Pryor W A, Nuggehalli S K, Scherer K V, Church D F
Biodynamics Institute, Louisiana State University, Baton Rouge 70803.
Chem Res Toxicol. 1990 Jan-Feb;3(1):2-7. doi: 10.1021/tx00013a001.
Electron spin resonance (ESR) analysis at room temperature of the particles produced during the aerobic pyrolysis of perfluoro polymers (PFP) shows the presence of end-chain peroxyl radicals. These radicals, which would normally have lifetimes of several seconds at most, are stabilized by being immobilized in the particles and decay at a rate of about 20%/day. Normally, radicals with this stability would not be expected to be reactive; however, these peroxyl radicals react with 3-chloropropene, with iodine in benzene, with methyl linoleate in methanol, and with aqueous liposomes from soy phosphatidylcholine. Also, stable radicals of this sort would not be expected to give spin adducts; however, when the particles are suspended in a benzene solution containing alpha-phenyl-N-tert-butylnitrone (PBN), they react to give the same series of spin adducts that are detected when the unfiltered smoke from the oxidative pyrolysis of perfluoro polymers is bubbled directly into PBN solutions. This appears to be the first report of the reaction of radicals entrapped in a solid with a spin trap. The nitroxide species produced by the PBN-particle reaction include a fluorine atom spin adduct, an oxy radical adduct, and benzoyl tert-butyl nitroxide (PBNOx), the oxidation product of the spin trap; all of these appear to arise from reaction of the particle-bound peroxyl radicals with the spin trap. Because the particles are in the highly respirable range (down to 0.01 micron), these entrapped peroxyl radicals may be carried deep within the lung when fumes from PFP pyrolysis are inhaled and would be expected to place an oxidative burden on the lung.(ABSTRACT TRUNCATED AT 250 WORDS)
在室温下对全氟聚合物（PFP）有氧热解过程中产生的颗粒进行电子自旋共振（ESR）分析，结果表明存在端链过氧自由基。这些自由基通常寿命最长为几秒，通过固定在颗粒中而稳定下来，并以约20%/天的速率衰减。通常情况下，具有这种稳定性的自由基预计不会具有反应活性；然而，这些过氧自由基会与3-氯丙烯、苯中的碘、甲醇中的亚油酸甲酯以及大豆磷脂酰胆碱的水性脂质体发生反应。此外，这种稳定的自由基预计不会产生自旋加合物；然而，当颗粒悬浮在含有α-苯基-N-叔丁基硝酮（PBN）的苯溶液中时，它们会发生反应，产生与将全氟聚合物氧化热解产生的未过滤烟雾直接鼓泡到PBN溶液中时检测到的相同系列的自旋加合物。这似乎是关于固体中捕获的自由基与自旋捕获剂反应的首次报道。PBN与颗粒反应产生的氮氧化物种类包括氟原子自旋加合物、氧自由基加合物以及自旋捕获剂的氧化产物苯甲酰叔丁基硝酮（PBNOx）；所有这些似乎都源于颗粒结合的过氧自由基与自旋捕获剂的反应。由于这些颗粒处于极易吸入的范围内（低至0.01微米），当吸入PFP热解产生的烟雾时，这些捕获的过氧自由基可能会深入肺部，并预计会给肺部带来氧化负担。（摘要截短为250字）
