Anthill Earth as a Gold Occurrence Indicator,and Gold Determination by Solid Sampling Flame Atomic Absorption Spectrometry

With the aim of avoiding cumbersome sample treatment, we present a device for the introduction of solid soil samples into AAS-flames for gold determination, as well as the proposition of earth from anthills as a gold occurrence indicator. A previous ground sample of anthill earth (0.50 mg) was weighed directly into a small recipient of polyethylene which was then connected to a sampling boronsilicate glass chamber. The sample was carried by an airflow (5 L min⁻¹) to a quartz cell positioned between the burner top and the optical beam. The generated atomic vapor produced a transient signal which was totally integrated in three seconds. The performance was compared with conventional flame atomic absorption spectrometry after proper sample digestion. No significant differences were observed between both procedures (mean deviation ±1.90%), and a LOQ of 0.03 μg Au was achieved using the proposed method. The anthill earth was found to be very suitable for indication of gold occurrence in soils and related materials.     

Amperometric Biosensor for Hydrogen Peroxide Based on Electrodeposited Sub-micrometer Gold Modified Glassy Carbon Electrode

IntroductionAmperometricbiosensorofhydrogenperoxideisofpracticalimportancebecauseofitswideapplicationsinchemical,biological,clinical,environmentalandmanyotherfields.Forimprovementofsensor抯quality,vari-ouskindsofchemicalmodificationmethodshavebeendevelopedforreducingredoxoverpotentialsofH2O2atelectrodesurfaces,increasingthedetectionsensitivity,linearrange,stabilityandlivetime.Ithasbeenshownthattheuseofsub-micrometersizedmetalparticlessuchasPt-blackcansignificantlyimprovethequalityofthebiosens…     

Synthesis, Chemical Characterization, and Molecular Structure of Au8{Fe(CO)4}4(dppe)2 and Au6Cu2{Fe(CO)4}4(dppe)2

The new Au₈{Fe(CO)₄}₄(P^P)₂ and Au₆Cu₂{Fe(CO)₄}₄(P^P)₂ (P^P=dppm, dppe) neutral cluster compounds were isolated in good yields by condensation of the [Au₃{Fe(CO)₄}₂(P^P)]^- anions with Au(SEt₂)Cl and CuCl, respectively, and have been characterized by IR, NMR and microanalyses. The molecular structures of Au₈{Fe(CO)₄}₄(dppe)₂ and Au₆Cu₂{Fe(CO)₄}₄(dppe)₂ have been determined by X-ray diffraction studies. Both molecules adopt a stereogeometry of the heavy atoms consisting of a triangulated and corrugated ribbon twisted around the elongation direction. Contrary to the expectations the latter displays the two copper atoms in the sites of highest connectivity. This implies that site exchange between copper and gold occurs during the synthesis.     

On the Structure and Formation of Self-Assembled Lattices of Gold Nanoparticles

The structure and ordering of nanoparticles of gold functionalized with n-alkyl thiol molecules are studied both experimentally and theoretically. Samples where produced using n=6 to n=16 alkyl thiol molecules. High Resolution Electron Microscopy coupled with image processing was used to study the gold particle structure. The details of the particle structure are discussed. We found that when the gold surface is saturated with thiol molecules there is some tendency to produce molecules with a disulphide structure. We also show that ordered arrays of particles can be produced using Langmuir-Blodgett techniques. The crystal structure of the films produced is studied and found to be 3D hcp. We also report that thiol covered gold particles with a size of 5 nm present a rounded shape suggesting that thiol molecules might induce an isotropic surface energy. It is found in the theoretical calculations that a strong bond between gold and sulphur is required to stabilize the complex metal-n-alkyl thiol. It is predicted that otherwise a heavily distorted nanocore will be formed. This is contrary to the observed structure of the particles.     

