Continuous free-flow electrophoresis of water-soluble monolayer-protected clusters

There has recently been a surge of interest in the properties and applications of monolayer protected clusters (MPCs). MPCs are metal nanoparticles that have unique optical, chemical, and electrochemical properties resulting from their small size. Because the size defines their properties, MPC particle size fractionation is important for control of the MPC characteristics for use in many potential applications. This paper explores the use of continuous free-flow electrophoresis (CFE) for the size fractionation of N-(2-mercaptopropionyl)glycine (tiopronin) monolayer protected gold clusters into monodisperse nanoparticle samples. CFE is a fractionation technique that isolates monodisperse particle sizes into several different collection vials on the tens of milligrams scale. This allows the MPCs to be separated based on their electrophoretic mobilities into isolated, monodisperse particles across a wide range of sizes. CFE separation of water-soluble tiopronin MPCs yielded fractions that varied in color, UV-visible spectra, transmission electron microscopy (TEM) size histograms, and solubility, indicating narrow size dispersity in the isolated fractions. UV-visible spectrophotometry verified the separation of the tiopronin MPCs through the inspection of surface plasmon resonance peak sizes for the different fractions. TEM was also used to verify the narrowed dispersity of MPC samples. The ability to separate water-soluble nanoparticles into 30 or more fractions in a continuous flow process will enable future studies on their size dependent properties.     

Temperature-dependent quantized double layer charging of monolayer-protected gold clusters

This paper describes low-temperature voltammetry of purified hexanethiolate-coated monolayer-protected Au140 clusters (C6 MPCs). Lowered temperatures enhance the resolution of quantized double layer (QDL) charging peaks in differential pulse voltammetry (DPV) observations. As many as 13 resolved peaks are seen in illustrative voltammetry at 263 K in CH2Cl2 solvent, and the concept of voltammetric peak capacity is introduced. For the one-electron MPC charge steps surrounding the E(PZC) of the MPC (small numbers of electrons added or removed from the core), the capacitance C(CLU) of the MPCs (measured from the voltage spacing between charging peaks) increases by approximately 15% as the solvent temperature is lowered from 273 to 210 K. The experimental C(CLU) temperature dependency (d[ln(C(CLU))]/dT approximately -0.0025, in 0.1 M electrolyte) is discussed in light of temperature dependencies of the compact and diffuse double layer capacitances. It is concluded that the observed temperature dependence is probably a mixed diffuse, compact dependence. The regular voltage spacing of MPC charging peaks near the potential of zero charge is generally consistent with electrical double layer properties, but the irregular pattern of charging of the nanoparticles seen at higher charge states suggests intervention of the incipient molecular behavior of Au140 cores in the spacing of energies at which further electrons are added or removed.     

The monolayer thickness dependence of quantized double-layer capacitances of monolayer-protected gold clusters

This report describes how the electrochemical double-layer capacitances of nanometer-sized alkanethiolate monolayer-protected Au clusters (MPCs) dissolved in electrolyte solution depend on the alkanethiolate chain length (C4 to C16). The double-layer capacitances of individual MPCs (C(CLU)) are sufficiently small (sub-attoFarad, aF) that their metal core potentials change by >0.1 V increments for single electron transfers at the electrode/solution interface. Thus, the current peaks observed are termed "quantized double layer charging peaks", and their spacing on the potential axis varies with C(CLU). Differential pulse voltammetric measurements of C(CLU) in solutions of core-size-fractionated (i.e., monodisperse) MPCs are compared to a simple theoretical model, which considers the capacitance as governed by the thickness of a dielectric material (the monolayer, whose chain length is varied) between concentric spheres of conductors (the Au core and the electrolyte solution). The experimental results fit the simple model remarkably well. The prominent differential pulse voltammetric charging peaks additionally establish this method, along with high-resolution transmission electron microscopy and laser ionization-desorption mass spectrometry, as a tool for evaluating the degree of monodispersity of MPC preparations. We additionally report on a new tactic for the preparation of monodisperse MPCs with hexanethiolate monolayers.     

HPLC of monolayer-protected gold nanoclusters

Polydisperse samples of Au nanoparticles protected with monolayers of hexanethiolate ligands (C6 MPCs) and with mixed monolayers of hexanethiolate and mercaptoundecanoic acid (C6/MUA MPCs) have been chromatographically separated using C8 120-A columns and acetone/ toluene mobile phase. The spectral details of eluted peaks and of quantized double-layer charging features in the differential pulse voltammetry of collected fractions were used to show that the elution orders of C6 MPC mixtures and of C6/MUA MPC mixtures were different. For C6 MPCs, the smallest MPCs were eluted first, whereas the smallest C6/MUA MPCs were eluted last. The reversal of order of elution was rationalized in terms of intermolecular interactions with the stationary phase, dominant for the C6 MPC, being suppressed by the heightened polarity of the monolayer surface of the C6/MUA MPCs, making a size exclusion mechanism dominant. The range of apparent core diameters of the separated nanoparticles was 1.3-2 nm.     

