Development of selective colorimetric probes for hydrogen sulfide based on nucleophilic aromatic substitution.
Development of selective colorimetric probes for hydrogen sulfide based on nucleophilic aromatic substitution.
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DOI：
10.1021/jo4008095
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发表时间：
2013-07-05
期刊：
影响因子：
--
通讯作者：
Pluth MD
中科院分区：
文献类型：
--
作者：
Montoya LA;Pearce TF;Hansen RJ;Zakharov LN;Pluth MD
硫化氢是一种重要的生物信号分子，也是重要的环境检测目标。开发H2S检测方法的一个主要挑战是将硫醇和其他亲核试剂的反应性与H2S分离。为了解决这一需求，开发了H2S与贫电子芳香族亲电试剂的亲核芳香取代（SNAr）反应作为分离H2S和硫醇反应性的策略。用H2S处理硝基苯并呋咱（7-硝基-1，2，3-苯并恶二唑，NBD）硫醚的水溶液导致硫醇挤出并形成硝基苯并呋咱硫醇（λmax = 534 nm）。这种反应性允许不需要的硫醚产物在与H2S反应时转化为所需的硝基苯并呋咱硫醇。采用Hammett线性自由能关系研究了反应的范围，确定的ρ = +0.34与提出的SN 2Ar反应机理一致。在缓冲液和血清中证明了开发的探针的功效，相关的亚微摩尔检测限低至190 nM（缓冲液）和380 nM（血清）。此外，硝基苯并呋咱亲电体与H2S的S形响应可以拟合以准确地定量H2S。开发的检测策略提供了一个多方面的H2S检测，我们预计将在未来的各种应用。
Hydrogen sulfide is an important biological signalling molecule and an important environmental target for detection. A major challenge in developing H2S detection methods is separating the often similar reactivity of thiols and other nucleophiles from H2S. To address this need, the nucleophilic aromatic substitution (SNAr) reaction of H2S with electron-poor aromatic electrophiles was developed as a strategy to separate H2S and thiol reactivity. Treatment of aqueous solutions of nitrobenzofurazan (7-nitro-1,2,3-benzoxadiazole, NBD) thioethers with H2S resulted in thiol extrusion and formation of nitrobenzofurazan thiol (λmax = 534 nm). This reactivity allows for unwanted thioether products to be converted to the desired nitrobenzofurazan thiol upon reaction with H2S. The scope of the reaction was investigated using a Hammett linear free energy relationship study, and the determined ρ = +0.34 is consistent with the proposed SN2Ar reaction mechanism. The efficacy of the developed probes was demonstrated in buffer and in serum with associated sub-micromolar detection limits as low as 190 nM (buffer) and 380 nM (serum). Furthermore, the sigmoidal response of nitrobenzofurazan electrophiles with H2S can be fit to accurately quantify H2S. The developed detection strategy offers a manifold for H2S detection that we foresee being applied in various future applications.
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