Seed‐Mediated Synthesis of Gold Tetrahedra in High Purity and with Tunable,Well‐Controlled Sizes

We report a facile synthesis of Au tetrahedra in high purity and with tunable, well‐controlled sizes via seed‐mediated growth. The success of this synthesis relies on the use of single‐crystal, spherical Au nanocrystals as the seeds and manipulation of the reaction kinetics to induce an unsymmetrical growth pattern for the seeds. In particular, the dropwise addition of a precursor solution with a syringe pump, assisted by cetyltrimethylammonium chloride and bromide at appropriate concentrations, was found to be critical to the formation of Au tetrahedra in high purity. Their sizes could be readily tuned in the range of 30–60 nm by simply varying the amount of precursor added to the reaction solution. The current strategy not only enables the synthesis of Au tetrahedra with tunable and controlled sizes but also provides a facile and versatile approach to reducing the symmetry of nanocrystals made of a face‐centered cubic lattice.     

Bimetallic Gold(I) Complexes with Ethynyl‐Helicene and Bis‐Phosphole Ligands: Understanding the Role of Aurophilic Interactions in their Chiroptical Properties

Monometallic gold(I)‐alkynyl‐helicene complexes ( 1 a , b ) and bimetallic gold(I)‐alkynyl‐helicene architectures featuring the presence ( 2 a , b ) or absence ( 3 a , b ) of aurophilic intramolecular interactions were prepared by using different types of phosphole ligands (mono‐phosphole L1 or bis‐phospholes L2 , 3 ). The influence of the Au^I d¹⁰ metal center(s) on the electronic, photophysical, and chiroptical properties of these unprecedented phosphole‐gold(I)‐alkynyl‐helicene complexes was examined. Experimental and theoretical results highlight the importance of ligand‐to‐ligand‐type charge transfers and the strong effect of the presence or absence of Au^I–Au^I interactions in 2 a , b .     

Low‐energy ion scattering: Determining overlayer thickness for functionalized gold nanoparticles

With the widespread use of engineered nanoparticles for biomedical applications, detailed surface characterization is essential for ensuring reproducibility and the quality/suitability of the surface chemistry to the task at hand. One important surface property to be quantified is the overlayer thickness of self‐assembled monolayer (SAM) functionalized nanoparticles, as this information provides insight into SAM ordering and assembly. We demonstrate the application of high sensitivity low‐energy ion scattering (HS‐LEIS) as a new analytical method for the fast thickness characterization of SAM functionalized gold nanoparticles (AuNPs). HS‐LEIS demonstrates that a complete SAM is formed on 16‐mercaptohexadecanoic acid (C16COOH) functionalized 14 nm AuNPs. HS‐LEIS also experimentally provides SAM thickness values that are in good agreement with previously reported results from simulated electron spectra for surface analysis of X‐ray photoelectron spectroscopy data. These results indicate HS‐LEIS is a valuable surface analytical method for the characterization of SAM functionalized nanomaterials. Copyright © 2013 John Wiley & Sons, Ltd.     

Formal (4+1) Cycloaddition of Methylenecyclopropanes with 7‐Aryl‐1,3,5‐cycloheptatrienes by Triple Gold(I) Catalysis

7‐Aryl‐1,3,5‐cycloheptatrienes react intermolecularly with methylenecyclopropanes in a triple gold(I)‐catalyzed reaction to form cyclopentenes. The same formal (4+1) cycloaddition occurs with cyclobutenes. Other precursors of gold(I) carbenes can also be used as the C₁ component of the cycloaddition.     

Electrochemical Detection of Thioether‐Based Fluorosurfactants in Aqueous Film‐Forming Foam (AFFF)

Using cyclic voltammetry (CV) and impedance (IMP), we report a simple approach to detect new fluorosurfactant ingredient formulated in aqueous film‐forming foam (AFFF), specifically the thioether‐based one. First, we employ ion chromatography (IC) to identify all possible elements with the help of chemical oxidation and infrared spectrum (IR) to identify all possible functional groups. We thus propose a possible thioether‐based molecular structure of fluorosurfactant formulated in AFFF. By studying the self‐assembled monolayer (SAM) formed on gold (Au) surface via thio‐Au bond, we establish a relationship between the SAM density and the amount of the thioether‐based fluorosurfactant for the AFFF detection. Solid phase extraction (SPE) and nanoporous Au electrode are employed to enhance the sensitivity. Consequently, a detection limit of 10 ppb (v/v) has been achieved for AFFF‐spiked tap water sample.