Suzuki-Miyaura coupling on heterogeneous palladium catalysts

Summary Five supported heterogeneous Pd catalysts have been prepared, characterized and found to be active and selective in the Suzuki-Miyaura coupling of boronic acids, and aromatic iodo and bromo compounds to form the corresponding biaryls in high selectivities. Reaction conditions, namely, the solvent, base (triethylamine, Na₂CO₃, Cs₂CO₃) and tetrabutylammonium chloride as an additive are shown to have profound effects on catalyst performance.</o:p>     

Reactor neutron activation analysis followed by characteristic X-ray spectrometry

The possibility of applications of characteristic X-rays from radioactive products of reactor neutron activation was investigated with particular emphasis on (n, ), n, n), (n, 2n), (n, p) and (n, ) products with long half-lives. The sensitivity and detection limits of silver, cerium, gadolinium, selenium, cadmium and europium have been investigated. The elements were studied both in a pure and in a matrix form, in both cases the samples were diluted with graphite (90%) to minimize matrix effects (absorption and enhancement).     

Analysis of bioactive eicosanoids in equine plasma by stable isotope dilution reversed-phase liquid chromatography/multiple reaction monitoring mass spectrometry

Oxidative metabolites of arachidonic acid (AA) are implicated in inflammation. Thus, we evaluated cycloxygenases (COXs) and lipoxygenases (LOs) mediated metabolism of AA to eicosanoids in equine plasma. Eicosanoids were extracted from plasma by two liquid-liquid extraction (LLE) steps; first was by chloroform/isopropanol and second by methyl-tert-butyl ether. For identification and quantification of 25 eicosanoids, a highly specific, selective and sensitive stable isotope dilution liquid chromatography (LC) multiple reaction monitoring (MRM) mass spectrometric (MS) method was developed. To avoid artifact formation of eicosanoids, deferoxamine was added to plasma to chelate residual transition metal ions. The calibration curve showed excellent linearity within 0.1 to 10 ng/mL. Slopes of the calibration curves generated by adding known quantities of eicosanoids in plasma were higher than those prepared in methanol/mobile phase A. Addition of deferoxamine decreased the slope of calibration curves generated using plasma. Limit of detection (LOD) was 1-10 pg on-column for 25 different eicosanoids. Inter-day accuracy was 86-111%, whereas intra-day accuracy was from 88-110%, and precision did not exceed 15% for all quality control (QC) samples. To evaluate the formation of eicosanoids, AA was exogenously added or endogenous AA was released from esterified lipids by calcium ionophore (CI) A23187 treatment of equine whole blood. Pre-treatment of equine whole blood with dexamethasone (DEX) significantly inhibited AA or CI A23187- mediated formation of eicosanoids. The validated method is now employed in studies undertaken to better understand the mechanism of action and pharmacokinetics/pharmacodynamics of eicosanoids after administration of glucocorticoids to horses. This method is reliably reproducible.     

Effect of patterns and inhomogeneities on the surface of waveguides used for optical waveguide lightmode spectroscopy applications

It has been found that patterns and inhomogeneities on the surface of the waveguide used for optical waveguide lightmode spectroscopy applications can produce broadening and fine structure in the incoupled light peak spectra. During cell spreading on the waveguide, a broadening of the incoupling peaks is observed, while regular microstructures on the incoupling grating produce shifts and splitting of the peaks. A theoretical model, based on the zigzag wave representation of light propagation in a planar optical waveguide has been developed in order to understand the physical background of the observed effects. Numerical results are given for the different cases observed, and they are compared with the experimental data. Several possible applications of these effects are considered. Received: 10 July 2000 / Revised version: 9 October 2000 / Published online: 21 February 2001     

pH induced interaction of DPPC with a fluorescent dye in Langmuir and Langmuir Blodgett (LB) films

This communication reports the investigation of the pH effects on the interaction of a well-known lung surfactant, Dipalmitoylphosphatidylcholine (DPPC) with water soluble highly fluorescent dye Rhodamine B (RhB) in complex Langmuir monolayers at the air–water interface. The ionic nature of DPPC changes with the pH of the subphase in the Langmuir trough. At sufficiently low pH it becomes cationic whereas at higher pH it can be presented with a negative net charge and at normal pH it is zwitterionic. Being zwitterionic, RhB molecules can interact with DPPC at normal and higher pH, whereas at lower pH the interaction becomes less probable. This has been investigated in details at the air–water interface in Langmuir trough as well as in Langmuir Blodgett (LB) film by employing surface pressure versus area per molecule (π–A) isotherms, compressibility study, in-situ Fluorescence Imaging Microscopy (FIM), UV-vis absorption spectroscopy and Atomic Force Microscopy (AFM) study.     

