Ozonolysis of a Series of Methylated Alkenes: Reaction Rate Coefficients and Gas‐Phase Products

The gas‐phase ozonolysis of three methylated alkenes, i.e., trans‐2,2‐dimethyl‐3‐hexene (22dM3H), trans‐2,5‐dimethyl‐3‐hexene (25dM3H), and 4‐methyl‐1‐pentene (4M1P), has been investigated in the presence of sufficient hydroxyl radical scavenger in a laminar flow reactor at ambient temperature (296 ± 2 K) and P = 1 atm of dry air (RH ≤ 5%). Ozone levels in the reactor were monitored by an automatic analyzer. Alkene and gas‐phase product concentrations were determined via online sampling either on three‐bed adsorbent cartridges followed by thermodesorption and GC/FID‐MS analysis or on 2,4‐dinitrophenylhydrazine (DNPH) cartridges for subsequent HPLC/UV analysis. Reaction rate coefficients of (3.38 ± 0.12) × 10^?17 for 22dM3H and (2.71 ± 0.26) × 10^?17 for 25dM3H, both in cm³ molecule^?1 s^?1 units, have been obtained under pseudo–first‐order conditions. Primary carbonyl products have been identified for the three investigated alkenes, and branching ratios are reported. In the case of 4M1P ozonolysis, the yield of a Criegee intermediate was indirectly determined. Kinetics and product study results are compared to those of literature when available. This work represents the first investigation of reaction products in the ozonolysis of 22dM3H, 25dM3H, and 4M1P in a flow reactor.     

Extrusion of pastes with a piston extruder for the determination of the local solid and fluid concentration, the local porosity and saturation and displacement profiles by means of NMR imaging

 Nuclear Magnetic Resonance (NMR) was used to investigate the extrusion behaviour of PTFE pastes in a ram extruder. By means of ¹H-NMR imaging (MRI) it is possible to determine the local proton density and therefore, the local fluid concentration. The ¹⁹F-MRI provides the local solid concentration. Thus the local saturation and the local porosity can be calculated with the information of the local fluid and solid concentration. Furthermore displacement profiles can be derived from NMR images by means of correlation techniques without any preparation or marking of the pastes. Received: 8 May 2000   Accepted: 1 May 2001     

Measurement of the Seperation between Atoms beyond Diffraction Limit

We propose a scheme to obtain the distance of two identical atoms placed inside the standing wave field by monitoring the collective resonance fluorescence spectrum emitted by the two particles. We find three different parameter ranges, depending on the distance of the atoms as compared to the transition wavelength. For large interparticle distances, dipole-dipole coupling is negligible, and the main system evolution arises from the interaction with the standing wave field. In the small-distance limit, the dynamics is dominated by the dipole-dipole interaction. Finally, in the intermediate region, a rich interplay of the various couplings arises, which however is lifted for strong driving laser fields. The present measurement procedure allows us to distinguish the three cases. In each of the cases, we show how to determine the distance of the two particles and their respective positions relative to the nodes of the standing wave field with fractional-wavelength precision.     

Palladium complexes of a chiral P,C-chelating phosphino-(sulfinylmethyl)phosphonium ylide ligand

A new type of phosphino-phosphonium ylide ligand bearing a chiral sulfinyl center affords a P,C-chelated palladium(II) complex with a resolved asymmetric ylidic carbon atom. According to ³¹P NMR analysis of the crude material, the diastereoselectivity of the complexation at room temperature is ca. 7:1. In the crystal state, an X-ray diffraction analysis of one epimer reveals a quasi C₂-symmetric chloro-bridged dinuclear structure, where the (S) configuration of the sulfur atom induces a (S) configuration of the ylidic carbon atom. A in situ Pd(0) catalyst generated from the phosphino-ylide and Pd(PPh₃)₄ promotes allylic substitution of 3-acetoxy-1,3-diphenylpropene by sodium malonate in 70% yield and 5% e.e.     

