Vujisić Ljubodrag V, Vučković Ivan M, Makarov Slobodan E, Ilić Bojan S, Antić Dragan Z, Jadranin Milka B, Todorović Nina M, Mrkić Ivan V, Vajs Vlatka E, Lučić Luka R, Curčić Božidar P M, Mitić Bojan M
Faculty of Chemistry, University of Belgrade, Studentski Trg 12-16, 11000 Belgrade, Serbia.
Naturwissenschaften. 2013 Sep;100(9):861-70. doi: 10.1007/s00114-013-1086-6. Epub 2013 Aug 2.
The geophilomorph centipede, Himantarium gabrielis, when disturbed, discharges a viscous and proteinaceous secretion from the sternal glands. This exudate was found by gas chromatography-mass spectrometry, liquid chromatography-high resolution mass spectrometry, liquid chromatography-mass spectrometry-mass spectrometry and NMR analyses to be composed of hydrogen cyanide, benzaldehyde, benzoyl nitrile, benzyl nitrile, mandelonitrile, mandelonitrile benzoate, 3,7,6O-trimethylguanine (himantarine), farnesyl 2,3-dihydrofarnesoate and farnesyl farnesoate. This is the first report on the presence of benzyl nitrile and mandelonitrile benzoate in secreted substances from centipedes. Farnesyl 2,3-dihydrofarnesoate is a new compound, while himantarine and farnesyl farnesoate were not known as natural products. A post-secretion release of hydrogen cyanide by reaction of mandelonitrile and benzoyl nitrile was observed by NMR, and hydrogen cyanide signals were completely assigned. In addition, a protein component of the secretion was analysed by electrophoresis which revealed the presence of a major 55 kDa protein. Analyses of the defensive exudates of other geophilomorph families should produce further chemical surprises.
土栖蜈蚣，加氏希曼蜈蚣，受到干扰时会从胸骨腺分泌出一种粘性蛋白质分泌物。通过气相色谱 - 质谱联用、液相色谱 - 高分辨率质谱、液相色谱 - 质谱 - 质谱联用和核磁共振分析发现，这种渗出物由氰化氢、苯甲醛、苯甲腈、苄腈、扁桃腈、扁桃腈苯甲酸酯、3,7,6 - O - 三甲基鸟嘌呤（希曼碱）、法尼基2,3 - 二氢法尼酸酯和法尼基法尼酸酯组成。这是关于苄腈和扁桃腈苯甲酸酯存在于蜈蚣分泌物质中的首次报道。法尼基2,3 - 二氢法尼酸酯是一种新化合物，而希曼碱和法尼基法尼酸酯此前并不为人所知是天然产物。通过核磁共振观察到扁桃腈和苯甲腈反应后会释放出氰化氢，并且氰化氢信号已完全确定。此外，通过电泳分析了分泌物中的蛋白质成分，结果显示存在一种主要的55 kDa蛋白质。对其他土栖蜈蚣科防御性渗出物的分析应该会带来更多化学上的惊喜。
