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

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.

证实了五配位三方双锥钯(II)与三(2-(二苯基膦)-乙基)膦(pp_3)配合物对轴向位置的硫醇硫原子的高选择性。为了将这种选择性应用于氨基酸的分离，将[Pd(pp_3)(CH_3CN)](BF_4)_2的乙腈溶液添加到含有四种氨基酸、L-丙氨酸、L-蛋氨酸的弱碱性水溶液中、L-青霉胺、L-半胱氨酸，并且用氯仿萃取所得复合物。氯仿溶液仅显示出 31 P NMR信号新分离出的L-半胱氨酸复合物。 L-半胱氨酸优于L-甲硫氨酸和L-青霉胺的原因是电子和空间原因。此外，我们已将选择性应用于谷胱甘肽中 L-半胱氨酸残基的检测以及还原型谷胱甘肽的测定。 pp_3 钯 (II) 络合物不会与氧化形式的谷胱甘肽反应形成 Throlato 络合物。这种氧化态的辨别能力对于生物氧化还原系统的研究非常有用。还表明谷胱甘肽复合物可用于区分有机锡化合物。

项目成果

Makoto Wakabayashi: "Pressure Studies on the motallation of Porphyrin-Carring Copolymers"Macromolecular Chemistry and Physics. 202. 3136-3141 (2001)

Makoto Wakabayashi：“卟啉携带共聚物运动的压力研究”高分子化学和物理。

Sen-ichi Aizawa: "Thiolato-Ligand Substitution Reaction with Halide Ions of Five-Coordinate Trigonal-Bipyramidal Palladium(II) Complexes with Tris(2-(diphenylphosphino)-ethyl)phosphine. Electronic and Steric Effects on the Reaction Mechanism"Bulletin of t

Sen-ichi Aizawa：“五配位三方双锥钯(II)配合物与三(2-(二苯基膦基)-乙基)膦的卤化物离子的硫醇基-配体取代反应。反应机理的电子和空间效应”公告

Sen-ichi Aizawa: "Circular Dichroism Spectrophotometric Determination of Metal Ions Using Optically Active Tris(thiolato) Type Rhodium(III) Complexes"Bulletin of the Chemical Society of Japan. 73・9. 2043-2050 (2000)

Sen-ichi Aizawa：“使用光学活性三(硫醇)型铑(III)络合物的圆二色性分光光度法测定金属离子”日本化学会公报73·9 (2000)。

Sen-ichi Aizawa: "Discrimination of Thiolate Group in L-Cysteinate and Glutathionate by Axial Coordination Site of Five-Coordinate Trigonal-Bipyramidal palladium(II) Complex with Tris(2-(diphenylphosphino)ethyl)phosphine"Chemistry Letters. ・12. 1412-1413

相泽千一：“通过五配位三方双锥钯(II)络合物与三(2-(二苯基膦)乙基)膦的轴向配位位点区分L-半胱氨酸和谷胱甘肽”化学快报·12。 1412-1413

Sen-ichi Aizawa: "Kinetic Effect of Zinc (II) and Cadmium (II) Ions on Configurational Inversion of Δ_<LLL>-fac (S) -Tris (L-cysteinato-N,S) cobalt (III) Complex"Analytical Sciences. (in press). (2001)

Sen-ichi Aizawa：“锌 (II) 和镉 (II) 离子对 Δ_<LLL>-fac (S) -Tris (L-cysteinato-N,S) 钴 (III) 络合物构型反转的动力学效应”分析科学（出版中）。