Isoprenoid Alcohols are Susceptible to Oxidation with Singlet Oxygen and Hydroxyl Radicals.
Isoprenoid Alcohols are Susceptible to Oxidation with Singlet Oxygen and Hydroxyl Radicals.
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DOI：
10.1007/s11745-015-4104-y
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发表时间：
2016-02
期刊：
影响因子：
1.9
通讯作者：
Swiezewska E
中科院分区：
文献类型：
--
作者：
Komaszylo Née Siedlecka J;Kania M;Masnyk M;Cmoch P;Lozinska I;Czarnocki Z;Skorupinska-Tudek K;Danikiewicz W;Swiezewska E
类异戊二烯作为所有活细胞的共同成分，暴露在氧化剂--活性氧物种中，例如，单线态氧或羟基自由基。尽管如此，聚异戊二烯类化合物的氧化产物从未被表征过。在本研究中，使用单线态氧(在过氧化氢/钼酸根存在下产生或在卟啉存在下光化学反应产生)、氧(由过氧化氢歧化产生)或羟基自由基(由过氧化氢/超声、UV/二氧化钛或UV/过氧化氢产生)体系对异戊二烯醇(Prenol-2和-10)进行化学氧化。用质谱仪(MS)和核磁共振(NMR)方法对产物羟基、过氧基和杂环衍生物的结构进行了研究。此外，电喷雾电离质谱仪似乎是一种有用的分析工具，可用于检测异戊二烯氧化产物(ESI-MS分析)以及根据选定离子的碎裂光谱确定其结构(ESI-MS/MS分析)。综上所述，首次发现了聚异戊二烯醇类化合物对各种氧化剂的敏感性。本文的在线版本(doi：10.1007/s11745-0154104-y)包含补充材料，授权用户可以使用。
Isoprenoids, as common constituents of all living cells, are exposed to oxidative agents—reactive oxygen species, for example, singlet oxygen or hydroxyl radicals. Despite this fact, products of oxidation of polyisoprenoids have never been characterized. In this study, chemical oxidation of isoprenoid alcohols (Prenol-2 and -10) was performed using singlet oxygen (generated in the presence of hydrogen peroxide/molybdate or upon photochemical reaction in the presence of porphyrin), oxygen (formed upon hydrogen peroxide dismutation) or hydroxyl radical (generated by the hydrogen peroxide/sonication, UV/titanium dioxide or UV/hydrogen peroxide) systems. The structure of the obtained products, hydroxy-, peroxy- and heterocyclic derivatives, was studied with the aid of mass spectrometry (MS) and nuclear magnetic resonance (NMR) methods. Furthermore, mass spectrometry with electrospray ionization appeared to be a useful analytical tool to detect the products of oxidation of isoprenoids (ESI–MS analysis), as well as to establish their structure on the basis of the fragmentation spectra of selected ions (ESI–MS/MS analysis). Taken together, susceptibility of polyisoprenoid alcohols to various oxidizing agents was shown for the first time. The online version of this article (doi:10.1007/s11745-015-4104-y) contains supplementary material, which is available to authorized users.