Lingli Wang, Jinhui Cao, Pu Wang, Yu Fu, Jialin Chen, Zhaohui Wang
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According to differences in alcohol-derived adducts (e.g., DMPO-CH<sub>2</sub>OH or DMPO-OCH<sub>3</sub>) while alcohol is attacked by <sup>•</sup>OH or DMPO<sup>•+</sup>, a nonradical mechanism is proposed for the BQ/DMPO system. This is further evidenced by the mass spectrometry data in which DMPO-OCH<sub>3</sub> has been identified in BQ (or chlorinated-BQ)/DMPO systems. <sup>17</sup>O incorporation experiments verify that hydroxyl oxygen in DMPO-OH originates from water. The DMPO-OH adduct might be formed via direct oxidation and water substitution or one-electron oxidation and nucleophilic addition. This study provides a peroxide-independent alternative route leading to DMPO-OH adduct in quinone-based systems, which has profound implications for assessing adverse health effects and even biogeochemical impacts of quinones if EPR is applied.</p>","PeriodicalId":29795,"journal":{"name":"Environment & Health","volume":"3 2","pages":"143-153"},"PeriodicalIF":0.0000,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11851217/pdf/","citationCount":"0","resultStr":"{\"title\":\"Hydroperoxide-Independent Generation of Spin Trapping Artifacts by Quinones and DMPO: Implications for Radical Identification in Quinone-Related Reactions.\",\"authors\":\"Lingli Wang, Jinhui Cao, Pu Wang, Yu Fu, Jialin Chen, Zhaohui Wang\",\"doi\":\"10.1021/envhealth.4c00142\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>Quinones, as highly redox active molecules in biology, are believed to react with hydroperoxides to produce highly reactive <sup>•</sup>OH, assuming that radical adducts are exclusively formed by the addition of free radicals to the spin trap as detected by the electron paramagnetic resonance (EPR) methodology. 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引用次数: 0
摘要
在生物学中,醌类作为高度氧化还原活性的分子,被认为与氢过氧化物反应产生高活性的•OH,假设自由基加合物完全是通过向电子顺磁共振(EPR)方法检测到的自旋阱中添加自由基形成的。在这里,发现了与•OH自由基捕获形成的相同的DMPO加合物的直接形成,而醌(即1,4-苯醌(BQ),甲基-BQ (2- me -BQ, 2,5- me -BQ, 2,6- me -BQ)和氯化-BQ (2- cl -BQ, 2,5- cl -BQ, 2,6- cl -BQ))与独立于过氧化物的自旋阱5,5-二甲基-1-吡咯啉n -氧化物(DMPO)相遇。根据醇衍生的加合物(如DMPO- ch2oh或DMPO- och3)在醇被•OH或DMPO•+攻击时的差异,提出了BQ/DMPO体系的非自由基机制。质谱数据进一步证明了这一点,其中DMPO- och3已在BQ(或氯化BQ)/DMPO系统中被鉴定出来。17O掺入实验证实了DMPO-OH中的羟基氧来源于水。DMPO-OH加合物可通过直接氧化和水取代或单电子氧化和亲核加成形成。本研究提供了一种不依赖过氧化物的醌类体系中dpo - oh加合物的替代途径,这对评估醌类的不良健康影响甚至生物地球化学影响具有深远的意义。
Hydroperoxide-Independent Generation of Spin Trapping Artifacts by Quinones and DMPO: Implications for Radical Identification in Quinone-Related Reactions.
Quinones, as highly redox active molecules in biology, are believed to react with hydroperoxides to produce highly reactive •OH, assuming that radical adducts are exclusively formed by the addition of free radicals to the spin trap as detected by the electron paramagnetic resonance (EPR) methodology. Here, direct formation of the same DMPO adduct as that formed by genuine radical trapping of •OH is discovered, while quinones (i.e., 1,4-benzoquinone (BQ), methyl-BQ (2-Me-BQ, 2,5-Me-BQ, 2,6-Me-BQ), and chlorinated-BQ (2-Cl-BQ, 2,5-Cl-BQ, 2,6-Cl-BQ)) meet with the spin trap 5,5-dimethyl-1-pyrroline N-oxide (DMPO), independent of peroxides. According to differences in alcohol-derived adducts (e.g., DMPO-CH2OH or DMPO-OCH3) while alcohol is attacked by •OH or DMPO•+, a nonradical mechanism is proposed for the BQ/DMPO system. This is further evidenced by the mass spectrometry data in which DMPO-OCH3 has been identified in BQ (or chlorinated-BQ)/DMPO systems. 17O incorporation experiments verify that hydroxyl oxygen in DMPO-OH originates from water. The DMPO-OH adduct might be formed via direct oxidation and water substitution or one-electron oxidation and nucleophilic addition. This study provides a peroxide-independent alternative route leading to DMPO-OH adduct in quinone-based systems, which has profound implications for assessing adverse health effects and even biogeochemical impacts of quinones if EPR is applied.
期刊介绍:
Environment & Health a peer-reviewed open access journal is committed to exploring the relationship between the environment and human health.As a premier journal for multidisciplinary research Environment & Health reports the health consequences for individuals and communities of changing and hazardous environmental factors. In supporting the UN Sustainable Development Goals the journal aims to help formulate policies to create a healthier world.Topics of interest include but are not limited to:Air water and soil pollutionExposomicsEnvironmental epidemiologyInnovative analytical methodology and instrumentation (multi-omics non-target analysis effect-directed analysis high-throughput screening etc.)Environmental toxicology (endocrine disrupting effect neurotoxicity alternative toxicology computational toxicology epigenetic toxicology etc.)Environmental microbiology pathogen and environmental transmission mechanisms of diseasesEnvironmental modeling bioinformatics and artificial intelligenceEmerging contaminants (including plastics engineered nanomaterials etc.)Climate change and related health effectHealth impacts of energy evolution and carbon neutralizationFood and drinking water safetyOccupational exposure and medicineInnovations in environmental technologies for better healthPolicies and international relations concerned with environmental health