Self-assembly of hard anions around cationic gold nanorods: potential structures for SERS.

The placement of polyoxometalates next to the surface of noble metallic nanoparticles has been found to enhance the surface-enhanced Raman scattering (SERS) effect. The enhancement is believed to stem from either charge (electrostatic attraction) or chemical effects. Anisotropic gold nanorods are recognized as useful nanostructures for SERS, mainly due to the high electric field enhancement at their ends.

Zeolite performance in removal of multicomponent heavy metal contamination from wastewater.

Efficient removal of heavy metal pollutants from wastewater by ion-exchange sorbents requires knowledge and understanding of the interplay between the adsorption patterns of the different components. The present study elucidates the simultaneous adsorption characteristics of six toxic heavy metal cations (Cd, Cr, Cu, Ni, Pb, and Zn) by two synthetic (13X and 4 A) and one natural (clinoptilolite) zeolite from solutions containing equimolar mixtures of the six metals. Equilibrium adsorption isotherms and equilibration dynamics were obtained by ICP-OES and complemented by EDXRF.

Argentometric chloride determination by inductively coupled plasma-optical emission spectroscopy in a wide range of sample matrices.

Chloride determination is of great importance, as chloride plays important roles in human health, pitting corrosion, environmental processes, and agriculture. However, chloride determination by inductively coupled plasma-optical emission spectroscopy (ICP-OES), one of the premier techniques used for elemental analysis, is currently limited to specific instrument types or requires the use of additional equipment. This work presents an argentometric method for the indirect measurement of chloride, applicable to any ICP-OES instrument.

Mixed-Ligand gold nanoparticles based optical sensor array for the recognition and quantification of seven toxic metals.

Sensor arrays use pattern recognition for the identification and quantification of analytes. In the presented work, a gold nanoparticle (GNP) based optical sensor array was employed to classify and quantify seven toxic metals (arsenic, barium, cadmium, cerium, chromium, lead, and mercury). The sensor array receptors were GNPs functionalized by mercaptoundecanoic acid, 2-mercaptoethanesulfonate, and a 1:1 mixture of the two ligands.

Determination of Uranium Isotopic Ratio by ICP-OES Using Optimal Sensitivity Position Analysis.

Isotopic composition analysis of natural and depleted uranium by inductively coupled plasma optical emission spectrometry (ICP-OES) requires the use of a high-resolution instrument due to the very slight isotopic shifts between the atomic emission spectra of the U and U isotopes. In this work, we show that conventional ICP-OES (without high-resolution optics) can be used for highly accurate uranium isotopic analysis, on par with the results obtained by ICP-MS. Such accurate measurements are achieved by applying a preparatory mathematical procedure termed the optimal sensitivity position (OSP) procedure.

Metallic-Nanoparticle-Based Sensing: Utilization of Mixed-Ligand Monolayers.

The last two decades have seen great advancements in fundamental understanding and applications of metallic nanoparticles stabilized by mixed-ligand monolayers. Identifying and controlling the organization of multiple ligands in the nanoparticle monolayer has been studied, and its effect on particle properties has been examined. Mixed-ligand protected particles have shown advantages over monoligand protected particles in fields such as catalysis, self-assembly, imaging, and drug delivery.

Direct Detection of Uranyl in Urine by Dissociation from Aptamer-Modified Nanosensor Arrays.

An ever-growing demand for uranium in various industries raises concern for human health of both occupationally exposed personnel and the general population. Toxicological effects related to uranium (natural, enriched, or depleted uranium) intake involve renal, pulmonary, neurological, skeletal, and hepatic damage. Absorbed uranium is filtered by the kidneys and excreted in the urine, thus making uranium detection in urine a primary indication for exposure and body burden assessment.

Improving the properties of a gold nanoparticle barium sensor through mixed-ligand shells.

This work proposes an improvement of gold nanoparticle sensors using mixed-ligand shells composed of ligands with a shared affinity. As a proof of concept, two ligands, 2-Sulfanylethanesulfonate (MSA) and 11-mercaptoundecanoic acid (MUA), sharing an affinity towards Ba were chosen. The two ligands were then combined in a mixed ligand shell, and the Ba sensor properties of both the mixed-ligand and mono-ligand shell nanoparticles were examined.

Rapid direct determination of tin in beverages using energy dispersive X-ray fluorescence.

This article presents a new method for the simpler and faster determination of tin in beverages using EDXRF. Absorption coefficients for aqueous calibration samples were calculated and shown to be nearly identical to those of the beverage samples, thus permitting the use of aqueous standard solutions for external calibration. Beverage samples could then be measured directly using the external calibration.

Polyoxometalate-Engineered Building Blocks with Gold Cores for the Self-Assembly of Responsive Water-Soluble Nanostructures.

