As a natural heme protein catalyzing the oxidation of sulfides to sulfoxides without sulfone formation, chloroperoxidase (CPO) is well suited for the degradation of sulfur mustard (HD), a persistent chemical warfare agent that has been widely disposed since World War II and continuously leaks into aquatic environments. Herein, we report the first systematic investigation of CPO-catalyzed degradation of HD and the potential application of CPO in destroying chemical weapons under mild conditions. The related Michaelis–Menten parameters (K_m = 0.17 mM, V_max = 0.06 mM s⁻¹ (R² = 0.935), and k_cat = 2717 s⁻¹) indicated nearly a prominent enzymatic efficiency. Under optimal conditions, 80% of HD was transformed to bis(2-chloroethyl) sulfoxide as identified by mass spectroscopy and nuclear magnetic resonance (NMR) spectroscopy. Other metabolites were also generated during the decontamination process. A plausible oxidation mechanism was proposed based on the degradation products, NMR titration experiments, and molecular dynamics simulations. CPO also promoted the degradation of other chemical weapon agents, namely, Lewisite (L) and venomous agent X (VX), thereby exhibiting a broad substrate scope. The high potential of the developed system for the decontamination of aquatic environments was demonstrated by the successful hatching of zebrafish embryos after HD degradation and the survival of zebrafish (Danio rerio, AB strain) larvae after the degradation of Agent Yellow (L + HD).

作为一种天然血红素蛋白，在不形成砜的情况下催化硫化物氧化为亚砜，氯过氧化物酶 (CPO) 非常适合硫芥 (HD) 的降解，这是一种自二战以来被广泛处置并不断泄漏的持久性化学战剂进入水生环境。在此，我们报告了 CPO 催化降解 HD 的首次系统研究，以及 CPO 在温和条件下销毁化学武器的潜在应用。相关的 Michaelis-Menten 参数（K _m  =  0.17 mM，V _max  =  0.06 mM s ^-1 ( R ² =  0.935)，和k _cat  = 2717 s ^-1) 表明几乎是显着的酶促效率。在最佳条件下，80% 的 HD 转化为双 (2-氯乙基) 亚砜，如质谱和核磁共振 (NMR) 光谱所鉴定。在去污过程中还产生了其他代谢物。基于降解产物、核磁共振滴定实验和分子动力学模拟，提出了一种合理的氧化机制。CPO还促进了其他化学武器剂的降解，即路易斯石（L）和毒剂X（VX），从而表现出广泛的底物范围。HD 降解后斑马鱼胚胎的成功孵化和斑马鱼的存活证明了开发的水生环境净化系统的巨大潜力（Danio rerio，AB菌株）黄剂降解后的幼虫（L  +  HD）。