Richmond Gregory S, Smith Terry K
Wellcome Trust Biocentre, Division of Biological Chemistry and Molecular Microbiology, College of Life Sciences, University of Dundee, Dundee DD1 5EH, Scotland, UK.
Biochem J. 2007 Jul 15;405(2):319-29. doi: 10.1042/BJ20070193.
Lysophospholipids are ubiquitous intermediates in a variety of metabolic and signalling pathways in eukaryotic cells. We have reported recently that lysoglycerophosphatidylcholine (lyso-GPCho) synthesis in the insect form of the ancient eukaryote Trypanosoma brucei is mediated by a novel phospholipase A1 (TbPLA1). In the present study, we show that despite equal levels of TbPLA1 gene expression in wild-type insect and bloodstream trypomastigotes, both TbPLA1 enzyme levels and lysoGPCho metabolites are approx. 3-fold higher in the bloodstream form. Both of these parasite stages synthesize identical molecular species of lysoGPCho. TbPLA1 null mutants in the bloodstream form of the parasite are viable, but are deficient in lysoGPCho synthesis, a defect that can be overcome by the expression of an ectopic copy of TbPLA1. The biochemical attributes of TbPLA1-mediated lysoGPCho synthesis were examined in vitro using recombinant TbPLA1. Although TbPLA1 possesses an active-site serine residue, it is insensitive to serine-modifying reagents, such as di-isopropyl fluorophosphate and PMSF, a characteristic shared by lipases that possess lid-sheltered catalytic triads. TbPLA1 does not require metal co-factors for activity, but it does require interfacial activation prior to catalysis. Results from size-exclusion chromatography and binding kinetics analysis revealed that TbPLA1 activation by Triton X-100/GPCho mixed micelle surfaces was not specific and did not require the pre-formation of a specific enzyme-substrate complex to achieve surface binding.
溶血磷脂是真核细胞中多种代谢和信号通路中普遍存在的中间体。我们最近报道,古老真核生物布氏锥虫的昆虫型中溶血甘油磷脂酰胆碱(lyso-GPCho)的合成是由一种新型磷脂酶A1(TbPLA1)介导的。在本研究中,我们发现尽管野生型昆虫型和血流型锥鞭毛体中TbPLA1基因表达水平相同,但血流型中的TbPLA1酶水平和lysoGPCho代谢产物均约高3倍。这两种寄生虫阶段合成的lysoGPCho分子种类相同。寄生虫血流型中的TbPLA1基因敲除突变体是有活力的,但lysoGPCho合成存在缺陷,该缺陷可通过表达TbPLA1的异位拷贝来克服。使用重组TbPLA1在体外研究了TbPLA1介导的lysoGPCho合成的生化特性。尽管TbPLA1具有一个活性位点丝氨酸残基,但它对丝氨酸修饰试剂如二异丙基氟磷酸酯和苯甲基磺酰氟不敏感,这是具有盖子遮蔽催化三联体的脂肪酶共有的特征。TbPLA1的活性不需要金属辅因子,但在催化之前确实需要界面激活。尺寸排阻色谱和结合动力学分析结果表明,Triton X-100/GPCho混合胶束表面对TbPLA1的激活不具有特异性,也不需要预先形成特定的酶-底物复合物来实现表面结合。