Activation and isomerization of n-butane on sulfated zirconia model systems--an integrated study across the materials and pressure gaps

Butane activation has been studied using three types of sulfated zirconia materials, single crystalline epitaxial films, nanocrystalline films, and powders. A surface phase diagram of zirconia in interaction with SO(3) and water was established by DFT calculations, which was verified by LEED investigations on single-crystalline films and by IR spectroscopy on powders. At high sulfate surface densities a pyrosulfate species is the prevailing structure in the dehydrated state; if such species are absent, the materials are inactive. Theory and experiment show that the pyrosulfate can react with butane to give butene, H(2)O and SO(2), hence butane can be activated via oxidative dehydrogenation. This reaction occurred on all investigated materials; however, isomerization could only be proven for powders. Transient and equilibrium adsorption measurements in a wide pressure and temperature range (isobars measured via UPS on nanocrystalline films, microcalorimetry and temporal analysis of products measurements on powders) show weak and reversible interaction of butane with a majority of sites but reactive interaction with <5 micromol g(-1) sites. Consistently, the catalysts could be poisoned by adding sodium to the surface in a ratio S/Na = 35. Future research will have to clarify what distinguishes these few sites.     

Dehydrogenation of dodecahydro-N-ethylcarbazole on Pd/Al2O3 model catalysts

To elucidate the dehydrogenation mechanism of dodecahydro-N-ethylcarbazole (H(12)-NEC) on supported Pd catalysts, we have performed a model study under ultra high vacuum (UHV) conditions. H(12)-NEC and its final dehydrogenation product, N-ethylcarbazole (NEC), were deposited by physical vapor deposition (PVD) at temperatures between 120 K and 520 K onto a supported model catalyst, which consisted of Pd nanoparticles grown on a well-ordered alumina film on NiAl(110). Adsorption and thermally induced surface reactions were followed by infrared reflection absorption spectroscopy (IRAS) and high-resolution X-ray photoelectron spectroscopy (HR-XPS) in combination with density functional theory (DFT) calculations. It was shown that, at 120 K, H(12)-NEC adsorbs molecularly both on the Al(2)O(3)/NiAl(110) support and on the Pd particles. Initial activation of the molecule occurs through C-H bond scission at the 8a- and 9a-positions of the carbazole skeleton at temperatures above 170 K. Dehydrogenation successively proceeds with increasing temperature. Around 350 K, breakage of one C-N bond occurs accompanied by further dehydrogenation of the carbon skeleton. The decomposition intermediates reside on the surface up to 500 K. At higher temperatures, further decay to small fragments and atomic species is observed. These species block most of the absorption sites on the Pd particles, but can be oxidatively removed by heating in oxygen at 600 K, fully restoring the original adsorption properties of the model catalyst.     

The adsorption of Xe and CO on Ag(111)

The adsorption of Xe and CO on Ag(111) in the range 66 to 123 K and 10^?7 to 10^?1 Pa has been studied by surface potential, low energy electron diffraction (LEED), Auger electron spectroscopy (AES) and electron energy loss spectroscopic (EELS) measurements. Isotherms derived from both surface potential and AES measurements for submonolayer Xe adsorption reveal successive stages and a two-dimensional phase change. Isosteric heats were 18 ± 1 kJ mol^?1. Temkin isotherms were observed for CO, the heat falling linearly with coverage from an initial value of 27 ± 1.5 kj mol^?1. No ordered CO overlayer structure could be detected. EEL spectra of clean Ag(111) agree with previous studies. Additional loss peaks were recorded for Xe and CO overlayers, and the assignment of the substrate loss features is discussed in relation to the effects of adsorption.