies have been performed on the [C(4)mim](+) salt which is formed following the oxidative dissolution of uranium(IV) oxide in [C(4)mim][NO3]. EXAFS analysis of the solution following UO2 dissolution indicates a mixture of uranyl nitrate and mu(4)-(O,O,O',O'-ethane-1,2-dioato)-bis[bis(nitrato-O,O)dioxouranate(VI)] anions are formed.

A highly efficient synthetic procedure for deuteriating imidazoles and imidazolium salts

Both substituted imidazoles and 1,3-dialkylimidazolium salts can be fully deuteriated on the heterocyclic ring using D2O over heterogeneous Pd catalysts: deuteriated 1-alkyl-3-methylimidazolium chloride and hexafluorophosphate ionic liquids can also be prepared in good yields utilising readily available and relatively low cost sources of deuterium.

Neoteric optical media for refractive index determination of gems and minerals

Refractive index determination of minerals and gems often requires their immersion in fluids with the same refractive index. However, these natural materials frequently have refractive indices above the ranges of common organic solvents. Most available high refractive index immersion materials are solid at room temperature, toxic, noxious, corrosive, carcinogenic, or any combination thereof. Since the physical properties of ionic liquids can be tuned by varying the cation and/or anion, we have developed immersion fluids for mineralogical studies which are relatively benign. We report here the syntheses of a range of ionic liquids ( many novel) based on the 1-alkyl-3-methylimidazolium cation, which all have refractive indices greater than 1.4, and can be used as immersion fluids for optical mineralogy studies. We further show that for a series of ionic liquids with the same anion, the refractive indices can be adjusted by systematic changes in the cation.