Kleerekoper Q, Howarth J W, Guo X, Solaro R J, Rosevear P R
Department of Biochemistry and Molecular Biology, University of Texas Medical School-Houston 77225, USA.
Biochemistry. 1995 Oct 17;34(41):13343-52. doi: 10.1021/bi00041a010.
Conformational changes in both free cardiac troponin C (cTnC) and in complex with a recombinant troponin I protein [cTnI(33-211), cTnI(33-80), or cTnI (86-211)] were observed by means of a combination of selective carbon-13 and spin labeling. The paramagnetic effect from the nitroxide spin label, MTSSL, attached to cTnC(C35S) at Cys 84 allowed measurement of the relative distances to the 13C-methyl groups of the 10 methionines of cTnC in the monomer or complex. All 10 1H-13C correlations in the heteronuclear single- and multiple-quantum coherence (HSMQC) spectrum of [13C-methyl] Met cTnC in the complex with cTnI(33-211) were previously assigned [Krudy, G. A., Kleerekoper, Q., Guo, X., Howarth, J. W., Solaro, R. J., & Rosevear, P. R. (1994) J. Biol. Chem. 269, 23731-23735]. In the presence of oxidized spin label, nine of the 10 Met methyl 1H-13C correlations of cTnC were significantly broadened in the cTnC(C35S) monomer. This suggests flexibility within the central helix, or interdomain D/E helical linker, bringing the N- and C-terminal domains in closer proximity than predicted from the crystallographic structure of TnC. In the spin-labeled cTnC(C35S). cTnI(33-211) complex only N-terminal Met methyl 1H-13C correlations of cTnC(C35S) were paramagnetically broadened beyond detection, whereas correlations for Met residues (103, 120, 137, and 157) in the C-terminal domain were not. Thus, complex formation with cTnI decreases interdomain flexibility and maintains cTnC in an extended conformation. This agrees with the recently published study suggesting that sTnC is extended when bound to sTnI [Olah, G. A., & Trewhella, J. (1994) Biochemistry 33, 12800-12806]. The recombinant N-terminal domain of cTnI, cTnI(33-80), gave similar results as observed with cTnI(33-211) when complexed with spin-labeled cTnC(C35S). However, complex formation with the C-terminal fragment, cTnI(86-211), which contains the inhibitory sequence, is insufficient to maintain cTnC extended to the amount observed with either cTnI(33-211) or cTnI(33-80); although compared to that observed in free cTnC, it does cause decreased flexibility in the interdomain linker. In the absence of the N-terminal domain of cTnI, there is a decrease in flexibility within the N-terminal domain of cTnC. Interestingly, the N-terminal domain of cTnC in the reduced spin-labeled complex with cTnI(86-211), in the presence of ascorbate, showed two distinct conformations which were not seen in the complex with cTnI(33-211).(ABSTRACT TRUNCATED AT 400 WORDS)
通过选择性碳 - 13和自旋标记相结合的方法,观察了游离心肌肌钙蛋白C(cTnC)以及与重组肌钙蛋白I蛋白(cTnI(33 - 211)、cTnI(33 - 80)或cTnI(86 - 211))形成复合物时的构象变化。附着在cTnC(C35S)第84位半胱氨酸上的氮氧自由基自旋标记MTSSL产生的顺磁效应,使得能够测量单体或复合物中cTnC的10个甲硫氨酸的13C - 甲基基团之间的相对距离。先前已对与cTnI(33 - 211)形成复合物的[13C - 甲基]Met cTnC的异核单量子和多量子相干(HSMQC)谱中的所有10个1H - 13C相关性进行了归属[Krudy, G. A., Kleerekoper, Q., Guo, X., Howarth, J. W., Solaro, R. J., & Rosevear, P. R. (1994) J. Biol. Chem. 269, 23731 - 23735]。在存在氧化自旋标记的情况下,cTnC(C35S)单体中10个甲硫氨酸甲基的1H - 13C相关性中有9个显著变宽。这表明中央螺旋或结构域间D/E螺旋连接区存在灵活性,使得N端和C端结构域比从TnC的晶体结构预测的距离更近。在自旋标记的cTnC(C35S).cTnI(33 - 211)复合物中,只有cTnC(C35S)的N端甲硫氨酸甲基1H - 13C相关性因顺磁作用而变宽至无法检测,而C端结构域中甲硫氨酸残基(103、120、137和157)的相关性则没有。因此,与cTnI形成复合物会降低结构域间的灵活性,并使cTnC保持伸展构象。这与最近发表的研究结果一致,该研究表明sTnC与sTnI结合时呈伸展状态[Olah, G. A., & Trewhella, J. (1994) Biochemistry 33, 12800 - 12806]。cTnI的重组N端结构域cTnI(33 - 80)与自旋标记的cTnC(C35S)形成复合物时,得到了与cTnI(33 - 211)类似的结果。然而,与包含抑制序列的C端片段cTnI(86 - 211)形成复合物时,不足以使cTnC伸展到与cTnI(33 - 211)或cTnI(33 - 80)观察到的相同程度;尽管与游离cTnC中观察到的情况相比,它确实导致结构域间连接区的灵活性降低。在没有cTnI的N端结构域时,cTnC的N端结构域内的灵活性降低。有趣的是,在存在抗坏血酸的情况下,与cTnI(86 - 211)形成的还原自旋标记复合物中cTnC的N端结构域呈现出两种不同的构象,这在与cTnI(33 - 211)形成的复合物中未观察到。(摘要截短至400字)