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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Spectroscopic investigation of the noncovalent association of the nerve agent simulant diisopropyl methylphosphonate (DIMP) with zinc(II) porphyrins
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Spectroscopic investigation of the noncovalent association of the nerve agent simulant diisopropyl methylphosphonate (DIMP) with zinc(II) porphyrins

机译：神经药模拟物磷酸二异丙酯（DIMP）与卟啉锌（II）非共价缔合的光谱研究

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摘要

Organophosphonates pose a significant threat as chemical warfare agents, as well as environmental toxins in the form of pesticides. Thus, methodologies to sense and decontaminate these agents are of significant interest. Porphyrins and metalloporphyrins offer an excellent platform to develop chemical threat sensors and photochemical degradation systems. These highly conjugated planar molecules exhibit relatively long-lived singlet and triplet states with high quantum yields and also form self-associated complexes with a wide variety of molecules. A significant aspect of porphyrins is the ability to functionalize the peripheral ring system either directly to the pyrrole rings or to the bridging methine carbons. In this report, steady-state absorption and fluorescence are utilized to probe binding affinities of a series of symmetric and asymmetric zinc(II) metalloporphyrins for the nerve agent simulant diisopropyl methylphosphonate (DIMP) in hexane. The red shifts in the absorption and emission spectra observed for all of the metalloporphyrins probed are discussed in the frame of Gouterman's four orbital model and a common binding motif involving coordination between the metalloporphyrin and DIMP via interaction between the zinc metal center of the porphyrin and phosphoryl oxygen of DIMP (Zn-O=P) is proposed.
机译：有机膦酸盐作为化学战剂以及农药形式的环境毒素，构成了重大威胁。因此，对这些试剂进行感测和净化的方法引起了极大的兴趣。卟啉和金属卟啉为开发化学威胁传感器和光化学降解系统提供了一个极好的平台。这些高度共轭的平面分子表现出相对长寿命的单重态和三重态，具有高量子产率，并且还与多种分子形成自缔合的复合物。卟啉的一个重要方面是能够直接将外围环系统功能化为吡咯环或桥接次甲基碳的功能。在此报告中，利用稳态吸收和荧光来探测一系列对称和不对称金属卟啉锌与神经毒剂模拟剂二异丙基甲基膦酸酯（DIMP）在己烷中的结合亲和力。在古特曼的四个轨道模型的框架内讨论了所探测到的所有金属卟啉的吸收光谱和发射光谱的红移，以及通过卟啉的锌金属中心与磷酰基之间的相互作用，涉及金属卟啉和DIMP之间协同作用的共同结合基序提出了DIMP（Zn-O = P）的氧。

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