Backbonding in Thorium(IV) and Uranium(IV) Diarsenido Complexes with tBuNC and CO

The coordination of tBuNC and CO with the diarsenido complexes (C₅Me₅)₂An(η²-As₂Mes₂), An=Th, U, has been investigated. For the first time, a comparison between isostructural complexes of Th^IV and U^IV has been possible with CO; density functional calculations indicated an appreciable amount of π backbonding that originates from charge transfer from an actinide-arsenic sigma bond. The calculated CO stretching frequencies in the Th^IV and U^IV diarsenido complexes are consistent with the experimental measurements, both show large shifts to lower frequency. We demonstrate that the π backbonding is crucial to explaining the red shifts of CO frequency upon An^IV complex formation. Interestingly, this interaction essentially correlates to the parallel orientation of π*(C−O) orbitals relative to the An−As bond.     

Cycloaddition mit ungesättigten Zuckern,VI Die Synthese Diastereomerer 4H-Pyrano [3, 4-d] Isoxazol-4-One

Abstract

By 1, 3-dipolar cycloaddition of benzonitrile oxide to 4, 6-di-O-acetyl-2, 3-dideoxy-D-erythro-hex-2-enono-1, 5-lactone (1), [3aR- (3aα, 6β,7α, 7aα)] - (2) and [3aS-(3aβ, 6β, 7α, 7aα)] -7- (acetyloxy) -6- (acetyloxymethyl) -3a, 6, 7, 7a-tetrahydro-3-phenyl-4H-pyrano [3, 4-d] isoxazole-4-one (3) were prepared in 58 and 7% yield respectively. From 2, [1′ R, 3aR-(3aα, 6β, 6aα)] -6-(1′, 2′-dihydroxymethyl)-6, 6a - dihydro-3-phenyl-furano [3, 4-d] isoxazole-4 (3aH) -one (5) was prepared by deacetylation. The structure of 3 was determined by X-ray analysis.     

Mass spectrometric analysis of ceramic components for solid oxide fuel cells

For the determination of trace impurities in ceramic components of solid oxide fuel cells (SOFCs), some mass spectrometric methods have been applied such as spark source mass spectrometry (SSMS), laser ionization mass spectrometry (LIMS), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and inductively coupled plasma mass spectrometry (ICP-MS). Due to a lack of suitable standard reference materials for quantifying of analytical results on La _x Sr _y MnO₃ cathode material a matrix-matched synthetic standard-high purity initial compounds doped with trace elements-was prepared in order to determine the relative sensitivity coefficients in SSMS and LA-ICP-MS. Radiofrequency glow discharge mass spectrometry (rf-GDMS) was developed for trace analysis and depth profiling of thick non-conducting layers. Surface analytical techniques, such as secondary ion mass spectrometry (SIMS) and sputtered neutral mass spectrometry (SNMS), were used to determine the element distribution on surfaces (homogeneity) and the surface contaminants of SOFC ceramic layers.Dedicated to Professor Dr. rer. nat. Hubertus Nickel on the occasion of his 65th birthday     

Regioselective Oxidative Ring Opening of Cyclopropyl Silyl Ethers: A Quantum Chemical Study

In contrast to the structurally and configurationally stable alkyl‐ or aryl‐substituted cyclopropyl radical cations, cyclopropyl silyl ethers undergo spontaneous ring opening upon oxidation whereby the endocyclic C? C(O‐TMS) bond is cleaved with remarkable selectivity. DFT calculations on 1‐trimethylsilyloxybicyclo[4.1.0]heptane show that this selectivity arises from the topology of the potential surface of the corresponding radical cation which is initially generated in a very steep region of the potential surface from where the steepest descent leads to cleavage of the endocyclic rather than the lateral C? C(OTMS) bond. Cleavage of the lateral bond leads to interesting conformational changes which are explored in detail.     

Bayesian‐type count data models with varying coefficients: estimation and testing in the presence of overdispersion

In this paper we study varying‐coefficient models for count data. A Bayesian approach is taken to model the variability of the regression parameters. Based on a Kalman filter procedure the varying coefficients are estimated as the mode of the posterior distribution. All hyperparameters, including an overdispersion parameter in the negative binomial varying‐coefficient model (NBVC), are estimated as ML‐estimators using an EM‐type algorithm. A bootstrapping test of the fixed‐coefficient hypothesis against a varying‐coefficient alternative is proposed, which is evaluated running a simulation study. The study shows that the choice of a suitable count data model is of special importance in the framework of varying‐coefficient models. The methodology is illustrated analysing the determinants of the number of individual doctor visits. Copyright © 2001 John Wiley & Sons, Ltd.     

Tuning the excitonic and plasmonic properties of copper chalcogenide nanocrystals

The optical properties of stoichiometric copper chalcogenide nanocrystals (NCs) are characterized by strong interband transitions in the blue part of the spectral range and a weaker absorption onset up to ~1000 nm, with negligible absorption in the near-infrared (NIR). Oxygen exposure leads to a gradual transformation of stoichiometric copper chalcogenide NCs (namely, Cu(2-x)S and Cu(2-x)Se, x = 0) into their nonstoichiometric counterparts (Cu(2-x)S and Cu(2-x)Se, x > 0), entailing the appearance and evolution of an intense localized surface plasmon (LSP) band in the NIR. We also show that well-defined copper telluride NCs (Cu(2-x)Te, x > 0) display a NIR LSP, in analogy to nonstoichiometric copper sulfide and selenide NCs. The LSP band in copper chalcogenide NCs can be tuned by actively controlling their degree of copper deficiency via oxidation and reduction experiments. We show that this controlled LSP tuning affects the excitonic transitions in the NCs, resulting in photoluminescence (PL) quenching upon oxidation and PL recovery upon subsequent reduction. Time-resolved PL spectroscopy reveals a decrease in exciton lifetime correlated to the PL quenching upon LSP evolution. Finally, we report on the dynamics of LSPs in nonstoichiometric copper chalcogenide NCs. Through pump-probe experiments, we determined the time constants for carrier-phonon scattering involved in LSP cooling. Our results demonstrate that copper chalcogenide NCs offer the unique property of holding excitons and highly tunable LSPs on demand, and hence they are envisaged as a unique platform for the evaluation of exciton/LSP interactions.