有机过氧化物安定性的差示扫描量热测定

1 引言有机过氧化物是一种自反应性物质.这类物质在制造、使用、贮存过程中或由于自分解发热、热积累导致燃烧、爆炸,或由于冲击、摩擦、电火花、明火等外部作用导致燃烧爆炸而造成人员伤亡.差示扫描量热法(DSC)、压力容器试验法(PVT)是评价这类物质安全性的基本方法.本文利用DSC法对7种有机过氧化物进行了加热分解试验研究,探讨其热安定性、发生热爆炸的难易程度及剧烈程度.     

Optical and electronic properties of siloxane-bridged cyclic dimers with naphthylene or pyrenylene moieties

The optical and electronic properties of novel siloxane-bridged cyclic dimers with naphthylene (CD1) or pyrenylene (CD2) moieties are described. CD1 and CD2 were obtained by the cyclic dimerization of 1,4-bis(dimethylhydroxysilyl)naphthalene (M1) and 1,6-bis(dimethylhydroxysilyl)pyrene (M2), respectively. CD1 and CD2 mainly exhibited the emission from their excimers owing to their short distances between aryl moieties in CD1 and CD2, which were determined to be 3.44 Å and 3.41 Å by the X-ray crystallographic analysis, respectively. The absorption spectra of CD2 in the presence of 7,7,8,8-tetracyanoquinodimethane (TCNQ) revealed that CD2 has the ability to form 1:1 charge-transfer complex with TCNQ, indicating the existence of the transannular π-π interaction between closely located pyrene components in CD2.     

On selfinjective semiprimary rings

In this note, we use a universal algebraic argument to show that modules with 0-limits need not be equationally compact, thus providing a counter-example to an open problem of Jensen and Lenzing.     

Electron excitation of the Schumann-Runge continuum, longest band, and second band electronic states in O2

We report measurements of differential and integral cross sections for electron excitation of the Schumann-Runge continuum, longest band, and second band electronic states in molecular oxygen. The energy range of the present study is 15-200 eV, with the angular range of the differential cross section (DCS) measurements from 2 to 130°. A generalized oscillator strength analysis is then employed in order to derive integral cross sections (ICSs) from the corresponding DCSs, and these ICSs are compared with relevant energy and oscillator strength scaled Born cross section (BEf-scaling [Y.-K. Kim, J. Chem. Phys. 126, 064305 (2007)]) results determined as a part of this investigation. Interestingly, while the present Schumann-Runge continuum and second band ICSs were in reasonable agreement with the respective BEf-scaling results, agreement for the longest band was poor below 100 eV with a possible reason for this apparently anomalous behavior being canvassed here. Finally, where possible all present data are compared with the results from earlier measurements and calculations with the level of agreement found being very good in some cases and marginal in others.     

Identification of gas emanated from human skin: methane, ethylene, and ethane.

We investigated whether methane, ethylene and ethane gas can be detected in gas emanating from human skin, which is called skin gas. Skin gas was collected with a homemade stainless-steel trap system, which was cooled with liquid nitrogen, and analyzed with a gas chromatograph fitted with a flame ionization detector (FID). Skin-gas samples were obtained by covering a hand for 30 min with a polyfluorovinyl bag in which pure helium gas was introduced. The bag, the trap system and GC were set up online to avoid any contamination by air. Methane, ethylene and ethane in skin gas were successfully collected at an average amount emanated for 30 min (from ten subjects) of 150 +/- 63, 20 +/- 11 and 17 +/- 8 [mean +/- SD] pg/cm2, respectively.     

Raman linewidth study of hydration structure of p-dioxane in aqueous solution

The isotropic linewidth of the CO stretching Raman line of p-dioxane at 835 cm^?1 has been measured at a variety of concentration in aqueous solution and in nonpolar tetrachloroethylene solution. The hydration structure of p-dioxane in aqueous solution has been investigated by a comparison of the experimental results obtained here with those for t-butyl alcohol in the preceding study. As a result, the present data prefer to the hydrogen-bond model rather than the clathrate model, proposed for the p-dioxane-water system.     

Magnetic field effects on electron transfer reactions involving sextet-spin (S = 5/2) intermediates generated on photoexcitation of a Cr(III)-porphyrin complex

The excited trip-sextet (⁶T₁) state of chloro-(3-methylimidazol)-(meso-tetraphenylporphyrinato) chromium(III) (Cr^IIIP) is quenched by 1,1′-dibenzyl-4,4′-bipyridinium (BV²⁺) in acetonitrile through electron transfer to give ⁵(Cr^IIIP^·+) and ²BV^·+. The intermediate is a geminate ion pair in the sextet (Sx) state ⁶[⁵(Cr^IIIP^·+) ²BV^·+], which decays through either the escape from a solvent cage to give the free ions or the spin conversion to the quartet (Qa) state followed by back electron transfer. The free ion yield (Φ_FI) increased with increasing magnetic field from 0 to 4 T and then slightly decreased from 4 T to 10 T. These magnetic field effects are explained as follows. Under low fields where the Zeeman splitting of the spin sublevels is lower than or comparable with the electron spin dipole—dipole interaction within ⁵(Cr^IIIP^·+), this interaction effectively induces the Sx → Qa conversion of [⁵(Cr^IIIP^·+)²BV⁺] to result in low Φ_FI values. Under high fields where the Zeeman splitting is larger than the dipole—dipole interaction, the Sx → Qa conversion is decreased with increasing field to cause higher Φ_FI values. The slight decrease in Φ_FI above 4 T may be due to the Δg mechanism.