Martin B M, Chibber B A, Maelicke A
J Biol Chem. 1983 Jul 25;258(14):8714-22.
We have chemically modified groups of amino acids in the sequence of alpha-cobratoxin and have studied the derivatives as to their affinity of binding to the acetylcholine receptor protein from Torpedo marmorata. (i) The toxin derivatives which were fully modified at lysine (penta-epsilon-N,N-dimethyl lysine; penta-epsilon-N-acetyl lysine), arginine (penta-N7,N8-(1,2-dihydroxycyclohex-1,2-ylene arginine), and tyrosine (mononitrotyrosine) all had significant remaining toxicity and affinity of binding. (ii) The "extra" disulfide of alpha-cobratoxin was selectively reduced and alkylated. Depending on the charge, size, and hydrophobicity of the attached groups, derivatives were obtained that bound to the acetylcholine receptor with higher (di-S-carboxyamidomethyl), about equal (di-S-pyridylethyl), or lower (di-iodoacetaminoethylnaphthylamine-5-sulfonic acid) affinity than the unmodified toxin. (iii) A fully reduced and carbamidomethylated derivative of alpha-cobratoxin obtained by repeating the procedure for selective reduction six times still bound with appreciable affinity (KD approximately 3 X 10(-6) M) to the acetylcholine receptor. We conclude that neither a single positively charged residue nor tyrosine nor the integrity of the disulfides is absolutely essential for toxicity. Furthermore, the single tyrosine and the area around the extra disulfide do not participate in the binding to the receptor. Together with previous findings on this interaction, this suggests a multipoint attachment of toxin and receptor involving several locally separate structural elements of the toxin.
我们对α-银环蛇毒素序列中的氨基酸基团进行了化学修饰,并研究了这些衍生物与电鳐乙酰胆碱受体蛋白的结合亲和力。(i)在赖氨酸(五-ε-N,N-二甲基赖氨酸;五-ε-N-乙酰赖氨酸)、精氨酸(五-N7,N8-(1,2-二羟基环己-1,2-亚基精氨酸)和酪氨酸(单硝基酪氨酸)上完全修饰的毒素衍生物都具有显著的剩余毒性和结合亲和力。(ii)α-银环蛇毒素的“额外”二硫键被选择性还原和烷基化。根据连接基团的电荷、大小和疏水性,获得了与未修饰毒素相比,以更高(二-S-羧酰胺甲基)、大致相等(二-S-吡啶基乙基)或更低(二碘乙酰氨基乙基萘胺-5-磺酸)亲和力与乙酰胆碱受体结合的衍生物。(iii)通过重复六次选择性还原程序获得的α-银环蛇毒素的完全还原和氨基甲酰甲基化衍生物仍以可观的亲和力(KD约为3×10-6M)与乙酰胆碱受体结合。我们得出结论,无论是单个带正电荷的残基、酪氨酸还是二硫键的完整性对于毒性都不是绝对必需的。此外,单个酪氨酸和额外二硫键周围的区域不参与与受体的结合。结合此前关于这种相互作用的研究结果,这表明毒素和受体通过多个位点结合,涉及毒素几个局部独立的结构元件。