Energetic ion bombardment of Ag surfaces by C<Stack><Subscript>60</Subscript><Superscript>+</Superscript></Stack> and Ga<Superscript>+</Superscript> projectiles

The ion bombardment-induced release of particles from a metal surface is investigated using energetic fullerene cluster ions as projectiles. The total sputter yield as well as partial yields of neutral and charged monomers and clusters leaving the surface are measured and compared with corresponding data obtained with atomic projectile ions of similar impact kinetic energy. It is found that all yields are enhanced by about one order of magnitude under bombardment with the C60+ cluster projectiles compared with Ga+ ions. In contrast, the electronic excitation processes determining the secondary ion formation probability are unaffected. The kinetic energy spectra of sputtered particles exhibit characteristic differences which reflect the largely different nature of the sputtering process for both types of projectiles. In particular, it is found that under C60+ impact (1) the energy spectrum of sputtered atoms peaks at significantly lower kinetic energies than for Ga+ bombardment and (2) the velocity spectra of monomers and dimers are virtually identical, a finding which is in pronounced contrast to all published data obtained for atomic projectiles. The experimental findings are in reasonable agreement with recent molecular dynamics simulations.     

Investigation of 2-[(<Emphasis Type="Italic">E</Emphasis>)-2-(4-diethylaminophenyl)-1-ethenyl]-1,3,3-trimethyl-3H-indolium as a new highly sensitive reagent for the spectrophotometric determination of nitrophenols

A new, simple, rapid, and sensitive spectrophotometric method has been developed for the determination of nitrophenols [picric acid (PA); dinitrophenols (DNP)] in wastewater samples. The method is based on the reaction of nitrophenols with 2-[(E)-2-(4-diethylaminophenyl)-1-ethenyl]-1,3,3-trimethyl-3 H-indolium chloride reagent to form the colored ion associates, which are extracted by organic solvents. The molar absorptivity of the ion associates of PA with the investigated reagent ranges from 8.3×10⁴ to 11.3×10⁴ L mol^–1 cm^–1, depending on the extractant. Because only PA is extracted in an acidic medium with the investigated reagent, but both PA and DNP are extracted in an alkaline medium, it is possible to determine both substances in a mixture. Appropriate reaction conditions have been established. The absorbance of the colored extracts obeys Beers law in the range of 0.04–4.58 mg L^–1 PA, 1.0–18.4 mg L^–1 2,4-DNP and 1.2–14.7 mg L^–1 2,6-DNP, respectively. The limit of detections, calculated from a blank test (n=10; P=0.95), are 0.05 mg L^–1 PA, 0.9 mg L^–1 (2,4-DNP), and 1.1 mg L^–1 (2,6-DNP), respectively.     

Application of stir bar sorptive extraction for wine analysis

Stir bar sorptive extraction (SBSE) coupled with gas chromatography/mass spectrometry (GC/MS) was used to analyse wine samples for three applications: flavour and compositional analysis; 2,4,6-trichloroanisole (TCA), a common off-aroma in wine; and agrochemicals. SBSE was found to be orders of magnitude more sensitive than modern conventional methodology, allowing for lower detection and quantitation levels, and improved confirmation of identity; SBSE often gave better signal to noise in scan mode than other methods in selective ion monitoring (SIM) mode. With the help of their characteristic mass spectra all agrochemicals could be identified unambiguously at concentrations of 10 microg L(-1) in wine and a further 100 constituents were detected in a Cabernet Sauvignon sample. Thus it is now possible to analyse complex samples such as wine by scan mode, with better confirmation of identity, and without sacrificing sensitivity, where previously SIM methodology had to be used.     

Determination of selenoamino acids by gas chromatography-mass spectrometry

The application of the recently introduced ethylchloroformate derivatization method for the separation and determination of selenomethionine and selenocystein in selenium-enriched yeast and yeast-free tablets by means of a gas chromatography-mass spectrometry (GC-MS) system has been studied. The efficiency of three methods for the extraction of selenomethionine from the tablets were compared. Total selenium content of the same tablets were measured using inductively coupled plasma (ICP)-MS and it was found that in the selenized yeast tablets about 80% of the total selenium is present as selenomethionine. The results were in agreement with the values in the labels and with the literature. The accuracy of the total selenium analysis was controlled by the analysis of a reference material.     

