Quantitative analysis of the antioxidant poly(1,2-dihydro-2,2,4-trimethylquinoline) (pTMQ) was conducted on pristine, thermally-aged, and gamma radiation-aged commercial cross-linked polyethylene-(XLPE-)based cable insulation material aged at temperatures 60, 90, and 115 °C, with gamma radiation exposure dose rates of 0, 120, 300, and 540 Gy/h for 15 days. The quantification of antioxidant was performed using pyrolysis gas chromatography-mass spectrometry (Py-GCMS). Oxidation induction time (OIT) was measured using differential scanning calorimetry (DSC) and correlation was made between the quantified depletion of antioxidant and measured OIT. It was observed that, in the case of isothermal aging, the quantity of antioxidant and OIT decreased with increasing gamma radiation dose. In the case of samples exposed to the same gamma radiation dose, the quantity of antioxidant and OIT were observed to decrease with increasing aging temperature. Depletion in the quantity of antioxidant relative to that in the pristine material ranged from 7 to 93% for differently aged samples. The measured decline in OIT ranged from 0 to 80%. Change in the quantity of antioxidant in the material was observed to follow the same trend as the change in OIT when the samples were aged under various conditions. The observations are explained in terms of the reaction between the antioxidant and free radicals created during exposure of the samples to thermal and gamma radiation. AbstractQuantitative analysis of the antioxidant poly(1,2-dihydro-2,2,4-trimethylquinoline) (pTMQ) was conducted on pristine, thermally-aged, and gamma radiation-aged commercial cross-linked polyethylene-(XLPE-)based cable insulation material aged at temperatures 60, 90, and 115 °C, with gamma radiation exposure dose rates of 0, 120, 300, and 540 Gy/h for 15 days. The quantification of antioxidant was performed using pyrolysis gas chromatography-mass spectrometry (Py-GCMS). Oxidation induction time (OIT) was measured using differential scanning calorimetry (DSC) and correlation was made between the quantified depletion of antioxidant and measured OIT. It was observed that, in the case of isothermal aging, the quantity of antioxidant and OIT decreased with increasing gamma radiation dose. In the case of samples exposed to the same gamma radiation dose, the quantity of antioxidant and OIT were observed to decrease with increasing aging temperature. Depletion in the quantity of antioxidant relative to that in the pristine material ranged from 7 to 93 % for differently aged samples. The measured decline in OIT ranged from 0 to 80 %. Change in the quantity of antioxidant in the material was observed to follow the same trend as the change in OIT when the samples were aged under various conditions, with a correlation coefficient of 0.82. The observations are explained in terms of the reaction between the antioxidant and free radicals created during exposure of the samples to thermal and gamma radiation.

The kinetics of the reaction of benzyl radicals with [L(1)(H(2)O)RhH{D}](2+) (L(1)=1,4,8,11-tetraazacyclotetradecane) were studied directly by laser-flash photolysis. The rate constants for the two isotopologues, k=(9.3±0.6) × 10(7) M(-1) s(-1) (H) and (6.2±0.3) × 10(7) M(-1) s(-1) (D), lead to a kinetic isotope effect k(H)/k(D)=1.5±0.1. The same value was obtained from the relative yields of PhCH(3) and PhCH(2)D in a reaction of benzyl radicals with a mixture of rhodium hydride and deuteride. Similarly, the reaction of methyl radicals with {[L(1)(H(2)O)RhH](2+) + [L(1)(H(2)O)RhD](2+)} produced a mixture of CH(4) and CH(3)D that yielded k(H)/k(D)=1.42±0.07. The observed small normal isotope effects in both reactions are consistent with reduced sensitivity to isotopic substitution in very fast hydrogen-atom abstraction reactions. These data disprove a literature report claiming much slower kinetics and an inverse kinetic isotope effect for the reaction of methyl radicals with hydrides of L(1)Rh.

An antheridiogen of Anemia mexicana Klotzsch has been partially characterized by combined gas chromatography-mass spectrometry and gas chromatography-Fourier transform/infra-red spectrometry. It is a C19-gibberellin(GA)-like compound with one carboxyl group, an exocyclic methylene group and a lactone ring. It also has one hydroxyl-group and one double-bond equivalent which has not been determined. On the basis of its mass spectrum, it is not identical to previously identified monohydroxy GAs with one ring double bond such as GA5, GA7, GA31 and GA62. By direct comparison of mass spectra, the antheridiogen of A. mexicana was also determined to be different from the antheridiogens of Anemia phyllitidis (L.) Swartz, Anemia hirsuta (L.) Swartz and Lygodium japonicum (Thunb.) Sw.

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Absolute rate constants are reported for the reaction of fluorine atoms with nitric oxide in the presence of the third bodies Ar, He, Ne, N2, NO, CO2, CF4, SF6, and C2F6. The values determined in the present study are compared to those found for reactions of Cl, H, and O with NO.