Carbon- and oxygen-centered radicals are equally important haptens of allylic hydroperoxides in allergic contact dermatitis.
Carbon- and oxygen-centered radicals are equally important haptens of allylic hydroperoxides in allergic contact dermatitis.
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以碳和氧为中心的自由基在过敏性接触性皮炎中是烯丙型氢过氧化物的同样重要的半抗原。
DOI：
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发表时间：
2008
影响因子：
4.1
通讯作者：
Anna Börje
中科院分区：
文献类型：
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作者：
Staffan Johansson;E. Giménez;M. Grøtli;A. Karlberg;Anna Börje
柠檬烯是当今西方国家最常用的香料化合物之一。当暴露在空气中时，它会自动氧化，形成氢过氧化物，这是一种强接触性过敏原。为了引起过敏性接触性皮炎（ACD），氢过氧化物被认为通过自由基途径与皮肤中的蛋白质共价结合。因此，由氢过氧化物形成的自由基的性质和反应是重要的。我们已经研究了自由基的形成，敏化潜力，三个烯丙基氢过氧化物。其中两种存在于柠檬烯的氧化混合物中，而第三种是合成的结构类似物。在自由基捕获实验中研究了由这些氢过氧化物形成的自由基的身份。以5，10，15，20-四苯基-21H，23H-卟吩氯化铁[Fe（III）TPPCl 3]为引发剂，1，1，3，3-四甲基异吲哚啉-2-氧为自由基捕获剂，进行了化学捕获实验.使用光解引发的电子顺磁共振实验进行了5-二乙氧基-磷酰基-5-甲基-1-吡咯啉N-氧化物和没有。我们的研究结果表明，所研究的氢过氧化物形成过氧，烯丙氧基，和环氧乙烷基carbinyl自由基的能力。这些自由基可以潜在地与蛋白质反应以形成与ACD相关的免疫原性半抗原-蛋白质复合物。在小鼠局部淋巴结试验中研究了氢过氧化物的致敏效力。所有这三种氢过氧化物被认为是有效的敏化剂与一些变化，这可能是有关的身份和数量的自由基形成。结果表明，碳和氧为中心的自由基是形成半抗原-蛋白质复合物的重要中间体，并且氢过氧化物的敏化效力与它们的结构有关。
Limonene is one of the most commonly used fragrance compounds in western countries today. When exposed to air, it autoxidises, forming hydroperoxides that are strong contact allergens. To cause allergic contact dermatitis (ACD), the hydroperoxides are considered to bind covalently to proteins in the skin via a radical pathway. Consequently, the nature and reactions of the radicals formed from the hydroperoxides are important. We have examined the radical formation from, and sensitizing potential of, three allylic hydroperoxides. Two of these are found in the oxidation mixture of limonene, while the third is a synthetic structural analogue. The identity of the radicals formed from these hydroperoxides has been studied in radical trapping experiments. Chemical trapping experiments were performed using 5,10,15,20-tetraphenyl-21 H,23 H-porphine iron(III) chloride [Fe(III)TPPCl 3] as an initiator and 1,1,3,3-tetramethylisoindolin-2-yloxyl as a radical trapper. Electron paramagnetic resonance experiments using photolysis for initiation were performed with and without 5-diethoxy-phosphoryl-5-methyl-1-pyrroline N-oxide. Our results demonstrate the ability of the studied hydroperoxides to form peroxyl, allyloxyl, and oxiranylcarbinyl radicals. These radicals can potentially react with proteins to form immunogenic hapten-protein complexes relevant for ACD. The sensitizing potency of the hydroperoxides was studied in the murine local lymph node assay. All three hydroperoxides were found to be potent sensitizers with some variations, which can be related to the identity and quantity of the radicals formed. The results indicate that both carbon- and oxygen-centered radicals are important intermediates in the formation of hapten-protein complexes and that the sensitizing potency of the hydroperoxides is related to their structures.