Maness Peter F, Cone Grant W, Ford David A, McCulla Ryan D
Department of Chemistry, Saint Louis University, St. Louis, Missouri.
Department of Biochemistry, Saint Louis University Medical School, St. Louis, Missouri.
Photochem Photobiol. 2023 Nov-Dec;99(6):1412-1419. doi: 10.1111/php.13803. Epub 2023 Mar 30.
Lipid oxidation by reactive oxygen species (ROS) provide several different oxidation products that have been implicated in inflammatory responses. Ground state atomic oxygen [O( P)] is produced by the photodeoxygenation of certain heterocyclic oxides and has a reactivity that is unique from other ROS. Due to the reactive nature of O( P), the site of O( P)-generation is expected to influence the products in heterogenous solutions or environments. In this work, the oxidation of low-density lipoprotein (LDL) by lipids with covalently bound O( P)-photoprecursors was compared to more hydrophilic O( P)-photoprecursors. Lipid oxidation products were quantified after Bligh-Dyer extraction and pentafluorobenzyl bromide (PFB) derivatization by GC-MS. Unlike the more hydrophilic O( P)-photoprecursors, the oxidation of LDL during the irradiation of lipid-(O P)-photoprecursor conjugates showed little quenching by the addition of the O( P)-scavenging sodium allyl sulfonate. This indicated that lipophilic O( P)-photoprecursors are expected to generate lipid oxidation products where other more hydrophilic O( P)-photoprecursors could be quenched by other reactive groups present in solution or the environment.
活性氧（ROS）引发的脂质氧化会产生几种不同的氧化产物，这些产物与炎症反应有关。基态原子氧[O( P)]由某些杂环氧化物的光脱氧作用产生，其反应活性与其他ROS不同。由于O( P)的反应特性，预计O( P)的产生位点会影响异质溶液或环境中的产物。在这项工作中，将具有共价结合O( P) - 光前体的脂质对低密度脂蛋白（LDL）的氧化与更具亲水性的O( P) - 光前体进行了比较。通过Bligh-Dyer萃取和五氟苄基溴（PFB）衍生化后，用气相色谱 - 质谱联用仪（GC-MS）对脂质氧化产物进行定量。与更具亲水性的O( P) - 光前体不同，在脂质 - (O P) - 光前体共轭物辐照期间LDL的氧化，通过添加O( P)清除剂烯丙基磺酸钠几乎没有淬灭作用。这表明亲脂性O( P) - 光前体有望产生脂质氧化产物，而其他更具亲水性的O( P) - 光前体可能会被溶液或环境中存在的其他反应性基团淬灭。
