Yoshino K, Takao T, Suhara M, Kitai T, Hori H, Nomura K, Yamaguchi M, Shimonishi Y, Suzuki N
Noto Marine Laboratory, Kanazawa University, Ishikawa, Japan.
Biochemistry. 1991 Jun 25;30(25):6203-9. doi: 10.1021/bi00239a018.
Eight sperm-activating peptides containing a novel amino acid were isolated from the egg jelly of the sea urchin Tripneustes gratilla. Accurate mass measurement of the peptide in FAB mass spectrometry showed that the mass of the novel amino acid residue was 224.978. On the basis of the isotopic ion distribution and the degree of unsaturation, the mass value indicated that the elemental composition of the amino acid residue was C9H8O1N1Br1, suggesting that the novel amino acid was bromophenylalanine. Proton NMR spectroscopy, amino acid analysis, and RP-HPLC with three synthetic isomers of bromophenylalanine demonstrated that o-bromophenylalanine was the novel amino acid. Derivatization of the amino acid with Marfey's reagent, (1-fluoro-2,4-dinitrophen-5-yl)-L-alanine amide (FDAA), further indicated that the amino acid was the L-isomer. In other sperm-activating peptides isolated from the egg jelly of the sea urchin, both m- and p-bromophenylalanines were discovered. The presence of m-bromophenylalanine has not been previously reported in natural products, while p-bromophenylalanine is found in theonellamide F, an antifungal bicyclic peptide from a marine sponge.
从海胆（T. gratilla）卵胶膜中分离出了8种含有新型氨基酸的精子激活肽。快原子轰击质谱法（FAB mass spectrometry）对该肽进行精确质量测定表明，新型氨基酸残基的质量为224.978。根据同位素离子分布和不饱和度，该质量值表明氨基酸残基的元素组成为C9H8O1N1Br1，这表明该新型氨基酸为溴苯丙氨酸。质子核磁共振光谱法、氨基酸分析以及使用溴苯丙氨酸的三种合成异构体进行的反相高效液相色谱法（RP-HPLC）表明，邻溴苯丙氨酸是这种新型氨基酸。用马尔费试剂（(1-氟-2,4-二硝基苯-5-基)-L-丙氨酸酰胺，FDAA）对该氨基酸进行衍生化，进一步表明该氨基酸为L-异构体。在从海胆卵胶膜中分离出的其他精子激活肽中，还发现了间溴苯丙氨酸和对溴苯丙氨酸。间溴苯丙氨酸在天然产物中尚未见报道，而对溴苯丙氨酸存在于一种来自海洋海绵的抗真菌双环肽——西奥内拉酰胺F中。