The controlled assembly of gold nanoparticles (AuNPs) with the size of quantum dots into predictable structures is extremely challenging as it requires the quantitatively and topologically precise placement of anisotropic domains on their small, approximately spherical surfaces. We herein address this problem by using polyoxometalate leaving groups to transform 2 nm diameter gold cores into reactive building blocks with hydrophilic and hydrophobic surface domains whose relative sizes can be precisely tuned to give dimers, clusters, and larger micelle-like organizations. Using cryo-TEM imaging and H DOSY NMR spectroscopy, we then provide an unprecedented "solution-state" picture of how the micelle-like structures respond to hydrophobic guests by encapsulating them within 250 nm diameter vesicles whose walls are comprised of amphiphilic AuNP membranes.

Microplasma-based flowing atmospheric-pressure afterglow (FAPA) source for ambient desorption-ionization mass spectrometry.

A new direct-current microplasma-based flowing atmospheric pressure afterglow (FAPA) source was developed for use in ambient desorption-ionization mass spectrometry. The annular-shaped microplasma is formed in helium between two concentric stainless-steel capillaries that are separated by an alumina tube. Current-voltage characterization of the source shows that this version of the FAPA operates in the normal glow-discharge regime.

Host-guest chemistry with water-soluble gold nanoparticle supraspheres.

The uptake of molecular guests, a hallmark of the supramolecular chemistry of cages and containers, has yet to be documented for soluble assemblies of metal nanoparticles. Here we demonstrate that gold nanoparticle-based supraspheres serve as a host for the hydrophobic uptake, transport and subsequent release of over two million organic guests, exceeding by five orders of magnitude the capacities of individual supramolecular cages or containers and rivalling those of zeolites and metal-organic frameworks on a mass-per-volume basis. The supraspheres are prepared in water by adding hexanethiol to polyoxometalate-protected 4 nm gold nanoparticles.

Use of Interrupted Helium Flow in the Analysis of Vapor Samples with Flowing Atmospheric-Pressure Afterglow-Mass Spectrometry.

The flowing atmospheric-pressure afterglow (FAPA) source was used for the mass-spectrometric analysis of vapor samples introduced between the source and mass spectrometer inlet. Through interrupted operation of the plasma-supporting helium flow, helium consumption is greatly reduced and dynamic gas behavior occurs that was characterized by schlieren imaging. Moreover, mass spectra acquired immediately after the onset of helium flow exhibit a signal spike before declining and ultimately reaching a steady level.

Polyoxometalate complexes of anatase-titanium dioxide cores in water.

Polyoxometalate (POM) cluster anions are shown to serve as covalently coordinated ligands for anatase-TiO2 nanocrystals, giving isolable assemblies uniquely positioned between molecular macroanions and traditional colloidal nanoparticles. Na(+) salts of the water-soluble polyanionic structures are obtained by reacting amorphous TiO2 with the 1 nm lacunary ion, Na7 [α-XW11 O39 ] (X=P(5+) ), at 170 °C, after which an average of 55 α-PW11 O39 (7-) clusters are found as pentadentate ligands for Ti(IV) ions covalently linked to 6 nm single-crystal anatase cores. The attached POMs are reversible electron acceptors, the reduction potentials of which shift in a predictable fashion by changing the central heteroatom, X, directly influencing a model catalytic reaction.

Regioselective placement of alkanethiolate domains on tetrahedral and octahedral gold nanocrystals.

Electrostatically stabilized monolayer shells of metal-oxide cluster anions (polyoxometalates, or POMs) on the surfaces of ca. 8 nm tetrahedral and octahedral gold nanocrystals regioselectively direct water-soluble alkanethiolate ligands to the corners and edges of the gold polyhedra.

Role of the alkali-metal cation size in the self-assembly of polyoxometalate-monolayer shells on gold nanoparticles.

Polyoxometalate (POM)-monolayer stability constants, K, for three POM anions vary with the cation size, in the same order as that for increasing ion-pair formation with α-SiW(11)O(39)(8-) (1) in the early nucleation phase of monolayer self-assembly: Li(+) < Na(+) < K(+) < Cs(+). Cryo-TEM images demonstrating the use of the cation size to rationally control monolayer formation provide definitive evidence that the POM monolayers are electrostatically stabilized (ionic) shells, analogous in that respect to the monolayer walls of "hollow" POM-macroanion vesicles.

Orientations of polyoxometalate anions on gold nanoparticles.

Cryogenic transmission electron microscopy of polyoxometalate-protected gold nanoparticles reveals that the Preyssler ion, [NaP(5)W(30)O(110)](14-), lies "face down" with its C(5) axis perpendicular to the gold surface, while the Finke-Droege ion, [P(4)W(30)Zn(4)(H(2)O)(2)O(112)](16-), is "tilted", with its long axis close to 60° from the normal to the surface.

Nucleation and island growth of alkanethiolate ligand domains on gold nanoparticles.

The metal oxide cluster α-AlW(11)O(39)(9-) (1), readily imaged by cryogenic transmission electron microscopy (cryo-TEM), is used as a diagnostic protecting anion to investigate the self-assembly of alkanethiolate monolayers on electrostatically stabilized gold nanoparticles in water. Monolayers of 1 on 13.8 ± 0.