Lachocki T M, Church D F, Pryor W A
Biodynamics Institute, Louisiana State University, Baton Rouge 70803.
Environ Res. 1988 Feb;45(1):127-39. doi: 10.1016/s0013-9351(88)80015-x.
We have detected free radicals in the gas-phase smoke resulting from the combustion of several household materials. Materials were pyrolyzed by rapid heating in a quartz ignition tube in a flowing air stream. The filtered smoke was bubbled into a dodecane solution of alpha-phenyl-N-t-butylnitrone (PBN), and the resulting nitroxide radicals were detected by electron spin resonance. Cellulosic materials (birch plywood, cellulose, 1R1 research cigarette tobacco, and yellow pine) and dried exterior paint produce about the same yield of trapped radicals. The smoke from polyethylene and rubber produce approximately 2-fold more radicals than the smoke from the cellulosic materials. Nylon smoke yields about 10-fold less radicals than the cellulosic materials. The smokes from polyvinyl chloride and polytetraflouroethylene do not produce detectable spin adducts of PBN by this method. Where radicals were trapped, oxygen-centered spin adducts predominated; lesser amounts of carbon-centered spin adducts and an oxidation product of PBN were observed. Different oxygen-centered radicals were detected from different materials, as judged from the variation observed in the hyperfine splitting constants of the principal spin adducts. When cellulose smoke is dissolved in solution, radicals continue to be produced for at least 20 min, suggesting the production of a metastable species in the gas phase that decomposes to form radicals in solution.
我们已经在几种家用材料燃烧产生的气相烟雾中检测到了自由基。材料在石英点火管中于流动的空气流中通过快速加热进行热解。将过滤后的烟雾鼓泡到α-苯基-N-叔丁基硝酮(PBN)的十二烷溶液中,通过电子自旋共振检测产生的氮氧自由基。纤维素材料(桦木胶合板、纤维素、1R1研究卷烟烟草和黄松)以及干燥的外墙涂料产生的捕获自由基产率大致相同。聚乙烯和橡胶产生的烟雾比纤维素材料产生的烟雾产生的自由基大约多2倍。尼龙烟雾产生的自由基比纤维素材料少约10倍。通过这种方法,聚氯乙烯和聚四氟乙烯产生的烟雾不会产生可检测到的PBN自旋加合物。在捕获自由基的地方,以氧为中心的自旋加合物占主导;观察到少量以碳为中心的自旋加合物和PBN的一种氧化产物。根据主要自旋加合物的超精细分裂常数的变化判断,从不同材料中检测到了不同的以氧为中心的自由基。当纤维素烟雾溶解在溶液中时,自由基至少会持续产生20分钟,这表明在气相中产生了一种亚稳物种,该物种在溶液中分解形成自由基。