结构对基于激发态分子内质子转移的膦氟化物 G 系列神经毒剂蒸汽检测传感器的影响

IF 3.5 Q2 CHEMISTRY, ANALYTICAL
Shengqiang Fan, Paul L. Burn, Ian R. Gentle and Paul E. Shaw
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引用次数: 0

摘要

激发态分子内质子转移(ESIPT)发光体的独特之处在于,相对于吸收光谱,发射光谱会发生明显的红移。在此,我们探讨了取代基对 2-[1-苯基-1H-菲咯并[9,10-d]咪唑-2-基]苯酚基 ESIPT 报告化合物薄膜检测 G 系列神经毒剂中含有的氟化氢的能力的影响。当 2-[1-苯基-1H-菲并[9,10-d]咪唑-2-基]苯酚基报告化合物的羟基被保护为硅基醚时,光致发光发射光谱具有振动结构,发射最大值在 370 nm 左右。当接触到 G 系列神经毒剂模拟物--氟磷酸二异丙酯中的氟化氢时,硅烷保护基团会被裂解,从而产生 ESIPT 发射,其最大峰值在 470 纳米左右,因此可以识别氟化氢的存在。研究发现,带有不同硅基保护基团的传感材料薄膜对环境条件的稳定性不同,与氟化氢的反应活性也不同,与较小的三甲基硅基醚相比,较大的硅基醚(如三乙基硅基醚和 t-丁基二甲基硅基醚)总体性能更好。研究发现,立体累赘或添加极性增溶基团会降低传感能力。最佳传感材料是亲脂性的,并含有一个 t-丁基二甲基硅基保护基团,其薄膜能够检测浓度为 0.1 ppm 的氟化氢,根据沙林纯度为 99%计算,可检测浓度为 1.2 ppm 的沙林,低于沙林的 LC50 5 分钟暴露限值 1.6-3.2 ppm。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Effect of structure on excited-state intramolecular proton transfer-based sensors for phosphonofluoridate G-series nerve agent vapour detection†

Effect of structure on excited-state intramolecular proton transfer-based sensors for phosphonofluoridate G-series nerve agent vapour detection†

Effect of structure on excited-state intramolecular proton transfer-based sensors for phosphonofluoridate G-series nerve agent vapour detection†

Excited-state intramolecular proton transfer (ESIPT) emitters are unique in that the emission is significantly red shifted relative to the absorption spectra. Herein we explore the effect of substituents on the ability of thin films of 2-[1-phenyl-1H-phenanthro[9,10-d]imidazol-2-yl]phenol-based ESIPT reporter compounds to detect hydrogen fluoride found in G-series nerve agents containing a phosphonofluoridate moiety. When the hydroxyl group of the 2-[1-phenyl-1H-phenanthro[9,10-d]imidazol-2-yl]phenol-based reporter compounds was protected as a silyl ether the photoluminescence emission spectra had vibrational structure and emission maxima at around 370 nm. The silyl protecting groups could be cleaved upon exposure to hydrogen fluoride in the G-series nerve agent simulant, di-iso-propyl fluorophosphate, leading to ESIPT emission with a peak maximum at around 470 nm, thus allowing identification of the presence of hydrogen fluoride. Films of the sensing materials with the different silyl protecting groups were found to have different stabilities to ambient conditions and reactivity with hydrogen fluoride, with the larger silyl ethers such as triethylsilyl and t-butyldimethyl silyl performing better overall when compared to the smaller trimethylsilyl ether. Steric encumberance or addition of polar solubilising groups was found to reduce the sensing capability. The optimal sensing material was lipophilic and contained a t-butyldimethyl silyl protecting group, with films capable of detecting hydrogen fluoride at a concentration of 0.1 ppm which, based on a sarin purity of 99%, would enable sarin to be detected at 1.2 ppm, which is below the LC50 five minute exposure limit for sarin of 1.6–3.2 ppm.

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