Lomize A L, Arsen'ev A S, Maslennikov I V, Bystrov V F
Bioorg Khim. 1990 Oct;16(10):1310-24.
The local structure (torsion angles phi, psi and chi 1 of amino acid residues) of insectotoxin I5A (35 residues) of scorpion Buthus eupeus has been determined from cross-peak integral intensities in two-dimensional nuclear Overhauser enhancement (NOESY) spectra and spin coupling constants of vicinal H--NC alpha--H and H--C alpha C beta--H protons. The local structure determination was carried out by fitting complete relaxation matrix of peptide unit protons (protons of a given residue and NH proton of the next residue in the amino acid sequence) with experimental NOESY cross-peak intensities. The obtained intervals of backbone torsional angles phi and psi consistent with NMR data were determined for all but Gly residues. The predominant C alpha--C beta rotamer of the side chain has been unambiguously determined for 42% of the insectotoxin amino acid residues whereas for another 46% residues experimental data are fitted equally well with two rotamers. Stereospecific assignments were obtained for 38% of beta-methylene groups. The determined torsional angles phi, psi and chi 1 correspond to the sterically allowed conformations of the amino acid residues and agree with the insectotoxin secondary structure established earlier by 1H NMR spectroscopy.
通过二维核Overhauser增强(NOESY)谱中的交叉峰积分强度以及邻位H-NCα-H和H-CαCβ-H质子的自旋耦合常数,确定了蝎子东亚钳蝎昆虫毒素I5A(35个残基)的局部结构(氨基酸残基的扭转角φ、ψ和χ1)。通过将肽单元质子(给定残基的质子和氨基酸序列中下一个残基的NH质子)的完整弛豫矩阵与实验性NOESY交叉峰强度进行拟合,来进行局部结构的确定。除甘氨酸残基外,确定了所有与NMR数据一致的主链扭转角φ和ψ的区间。已明确确定了42%的昆虫毒素氨基酸残基侧链的主要Cα-Cβ旋转异构体,而另外46%的残基的实验数据与两种旋转异构体的拟合效果同样良好。对38%的β-亚甲基进行了立体特异性归属。所确定的扭转角φ、ψ和χ1对应于氨基酸残基的空间允许构象,并且与先前通过1H NMR光谱确定的昆虫毒素二级结构一致。