Department of Applied Biological Chemistry, Faculty of Agriculture, Kindai University, 3327-204 Nakamachi, Nara 631-8505, Japan.
Agricultural Technology and Innovation Research Institute, Kindai University, 3327-204 Nakamachi, Nara 631-8505, Japan.
J Agric Food Chem. 2022 Jul 20;70(28):8645-8652. doi: 10.1021/acs.jafc.2c02365. Epub 2022 Jul 6.
Natural pesticides pyrethrins biosynthesized by are biodegradable and safer insecticides for pest insect control. TcGLIP, a GDSL lipase underpinning the ester bond formation in pyrethrins, exhibits high stereo-specificity for acyl-CoA and alcohol substrates. However, it is unknown how the enzyme recognizes the other structural features of the substrates and whether such specificity affects the product amount and composition in We report here that the cysteamine moiety in (1,3)-chrysanthemoyl CoA and the conjugated diene moiety in ()-pyrethrolone play key roles in the interactions with TcGLIP. CoA released from chrysanthemoyl CoA in the pyrethrin-forming reaction reduces the substrate affinity for TcGLIP by feedback inhibition. ()-Pyrethrolone shows the highest catalytic efficiency for TcGLIP, followed by ()-cinerolone and ()-jasmololone, contributing, at least in part, to determine the pyrethrin compositions in .
由 生物合成的天然杀虫剂除虫菊酯是可生物降解的，对防治害虫的杀虫剂更安全。TcGLIP 是一种 GDSL 脂肪酶，为除虫菊酯中的酯键形成提供支撑，它对酰基辅酶 A 和醇底物表现出高度的立体特异性。然而，目前尚不清楚该酶如何识别底物的其他结构特征，以及这种特异性是否会影响产物的数量和组成。我们在这里报告，(1,3)-菊酰辅酶 A 中的半胱胺部分和 ()-除虫菊醇酮中的共轭二烯部分在与 TcGLIP 的相互作用中发挥关键作用。除虫菊酯形成反应中从菊酰辅酶 A 释放的辅酶 A 通过反馈抑制降低了 TcGLIP 对底物的亲和力。()-除虫菊醇酮对 TcGLIP 表现出最高的催化效率，其次是 ()-丙烯菊酯和 ()-茉莉酮，这至少部分有助于确定 的除虫菊酯组成。
