Application of the Recognizing Ability for L-Cysteine Residue to Peptide-Analysis using the Trigonal-Bipyramidal Palladium(II) Complex

L-半胱氨酸残基识别能力在三角双锥钯(II)络合物肽分析中的应用

• 批准号: 12640583
• 负责人: AIZAWA Sen-ichi
• 金额: $ 2.3万
• 依托单位: Toyama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12640583/
• 关键词: Trigonal-bipyramidal palladium(II) complex; L-Cysteine residue; Thiolate sulfur; Molecular Recognition; Glutathione; 含硫ペプチド; 分子認識; Trigonal-bipyramidal palladium(II) complex; L-Cysteine residue; Thiolate sulfur; Molecular Recognition; Glutathione; 含硫ペプチド; 分子認識

The high selectivity for the thiolato sulfur atom in the axial position of the five-coordinate trigonal-bipyramidal palladium(II) complexes with tris (2-(diphenylphosphino) -ethyi)phosphine (pp_3 ) was confirmed. In order to apply such a selectivity to separation of amino acids, an acetonitrile solution of [Pd(pp_3)(CH_3CN)](BF_4)_2 was added to a weakly basic aqueous solution containing four amino acids, L-alanine, L-methionine, L-penicillamine, L-cysteine, and the resultant complex is extracted with chloroform, The chloroform solution showed only the ^<31>P NMR signals for the L-cysteinato complex which was newly isolated. The preference for L-cysteine over L-methionine and L-penicillamine is explained by the electronic and steric reasons. Furthermore, we have applied the selectivity to detection of the L-cysteine residue in glutathione and to determination of the reduced form of glutathione. The pp_3 palladium(II) complex did not react to form a throlato complex with the oxidized form of glutathione. Such a discriminating ability for the oxidation state is quite useful for investigation of the biological redox system. It was also indicated that the glutathionato complex is useful for discrimination of the organotin compounds.

确认了硫代二坐三角双锥体钯（II）配合物与Tris（2-（二苯基磷酸）-Ethyi）磷酸（PP_3）的高选择性的高选择性。 In order to apply such a selectivity to separation of amino acids, an acetonitrile solution of [Pd(pp_3)(CH_3CN)](BF_4)_2 was added to a weakly basic aqueous solution containing four amino acids, L-alanine, L-methionine, L-penicillamine, L-cysteine, and the resultant complex is extracted with chloroform, The chloroform solution仅显示新分离的L-Cysteinato复合物的 ^<31> P NMR信号。通过电子和空间原因解释了对L-半胱氨酸而不是L-甲基二氨酸和L-苯胺的偏爱。此外，我们已经将选择性应用于谷胱甘肽中L-半胱氨酸残基的检测并确定谷胱甘肽的还原形式。 PP_3钯（II）复合物没有反应形成与谷胱甘肽的氧化形式的throlato络合物。这种氧化状态的这种区分能力对于研究生物氧化还原系统非常有用。还表明谷胱甘肽复合物可用于区分器官蛋白化合物。