Persson Egon, Madsen Jesper J, Olsen Ole H
Haemophilia Biology, Novo Nordisk A/S, Novo Nordisk Park, DK-2760, Måløv, Denmark.
Protein Sci. 2014 Dec;23(12):1717-27. doi: 10.1002/pro.2553. Epub 2014 Oct 14.
Formation of the factor VIIa (FVIIa)-tissue factor (TF) complex triggers the blood coagulation cascade. Using a structure-based rationale, we investigated how the length of the linker region between the two epidermal growth factor (EGF)-like domains in FVIIa influences TF binding and the allosteric activity enhancement, as well as the interplay between the γ-carboxyglutamic acid (Gla)-containing and protease domains. Removal of two residues from the native linker was compatible with normal cofactor binding and accompanying stimulation of the enzymatic activity, as was extension by two (Gly-Ser) residues. In sharp contrast, truncation by three or four residues abolished the TF-mediated stabilization of the active conformation of FVIIa and abrogated TF-induced activity enhancement. In addition, FVIIa variants with short linkers associated 80-fold slower with soluble TF (sTF) as compared with wild-type FVIIa, resulting in a corresponding increase in the equilibrium dissociation constant. Molecular modeling suggested that the shortest FVIIa variants would have to be forced into a tense and energetically unfavorable conformation in order to be able to interact productively with TF, explaining our experimental observations. We also found a correlation between linker length and the residual intrinsic enzymatic activity of Ca(2+)-free FVIIa; stepwise truncation resulting in gradually higher activity with des(83-86)-FVIIa reaching the level of Gla-domainless FVIIa. The linker appears to determine the average distance between the negatively charged Gla domain and a structural element in the protease domain, presumably of opposite charge, and proximity has a negative impact on apo-FVIIa activity.
因子VIIa(FVIIa)-组织因子(TF)复合物的形成触发了血液凝固级联反应。基于结构原理,我们研究了FVIIa中两个表皮生长因子(EGF)样结构域之间连接区的长度如何影响TF结合和变构活性增强,以及含γ-羧基谷氨酸(Gla)结构域和蛋白酶结构域之间的相互作用。从天然连接区去除两个残基与正常辅因子结合及伴随的酶活性刺激相容,增加两个(甘氨酸-丝氨酸)残基也是如此。形成鲜明对比的是,截断三个或四个残基消除了TF介导的FVIIa活性构象的稳定,并消除了TF诱导的活性增强。此外,与野生型FVIIa相比,连接区短的FVIIa变体与可溶性TF(sTF)的结合速度慢80倍,导致平衡解离常数相应增加。分子建模表明,最短的FVIIa变体必须被迫进入一种紧张且能量不利的构象,才能与TF进行有效的相互作用,这解释了我们的实验观察结果。我们还发现连接区长度与无Ca(2+)的FVIIa的残余内在酶活性之间存在相关性;逐步截断导致des(83-86)-FVIIa的活性逐渐升高,达到无Gla结构域的FVIIa的水平。连接区似乎决定了带负电荷的Gla结构域与蛋白酶结构域中一个可能带相反电荷的结构元件之间的平均距离,且距离接近对脱辅基FVIIa活性有负面影响。