Unions and Intersections of Families of Lp-Spaces

Let L^Ψ and E^Ψ be the ORLICZ space and the space of finite elements respectively, on a measure space (Ω, Σ, μ), and let T ? (0, ∞). It is proved that if inf {p: p ? T} ? T or sup {p: p ? T} ? T and μ is an infinite atomless measure, then there is no ORLICZ function Ψ such that: \documentclass{article}\pagestyle{empty}\begin{document}$ L^\varphi = Lin\mathop { \cup L^p }\limits_{p\varepsilon T} $\end{document} or \documentclass{article}\pagestyle{empty}\begin{document}$ E^\varphi = Lin\mathop { \cup L^p }\limits_{p\varepsilon T} $\end{document} and moreover, there is no ORLICZ function Ψ such that: \documentclass{article}\pagestyle{empty}\begin{document}$ L^\varphi = Lin\mathop { \cap L^p }\limits_{p\varepsilon T} $\end{document} or \documentclass{article}\pagestyle{empty}\begin{document}$ E^\varphi = Lin\mathop { \cap L^p }\limits_{p\varepsilon T} $\end{document}.     

Thermal decomposition of pentacoordinate uranium(VI) complexes

The thermal decomposition of some mixed uranyl complexes with Schiff bases and DMSO, EtOH or (Ph)₃PO as neutral ligand, were investigated and the corresponding activation energy, E*_a, and enthalpy of dissociation, ΔH_d, values were calculated.

The results obtained indicate that for the same neutral ligand, the thermal stability of the uranyl complexes is influenced by the Schiff base used; for the same Schiff base, the presence of (Ph)₃PO results in a greater thermal stability of the mixed complexes than when the other two neutral ligands are present.     

Oxidation of steroid α-diketones by thallium (III) acetate : Crystal and molecular structure of a spiro-cyclopentan-a,s-indaceno derivative obtained from 3,4-diketo steroids

Treatment of 2,3-diketo-cholestane (1) with thallium triacetate in acetic acid afforded mainly 3α-carbomethoxy-A-nor-5α-cholestan-2-one (2). Under similar conditions, the 3,4-diketo steroids (3 and 4) underwent extensive rearrangement affording spiro-lactones (9 and 10), in low yields. The structural assignment of the spiro-cholestane derivative was supported by crystallographic X-ray analysis. This product was the result of A and B-ring contractions followed by acid-catalysed cyclization of an unsaturated carboxy intermediate.     

A vanadium-51 NMR study of the binding of vanadate and peroxovanadate to proteins

51V quadrupolar central transition NMR spectra of buffered (pH 7.6-8.0) solutions of bovine apo-transferrin (Tf) and bovine prostatic acid phosphatase (Pp) treated with vanadate show normal features (chemical shifts between -515 and -542 ppm) corresponding to the complexation of VO2+ to the Tf binding site and the Pp active centre, respectively. Addition of H2O2 leads to the temporary formation of complexed VO(O2)+ (delta approximately -595). Vanadate-dependent bromoperoxidase from the alga Ascophyllum nodosum exhibits an unusually high shielding both for the native (delta = -931) and the peroxo form (delta = -1135) of the enzyme. A resonance at -471 ppm is traced back to an inactive form with oxovanadium(V) in a trigonal-bipyramidal array.     

Cyclisations par l'intermédiaire de fonctions phénylthioet phénoxy-carbamyle. I. Diphényl-1,2-alcoyl-5-dioxo-3,6-hexahydro-triazines-1,2,4

The N-(p-nitrophenoxy-carbonyl) and N-(phenylthio-carbonyl) derivatives of α-amino-acyl-hydrazides cyclize in presence of diazomethane, yielding hexahydro-1, 2, 4-triazines with simultaneous formation of p-nitro-anisole or thio-anisole respectively. The molecules with a phenoxycarbonyl function such as N-(phenoxycarbonyl)-glycyl-(N, N′-diphenylhydrazide) give the corresponding ring products and anisole only in solvents with high dielectric constant (e.g. nitromethane). The phenylthio-carbonyl derivatives give the same ring products in presence of lead acetate by the intervention of HO^?. The p-nitrophenoxycarbonyl derivatives give rise to the same cyclisations in the presence of pyridine by the intermediate of carbamyle-pyridinium ion acting as electrophile. These different types of intramolecular reactions are illustrated by the formation of 1, 2-diphenyl-5-alcoyl-3, 6-dioxo-1, 2, 4-hexahydro-triazines.