Ishida Yuko, Kuwahara Yasumasa, Dadashipour Mohammad, Ina Atsutoshi, Yamaguchi Takuya, Morita Masashi, Ichiki Yayoi, Asano Yasuhisa
Biotechnology Research Center and Department of Biotechnology, Toyama Prefectural University, 5180 Kurokawa, Imizu, Toyama 939-0398, Japan.
Asano Active Enzyme Molecule Project, ERATO, JST, 5180 Kurokawa, Imizu, Toyama 939-0398, Japan.
Sci Rep. 2016 Jun 6;6:26998. doi: 10.1038/srep26998.
Soldiers of some eusocial insects exhibit an altruistic self-destructive defense behavior in emergency situations when attacked by large enemies. The swarm-forming invasive millipede, Chamberlinius hualienensis, which is not classified as eusocial animal, exudes irritant chemicals such as benzoyl cyanide as a defensive secretion. Although it has been thought that this defensive chemical was converted from mandelonitrile, identification of the biocatalyst has remained unidentified for 40 years. Here, we identify the novel blood enzyme, mandelonitrile oxidase (ChuaMOX), which stoichiometrically catalyzes oxygen consumption and synthesis of benzoyl cyanide and hydrogen peroxide from mandelonitrile. Interestingly the enzymatic activity is suppressed at a blood pH of 7, and the enzyme is segregated by membranes of defensive sacs from mandelonitrile which has a pH of 4.6, the optimum pH for ChuaMOX activity. In addition, strong body muscle contractions are necessary for de novo synthesis of benzoyl cyanide. We propose that, to protect its swarm, the sacrificial millipede also applies a self-destructive defense strategy-the endogenous rupturing of the defensive sacs to mix ChuaMOX and mandelonitrile at an optimum pH. Further study of defensive systems in primitive arthropods will pave the way to elucidate the evolution of altruistic defenses in the animal kingdom.
一些群居性昆虫的兵蚁在遭遇大型敌人攻击的紧急情况下会表现出一种利他性的自我毁灭防御行为。会形成群体的入侵性千足虫——花莲栉带千足虫,它并非群居性动物,会分泌刺激性化学物质,如苯甲酰氰作为防御性分泌物。尽管人们一直认为这种防御性化学物质是由苯乙腈转化而来,但40年来生物催化剂的身份一直未得到确认。在此,我们鉴定出一种新型血液酶——苯乙腈氧化酶(ChuaMOX),它能以化学计量的方式催化氧气消耗,并将苯乙腈转化为苯甲酰氰和过氧化氢。有趣的是,该酶活性在血液pH值为7时受到抑制,并且这种酶被防御囊膜与苯乙腈分隔开,苯乙腈的pH值为4.6,这是ChuaMOX活性的最适pH值。此外,从头合成苯甲酰氰需要强烈的身体肌肉收缩。我们提出,为了保护其群体,这种自我牺牲的千足虫还采用了一种自我毁灭防御策略——防御囊的内源性破裂,以便在最适pH值下将ChuaMOX和苯乙腈混合。对原始节肢动物防御系统的进一步研究将为阐明动物王国中利他性防御的进化铺平道路。