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首页> 外文期刊>Environmental Science & Technology >Development of N-Cyclopropylanilines to Probe the Oxidative Properties of Triplet-State Photosensitizers
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Development of N-Cyclopropylanilines to Probe the Oxidative Properties of Triplet-State Photosensitizers

机译：N-环丙基苯胺的开发以探测三重态光敏剂的氧化性能

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Anilines have been shown to be especially susceptible to single-electron oxidation by excited triplet-state photosensitizers ((3)sens*), and thus, are good potential candidates to probe the oxidative properties of triplet-state chromophoric dissolved organic matter ((CDOM)-C-3*). However, steady-state experiments tend to underestimate their rate of oxidation by (CDOM)-C-3* due to radical cation quenching (i.e., aniline(center dot+) - aniline) by antioxidant moieties present in DOM. We envisioned the potential utility of N-cyclopropylaniline (CPA) to overcome this limitation, as it is known to undergo spontaneous, irreversible cyclopropyl ring-opening after an initial single-electron oxidation. To test this, first a set of CPA analogs was synthesized and then paired with a model sensitizer and antioxidant, or various DOM isolates, to examine their reactivity and susceptibility to antioxidant quenching during steady-state photolysis experiments. Next, time-resolved measurements of CPA and CPA analog oxidation were obtained by laser flash photolysis through direct observation of (3)sens* and radical cations of CPA and CPA analogs. Finally, CPA photolysis products were isolated by semi-preparative high-performance liquid chromatography and identified by nuclear magnetic resonance spectroscopy. Outcomes of this work, including oxidation bimolecular rate constants of CPA and CPA analogs (similar to 9 x 10(8) to 4 x 10(9) M-1 s(-1)), radical cation lifetimes of CPA and its analogs (140-580 ns), and identified ring-opened products, support the usefulness of cyclopropylanilines as single-electron transfer probes in photosensitized aqueous solutions.
机译：苯胺已显示出特别容易受到激发的三重态光敏剂（（3）sens *）的单电子氧化的影响，因此是探测三重态发色团溶解的有机物（（CDOM） ）-C-3 *）。但是，由于DOM中存在的抗氧化剂部分导致自由基阳离子淬灭（即苯胺（中心点+）->苯胺），稳态实验往往会低估它们被（CDOM）-C-3 *氧化的速率。我们设想了N-环丙基苯胺（CPA）克服这一局限性的潜在用途，因为众所周知，在最初的单电子氧化后，它会自发发生不可逆的环丙基开环。为了测试这一点，首先合成了一组CPA类似物，然后与模型敏化剂和抗氧化剂或各种DOM分离物配对，以检查它们在稳态光解实验中的反应性和对抗氧化剂猝灭的敏感性。接下来，通过直接观察CPA和CPA类似物的（3）sens *和自由基阳离子，通过激光闪光光解法获得了CPA和CPA类似物氧化的时间分辨测量结果。最后，通过半制备型高效液相色谱法分离了CPA光解产物，并通过核磁共振波谱法进行了鉴定。这项工作的成果，包括CPA和CPA类似物的氧化双分子速率常数（类似于9 x 10（8）至4 x 10（9）M-1 s（-1）），CPA及其类似物的自由基阳离子寿命（ 140-580 ns）并鉴定出开环产物，证明环丙基苯胺在光敏水溶液中作为单电子转移探针的有用性。

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  • 来源
    《Environmental Science & Technology》 |2019年第9期|4813-4822|共10页
  • 作者

    Pflug Nicholas C.; Schmitt Markus; McNeill Kristopher;

  • 作者单位

    Swiss Fed Inst Technol, Inst Biogeochem & Pollutant Dynam, CH-8092 Zurich, Switzerland;

    Swiss Fed Inst Technol, Inst Biogeochem & Pollutant Dynam, CH-8092 Zurich, Switzerland;

    Swiss Fed Inst Technol, Inst Biogeochem & Pollutant Dynam, CH-8092 Zurich, Switzerland;

  • 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);
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