N-labelling studies of the reaction of 2,6-di-t-butyl-4-methyl-4-nitrocyclohexa-2,5-dienone with nitrogen dioxide; A revised mechanism

Reaction of the ¹⁵N-4-nitrodienone (1) with excess nitrogen dioxide in benzene for 16 h gives the 4,5,6-trinitro ketone (2), labelled (¹⁵NO₂) at C6 but not at C4, and recovered 4-nitrodienone (1) in which extensive loss of ¹⁵NO₂ has occurred. The mechanistic implications of these and related results are discussed.     

Periodic behavior of the stochastic Brusselator in the mean-field limit

Summary We prove a propagation of chaos result for the mean-field limit of a model for a trimolecular chemical reaction called Brusselator. Then we show that the pair of nonlinear (i.e. law-dependent) stochastic differential equations describing the evolution of the concentration of the molecules at a given site in the mean field limit has a solution with a periodic law (in t). Finally we identify the limit and establish a central limit theorem for the periodic law in the case where the noise tends to zero.Part of this work was performed while on leave at the Department of Mathematics and Statistics, Carleton University, Ottawa, Canada and supported by NSERC operating grants of M. Csörgö and D. Dawson     

Elementarteiler von Inzidenzmatrizen symmetrischer Blockpläne

By a study of the integral code generated by the rows of the incidence matrix and its extention the following results are obtained: Let d ₁,...,d _V(d ₁|d ₂,d ₂|d ₃...) be the elementary divisors of the incidence matrix of a symmetric (v,n+, ) design. Then d _v=(n+)n/g.c.d. (n, ). Moreover, if p is a prime such that p|n, p and if x _p denotes the p-part of x, then (d _id_v+2–i) _p =n _p for 2iv. For projective planes it can be shown that d ₁=···=d _3n–2=1, hence and . The paper also contains some results about elementary divisors of incidence matrices G satisfying the condition G ^tG=nI+ J.

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Elementarteiler von Inzidenzmatrizen symmetrischer Blockpläne

     

On the low temperature magnetic properties of some sulfites of divalent iron

Zero field Mössbauer spectra and powder susceptibility measurements show that the condensed, hydrogen bonded network compound FeSO₃ 3H₂O orders antiferromagnetically (T_Néel 9.5 K). The related anhydrous material FeSO₃ also shows antiferromagnetic exchange but no evidence of long range three-dimenstional magnetic order to as low as 1.4 K.Supported by the U.S. National Science Foundation Division of Materials Research—Solid State Chemistry Program Grant No. DMR 8313710.     

Phase Diagram and Properties of Glasses of the System Sb<Subscript>2</Subscript>S<Subscript>3</Subscript>-AgI

The phase diagram of the system Sb₂S₃-AgI was constructed from data of the differential thermal and X-ray phase analyses. The physicochemical properties of glassy and crystalline alloys were studied.     

Coordination modes of 2-hydroxynicotinic acid in second- and third-row transition metal complexes

The new Pd(II), Pt(II), Re(V), Mo(VI) and W(VI) complexes of 2-hydroxynicotinic acid (H₂nicO), trans-[PdCl(HnicO)(PPh₃)₂]·0.75CH₃CN (1), K[PdCl(HnicO)₂]·H₂O (2), [Pd(HnicO)₂(bipy)] (3), cis-[PtCl(HnicO)(PPh₃)₂]·0.75CH₃OH·0.5H₂O (4), [PtCl(HnicO)(bipy)] (5), cis-[ReOI₂(HnicO)(PPh₃)] (6), Na₂[Mo₂O₆(HnicO)₂]·5H₂O (7), Na₂[Mo₄O₁₂(HnicO)₂]·2H₂O (8) and Na₂[W₂O₆(HnicO)₂]·5H₂O (9) have been prepared. The crystal structures of 1 and 4, were determined by X-ray diffraction and show the HnicO⁻ ligand coordinated to palladium or platinum through the nitrogen atom only. Infrared, Raman, ¹H and ¹³C{¹H} NMR spectroscopic data for the complexes are presented and are in agreement with the crystallographic results.     

An electrochemical investigation on (MoO<Subscript>3</Subscript>+PVP+PVA) nanobelts for lithium batteries

Molybdenum trioxide (MoO₃) xerogel films modified with poly(vinyl alcohol)+poly(vinyl pyrrolidone) (PVP+PVA) polyblends were obtained by ion-exchange method with sol-gel technique. Investigations were conducted using X-ray “diffractometry”, Fourier transform infrared spectroscopy, and cyclic voltammetry. The results show that the H atoms in polyblend are H-bonded with the O atoms in the Mo=O bonds of MoO₃ xerogel, which effectively shield the electrostatic interaction between MoO₃ interlayer and Li⁺ ions when MoO₃ xerogel is modified by the intercalation of (PVP+PVA). The reversibility of the insertion/extraction of Li⁺ ions is greatly improved by the modification with polyblend of MoO₃ nanocomposite films. MoO₃ and (PVP+PVA) _x MoO₃ (x = 0, 0.5) nanobelts were obtained by a simple hydrothermal process from MoO₃ sol. The electrochemical cells with configuration Li/(LiPF₆+EC+DMC)/MoO₃ modified by (PVP+PVA) were fabricated and their discharge profiles studied.     

Acetoxyphenylketene. Reaction with biacetyl

The generation of acetoxyphenylketene (4) in the cold in the presence of biacetyl yields the single β-lactone $\text{12B}$, which undergoes a novel rearrangement to the tricyclic orthoester lactone $\text{11}$ above 130°.