Rapid catalytic transfer reduction of aromatic nitro compounds to hydroxylamines

A general method has been developed for the rapid, metal-catalysed transfer reduction of nitro compounds to N-substituted hydroxylamines.     

Nanovoid relaxation in a series of copolyester glasses under cyclic loading using synchronous PALS

This study examines if correlation between a specific molecular motion and the growth and relaxation of nanovoids, which are precursors to crazes, can be established. A novel technique, positronium annihilation lifetime spectroscopy (PALS) synchronized with cyclic stress, is reported. In this technique the positronium annihilation signal was accumulated in sixteen channels corresponding to sixteen phases of the sinusoidal load, which allowed statistically significant data for nanovoid generation and relaxation due to the fluctuating stress to be accumulated. This technique was applied to a series of copolymers of poly(ethylene terephthalate) (PET) and poly(1,4-cyclohexylenedimethylene terephthalate) (PCT). Previous studies have shown that the cyclohexylene rings in the main chain of PCT actively undergo chair-boat-chair conformational transitions in the glassy PCT at around room temperature. The PET-co-PCT series was also chosen for this study because the crazing stress increases systematically with the cyclohexylene content. The synchronized PALS data are consistent with the hypothesis that transient nanovoids generated by the cyclic stress in polymers containing more cyclohexylene rings relax more readily than those with fewer rings. The results also correlate well with the crazing stress in this series of copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1410–1417, 2007     

Paracetamol oxidation: synthesis and reactivity of N-acetyl-p-benzoquinoneimine

A convenient synthesis of N-acetyl-p-benzoquinoneimine is described, its reaction with glutathione and N-acetyl cysteine proceeds not only by adduct formation but also by a reductive pathway.     

Laser excitation spectra of He2

Metastable $\text{a(2sσ)}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ He₂ molecules are produced by a dc discharge in a flowing He stream. Laser excitation downstream of the discharge produces excitation spectra for a number of He₂ states. LIF spectra are observed for the $\text{(npπ)}{}^3\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ series for n = 4–9, excepting 5 and the $\text{(npπ)}{}^3\text{Π}{}_{\mathrm{g}}$ series for n = 5–15.     

Gas phase infrared multiple-photon dissociation spectra of methanol, ethanol and propanol proton-bound dimers, protonated propanol and the propanol/water proton-bound dimer

The infrared multiphoton dissociation (IRMPD) spectra of three homogenous proton-bound dimers are presented and the major features are assigned based on comparisons with the neutral alcohol and with density functional theory calculations. As well, the IRMPD spectra of protonated propanol and the propanol/water proton-bound dimer (or singly hydrated protonated propanol) are presented and analysed. Two primary IRMPD photoproducts were observed for each of the alcohol proton bound dimers and were found to vary with the frequency of the radiation impinging upon the ions. For example, when the proton-bound dimer absorbs weakly a larger amount of S(N)2 product, protonated ether and water, are observed. When the proton-bound dimer absorbs more strongly, an increase in the simple dissociation product, protonated alcohol and neutral alcohol, is observed. With the aid of RRKM calculations this frequency dependence of the branching ratio is explained by assuming that photon absorption is faster than dissociation for these species and that only a few photons extra are necessary to make the higher-energy dissociation channel (simple cleavage) competitive with the lower energy (S(N)2) reaction channel.     

Super-multiplicativity and a lower bound for the decay of the signature of a path of finite length

For a path of length $L>0$, if for all $n\ge 1$, we multiply the n-th term of the signature by $n!L^{?n}$, we say that the resulting signature is ‘normalised’. It has been established (T. J. Lyons, M. Caruana, T. Lévy, Differential equations driven by rough paths, Springer, 2007) that the norm of the n-th term of the normalised signature of a bounded-variation path is bounded above by 1. In this article, we discuss the super-multiplicativity of the norm of the signature of a path with finite length, and prove by Fekete's lemma the existence of a non-zero limit of the n-th root of the norm of the n-th term in the normalised signature as n approaches infinity.