AMPPD化学发光在不同声音中的作用机理,Journal of Chemical Theory and Computation

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AMPPD化学发光在不同声音中的作用机理
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2013-04-24 00:00:00 , DOI: 10.1021/ct400206k
Ling Yue ₁ , Ya-Jun Liu ₁

Affiliation

3-（2'-螺金刚烷基）-4-甲氧基-4-（3″-磷酰氧基）-苯基-1,2-二氧杂环丁烷（AMPPD或m - AMPPD）的化学发光现象已常规应用于临床诊断。尽管AMPDD化学发光免疫分析是最成功的免疫分析之一，但AMPPD化学发光的机制仍然未知。的AMPPD化学发光过程包括三个步骤：AMPPD酶促触发，以产生3-（2'- spiroadamantyl）-4-甲氧基-4-（3“ -羟基苯基）-1,2-二氧杂环丁烷（米- AMPD）; m - AMPD分解成激发态甲基米-oxybenzoate阴离子（米- MOB ^-）; 激发态米- MOB ^-松弛到其基态并发光。显然，中间步骤对于化学发光至关重要，并且由于实验和理论上的困难而尚未得到很好的理解。我们对m - AMPD及其对位异构体p - AMPD的化学发光分解机理进行了首次理论研究。，除了密度泛函方法外，还使用完整的活动空间自洽场和二阶多配置摄动方法。这项研究表明（1）分子内化学引发的电子交换发光（CIEEL）或协同电荷转移（CT）机理都不能很好地描述m-和p - AMPD的分解。取而代之的是，它们的分解是根据我们先前提出的逐渐可逆的CT引发的发光机制进行的。（2）m-和p - AMPD的不同稳定性化学激发态可能是其化学发光效率差异很大的基础。（3）化学发光效率与电子给体在芳香环上的位置之间的关系，即所谓的“奇/偶选择规则”，不能完全解释二氧环乙烷的化学发光效率。奇/偶选择规则仅适用于部分二氧环乙烷，因为它不能捕获化学发光与供体之间关系的起源。我们发现，起源包括结合，诱导和空间效应的组合。基于这些效果的组合，我们在理论上设计了一些1,2-二氧杂环丁烷，以指导实验人员合成这些出色的化学发光分子。

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Mechanism of AMPPD Chemiluminescence in a Different Voice

The chemiluminescence phenomenon of 3-(2′-spiroadamantyl)-4-methoxy-4-(3″-phosphoryloxy)-phenyl-1,2-dioxetane (AMPPD or m-AMPPD) has been routinely applied in clinical diagnostics. Although the AMPDD chemiluminescence immunoassay is one of the most successful immunoassays, the mechanism of AMPPD chemiluminescence remains largely unknown. The AMPPD chemiluminescence process is composed of three steps: AMPPD is enzymatically triggered to produce 3-(2′-spiroadamantyl)-4-methoxy-4-(3″-hydroxyphenyl)-1,2-dioxetane (m-AMPD); m-AMPD decomposes into the excited-state methyl m-oxybenzoate anion (m-MOB^–); the excited-state m-MOB^– relaxes to its ground state and emits light. Obviously, the middle step is critical for the chemiluminescence and has not been well understood because of both experimental and theoretical difficulties. We performed the first theoretical study on the chemiluminescent decomposition mechanism of m-AMPD and its para isomer, p-AMPD, using the complete active space self-consistent field and the second-order multiconfigurational perturbation methods in addition to the density functional method. This investigation revealed that (1) neither the intramolecular chemical initiated electron exchange luminescence (CIEEL) nor the concerted charge transfer (CT) mechanism can describe the decomposition of m- and p-AMPD well. Instead, their decomposition occurs according to our previously proposed mechanism of gradually reversible CT-initiated luminescence. (2) The different stabilities of the m- and p-AMPD chemiexcited states might be the basis for the large difference in their chemiluminescence efficiencies. (3) The relationship between the chemiluminescence efficiency and the position of the electron donor on the aromatic ring, the so-called “odd/even selection rule,” does not fully explain the chemiluminescence efficiency of dioxetanes. The odd/even selection rule is only correct for partial dioxetanes, because it does not capture the origin of the relationship between the chemiluminescence and the donor. We revealed that the origin consists of a combination of conjugation, induction, and steric effects. On the basis of this combination of effects, we theoretically designed some 1,2-dioxetanes to guide experimentalists in the synthesis of these excellent chemiluminescent molecules.

更新日期：2013-04-24

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