Dendritic functionalization of monolayer-protected gold nanoparticles

This paper describes the facile synthesis of nanoparticle-cored dendrimers (NCDs) and nanoparticle megamers from monolayer-protected gold clusters using either single or multi-step reactions. First, 11-mercaptoundecanoic acid/hexanethiolate-protected gold clusters were synthesized using the Schiffrin reaction followed by the ligand place-exchange reaction. A convergent approach for the synthesis of nanoparticle-cored dendrimers uses a single step reaction that is an ester coupling reaction of hydroxy-functionalized dendrons with carboxylic acid-functionalized gold clusters. A divergent approach, which is based on multi-step reactions, employs the repetition of an amide coupling reaction and a Michael addition reaction to build polyamidoamine dendritic architectures around a nanoparticle core. Nanoparticle megamers, which are large dendrimer-induced nanoparticle aggregates with an average diameter of more than 300 nm, were prepared by the amide coupling reaction between polyamiodoamine [G-2] dendrimers and carboxylic acid-functionalized gold clusters. ¹H NMR spectroscopy, FT-IR spectroscopy, thermogravimetric analysis (TGA), and transmission electron microscopy (TEM) were used for the characterization of these hybrid nanoparticles.     

Redox and double-layer charging of phenothiazine functionalized monolayer-protected clusters

Monolayer-protected Au clusters (MPCs) have been prepared with mixed monolayers of alkanethiolates and alkanethiolates terminally omega-functionalized with phenothiazine. The mixed monolayer MPCs can contain as many as 10 phenothiazines/MPC; these electron donors are electroactive in rapid, successive one-electron reactions. Surface adsorption of the functionalized MPCs is evident in cyclic voltammetry. Double-potential-step chronocoulometry with incremented potential steps was applied to unfunctionalized hexanethiolate-coated MPCs and to those functionalized with phenothiazine to analyze the coupling between the diffusion-controlled double-layer charging of the MPC cores and the oxidation of the phenothiazine centers. Apparent changes in ordering of the MPC alkanethiolate chains were observed with infrared spectroscopy in solutions of MPCs where alcohol, carboxylic acid, or phenothiazine moieties had been incorporated into the monolayer.     

DNA binding of an ethidium intercalator attached to a monolayer-protected gold cluster

Ethidium intercalation has been investigated as a means of inducing binding of Au nanoparticles to DNA. The ethidium sites are attached to the nanoparticles as thiolate ligands, using 3,8-diamino-5-mercaptododecyl-6-phenylphenanthridinium (ethidium thiolate). Each nanoparticle bears only one or two ethidium thiolate ligands. The rest of the thiolate monolayer ligands on the monolayer-protected Au clusters (MPCs) were either N-(2-mercaptopropionyl)glycine (tiopronin/ethidium MPC) or trimethyl(mercaptoundecyl)ammonium (TMA/ethidium MPC). In solution mixtures of DNA and MPCs, the energy-transfer quenching of the ethidium ligands by the metal-like MPC core is partially released by ethidium binding to DNA, as observed by an increase in the intensity of ethidium fluorescence. Binding of the cationic TMA/ethidium MPC to DNA was efficient and rapid. The negatively charged tiopronin/ethidium MPC, in contrast, exhibits slow intercalation kinetics, relative to ethidium cation not attached to an MPC. The slow kinetics were analyzed as two competing binding interactions. The tiopronin/ethidium MPC binding to DNA was imaged by AFM.     

Mixed monolayer-protected gold nanoclusters as selective peptide extraction agents for MALDI-MS analysis

Cationic and anionic nanoparticles selectively target peptides with low and high isoelectric points, respectively. Additionally, their high surface area-to-volume ratios make these nanoparticles (approximately 2-nm core diameter) very efficient extraction and concentration agents. Upon extraction, the peptide-bound nanoparticles can be analyzed by MALDI-MS to provide highly sensitive detection of the targeted peptides. We demonstrate that MALDI-MS can detect peptide concentrations as low as 500 pM from 250-microL solutions using these nanoparticle scaffolds as extraction and concentration agents.     

Sorptive behavior of monolayer-protected gold nanoparticle films: implications for chemical vapor sensing

Monolayer-protected gold nanoparticle materials were synthesized and characterized for use as sorptive layers on chemical sensors. Thiols investigated as monolayer-forming molecules included dodecanethiol, benzenethiol, 4-chlorobenzenethiol, 4-bromobenzenethiol, 4-(trifluoromethyl)benzenethiol, 4-hydroxybenzenethiol, and 4-aminobenzenethiol. Films of selected monolayer-protected nanoparticle (MPN) materials were deposited on thickness shear mode devices and vapor uptake properties were measured at 298 K. Many, but not all, MPN-based sensing layers demonstrated rapid and reversible uptake of vapors, and sorptive selectivity varies with the monolayer structure. The mass of vapor sorbed per mass of sorptive material was determined and compared with poly(isobutylene) and poly(epichlorohydrin) as examples of simple sorptive polymers that have been used on vapor sensors. The nanoparticle-based films considered here were less sorptive than the selected polymers on a per-mass basis. Partition coefficients, which measure the mass of vapor sorbed per volume of the sorptive phase, were estimated for these MPN materials and found to be comparable to or less than those of the polymer layers. Implications for the roles of sorption and transduction in determining the performance of chemical sensors coated with nanoparticle-based films are discussed.     

