Institute for Medical Research and Occupational Health, HR-10000, Zagreb, Croatia.
Skaggs Institute for Chemical Biology, The Scripps Research Institute, La Jolla, CA, 92037, USA.
Chemistry. 2019 Mar 15;25(16):4100-4114. doi: 10.1002/chem.201805051. Epub 2019 Feb 14.
Acetylcholinesterase (AChE), an enzyme that degrades the neurotransmitter acetylcholine, when covalently inhibited by organophosphorus compounds (OPs), such as nerve agents and pesticides, can be reactivated by oximes. However, tabun remains among the most dangerous nerve agents due to the low reactivation efficacy of standard pyridinium aldoxime antidotes. Therefore, finding an optimal reactivator for prophylaxis against tabun toxicity and for post-exposure treatment is a continued challenge. In this study, we analyzed the reactivation potency of 111 novel nucleophilic oximes mostly synthesized using the CuAAC triazole ligation between alkyne and azide building blocks. We identified several oximes with significantly improved in vitro reactivating potential for tabun-inhibited human AChE, and in vivo antidotal efficacies in tabun-exposed mice. Our findings offer a significantly improved platform for further development of antidotes and scavengers directed against tabun and related phosphoramidate exposures, such as the Novichok compounds.
乙酰胆碱酯酶(AChE)是一种能降解神经递质乙酰胆碱的酶,当它与有机磷化合物(OPs)如神经毒剂和杀虫剂发生共价抑制时,可以被肟类化合物重新激活。然而,由于标准吡啶醛肟解毒剂对 tabun 的重新激活效果较低,tabun 仍然是最危险的神经毒剂之一。因此,寻找一种最佳的重激活剂来预防 tabun 毒性和用于暴露后的治疗仍然是一个持续的挑战。在这项研究中,我们分析了 111 种新型亲核肟类化合物的重新激活能力,这些肟类化合物主要是使用铜催化的叠氮-炔环加成反应(CuAAC)三唑连接的炔烃和叠氮化物构建块合成的。我们发现了几种肟类化合物,它们对 tabun 抑制的人乙酰胆碱酯酶具有显著提高的体外重新激活潜力,并在 tabun 暴露的小鼠中具有显著提高的体内解毒效果。我们的研究结果为进一步开发针对 tabun 和相关膦酰胺暴露的解毒剂和清除剂提供了一个显著改进的平台,例如 Novichok 化合物。