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Fundamental Studies of the Singlet Oxygen Reactions with the Potent Marine Toxin Domoic Acid

机译:用有效的海洋毒素毒素大气酸的单线氧反应的基础研究

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摘要

Domoic acid (DA), a potent marine toxin, is readily oxidized upon reaction with singlet oxygen (~1O_2). Detailed product studies revealed that the major singlet oxygenation reaction pathways were the [2 + 2] cycloaddition (60.2%) and ene reactions (39.8%) occurring at the Z double bond. Diene isomerization and [4 + 2] cycloaddition, common for conjugated diene systems, were not observed during the singlet oxygenation of DA. The bimolecular rate constant for the DA reaction with ~1O_2 determined by competition kinetics was 5.1 × 10~5 M~(-1) s~(-1). Based on the rate constant and steady-state concentrations of ~1O_2 in surface waters, the environmental half-life of DA due to singlet oxygen-induced transformations is between 5 and 63 days. The ~1O_2 reaction product mixture of DA did not exhibit significant biological activity based on ELISA studies, indicating that singlet oxygenation could be an important natural detoxification process. The characteristic oxidation products can provide valuable markers for the risk assessment of DA-contaminated natural waters.
机译:在与单线氧(〜1O_2)反应时,大使酸(DA)易于氧化在反应时易氧化(〜1O_2)。详细的产品研究表明,在Z双键时,主要单次氧合反应途径是[2 + 2]环加成(60.2%)和烯醇反应(39.8%)。在DA的单次氧合期间未观察到缀合的二烯系统的二烯异构化和[4 + 2]环加成,共轭二烯系统。通过竞争动力学确定的〜1O_2的DA反应的双分子率常数为5.1×10〜5m〜(-1)S〜(-1)。基于表面水中〜1O_2的速率恒定和稳态浓度,由于单线态氧诱导的转化导致的DA的环境半衰期为5至63天。 DA的〜1O_2反应产物混合物没有基于ELISA研究表现出显着的生物活性,表明单线氧合可能是一个重要的天然解毒过程。特征氧化产品可以为DA污染的天然水域的风险评估提供有价值的标记。

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  • 来源
    《Environmental Science & Technology》 |2020年第10期|6073-6081|共9页
  • 作者单位

    Department of Chemistry and Biochemistry Florida International University Miami Florida 33199 United States;

    Department of Chemistry and Biochemistry Florida International University Miami Florida 33199 United States;

    Department of Chemistry and Biochemistry Florida International University Miami Florida 33199 United States;

  • 收录信息 美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
  • 原文格式 PDF
  • 正文语种 eng
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