Anisotropic growth of gold clusters to gold nanocubes under UV irradiation

A chiral reagent, 2-naphthol, has been introduced under alkaline solution as a reductant for HAuCl(4) in CTAB micelle to produce exclusively cubic gold nanoparticles under UV photoactivation. Prolonged irradiation helped the digestion of the primarily evolved spherical particles into smaller gold nanocubes, which then act as tiny cubic seeds, leading to the formation of larger nanocubes. The smaller cubes take the assistance of CTAB under alkaline condition to serve as the seed in directing the transformation of all the spherical colloids into cubic shapes under continuous irradiation via Ostwald ripening. The shape transformation of the nanoparticles has been monitored by repetitive TEM imaging and absorption spectral analysis. The FTIR analysis proves that the gold nanocubes are capped by CTAB. The XRD pattern authenticates the formation of the fcc gold nanocubes. GCMS studies in turn confirmed the presence of hydroxylation of 2-naphthol in the course of the reaction, leaving exclusively cubic gold nanoparticles at the final stage of the photoactivation reaction.     

A structural mass spectrometry strategy for the relative quantitation of ligands on mixed monolayer-protected gold nanoparticles

It is becoming increasingly common to use gold nanoparticles (AuNPs) protected by a heterogeneous mixture of thiolate ligands, but many ligand mixtures on AuNPs cannot be properly characterized due to the inherent limitations of commonly used spectroscopic techniques. Using ion mobility-mass spectrometry (IM-MS), we have developed a strategy that allows measurement of the relative quantity of ligands on AuNP surfaces. This strategy is used for the characterization of three samples of mixed-ligand AuNPs: tiopronin:glutathione (av diameter 2.5 nm), octanethiol:decanethiol (av diameter 3.6 nm), and tiopronin:11-mercaptoundecyl(poly ethylene glycol) (av diameter 2.5 nm). For validation purposes, the results obtained for tiopronin:glutathione AuNPs were compared to parallel measurements using nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry (MS) without ion mobility separation. Relative quantitation measurements for NMR and IM-MS were in excellent agreement, with an average difference of less than 1% relative abundance. IM-MS and MS without ion mobility separation were not comparable, due to a lack of ion signals for MS. The other two mixed-ligand AuNPs provide examples of measurements that cannot be performed using NMR spectroscopy.     

Synthesis of anisotropic gold nanoparticles in a water-soluble polymer

Anisotropic gold nanoparticles have been synthesized by a UV irradiation technique through the interaction of HAuCl₄ and a stabilizing agent, poly (vinyl pyrrolidone) (PVP). The effect of irradiation time on the size and shape of gold nanoparticles was investigated by UV-visible spectroscopy and Transmission Electron Microscopy (TEM). The absorption spectra of all samples show a broad band with the characteristic surface plasmon resonance (SPR) peak visible at around 530 nm. The presence of an additional low intensity absorption peak at a longer wavelength suggests the presence of non-spherical nanoparticles. The TEM measurements show evidence of particle shapes such as spheres, hexagons, decahedrons and truncated triangles as the reaction proceeded from 5 min to 24 h. The variation in particle shape is probably due to the effect of the reduced gold to PVP ratio as the reaction proceeds.     

Ion-pair extraction system for the mutual separation of lanthanides using divalent quadridentate schiff bases

For the selective extraction of trivalent lanthanides, the use of quadridentate divalent phenolic Schiff bases, such as N,N'-bis(5-nitrosalicilidene)ethylenediamine (H(2)Nsalen) and N,N'-bis(5-nitrosalicilidene)-o-phenylenediamine (H(2)Nsaloph), was investigated. Lanthanides made anionic 1:2 complexes with these ligands and could be extracted into nitrobenzene as ion-pairs with a suitable monovalent countercation in the aqueous phase, after which the ion-pair was dissociated almost perfectly. Although the order of the extractability of lanthanides between these ligands was H(2)Nsaloph > H(2)Nsalen, the mutual selectivity of them in the H(2)Nsalen system was higher than that in H(2)Nsaloph. Furthermore, with decreasing the size of the countercation, the mutual selectivity was enhanced although the extractability was lowered. A H(2)Nsalen-KCl extraction system, selected as an example, showed selectivity between lanthanides comparable with those of the better of other systems reported previously.