Underpotential deposition of tin(II) on a gold disc electrode and determination of tin in a tin plate sample

This work describes a study of the underpotential deposition (UPD) of Sn²⁺ on a polycrystalline gold disc electrode using cyclic voltammetry (CV) and chronocoulometry (CC). Sn²⁺ ions showed well-defined peaks from UPD and UPD stripping (UPD-S) in 1 mol/L HCl solutions, while bulk deposition (BD) and BD stripping (BD-S) of the ions were also observed. The measured UPD shifts, E_UPD, between the UPD-S and the BD-S peaks were more than 200 mV. The UPD charge and the surface coverage of tin were measured by CC. A new method for determining Sn²⁺ was therefore developed, based on the excellent electrochemical properties of the Au/Sn UPD system. A plot of the UPD-DPASV (differential pulse anodic stripping voltammetry) signal versus the Sn(II) concentration was obtained for [Sn(II)] of 1.98×10^–7 to 3.64×10^–5 M. The method developed here has been applied to determine the tin in a tin plate sample.     

Preparation of Tin Oxide-Based Metal Oxide Particles

Tin oxide-doped hybrid particles were prepared by a wet chemical process with organic-inorganic (phenyl/silica) hybrid particles in an alcoholic solution. The phenyl/silica hybrid particles, with a diameter of ca. 790 nm were used as a new support material for tin oxide (SnO₂) particles from tin(IV) chloride. The surface of the particles was modified via nitration of aromatic groups in the particles, to promote formation of the tin oxide coating on the particles. The thickness and surface morphology of the tin oxide layer coated on the nitrated-phenyl/silica hybrid particles could be controlled by varying the tin(IV) chloride concentration and reaction time. The size and morphology of the resultant particles were investigated with field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). The particles obtained were also characterised by infrared (FTIR) and solid-state ¹³C magic angle spinning nuclear magnetic resonance (¹³C-CP/MAS NMR) spectroscopy. The effect of processing parameters on the crystallinity and structure of the doped hybrids were confirmed by X-ray diffraction (XRD) patterns.     

Some trends in the development of microplasmas for spectrochemical analysis

The development of microplasmas for spectrochemical analysis by optical methods is discussed. Recent achievements in miniaturization are highlighted, especially for three types of plasmas, namely high-frequency plasmas, dc-discharges and microwave plasmas. The potentials of each of these groups of plasmas as sources for atomic emission spectrometry are discussed. Literature citations and experiments indicate that the plasmas are also very useful as atom reservoirs for atomic absorption spectrometry. Methods of sampling, including feeding with gas chromatography effluents, the use of electrothermal vaporization, and the evolution of gaseous species (as shown for the case of Hg vapor), are discussed as prominent interfaces to make use of these sources for elemental analysis.     

Molecular beams and model catalysis: activity and selectivity of specific reaction centers on supported nanoparticles.

Reaction kinetics on nanometer-scale particles are different from those on extended surfaces of bulk materials. This fact has been utilized for a long time to empirically maximize the performance of heterogeneous catalysts, but the understanding of the underlying effects is poor at the microscopic level. Modern molecular beam-based methods, however, allow us to derive very detailed kinetic information on catalytically active surfaces. In combination with structurally highly controlled model catalysts, microscopic insights into the activity and selectivity of specific reaction centers on catalyst nanoparticles can be obtained. This combined approach is illustrated through simple model reactions.     

Efficient synthesis of enynecarbamates and their ring-closing metathesis/[4 + 2] Diels-Alder cycloaddition: synthesis of hexahydroisoquinolines

Enynes 5a-g were prepared in moderate to good yields from 1-(triphenylphosphoranylideneaminoalkyl)benzotriazoles. Ring-closing metathesis of 5a-f afforded functionalized dienes 6a-f, respectively, which were used in a Diels-Alder cycloaddition reaction in the synthesis of the corresponding hexahydroisoquinoline derivatives 7a-f.