将无机抗肿瘤药物顺铂与二肽半胱氨酸甘氨酸（CysGly）在溶液中反应，并以其作为谷胱甘肽功能模型，通过电喷雾电离质谱法（ESI-MS）对反应产物进行了分析。选择性复合物，即初级取代产物顺-[PtCl（NH3）2（CysGly）]+和螯合物顺-[PtCl（NH3）（CysGly）]+，经过红外多光子解离（IRMPD）光谱学分析，得到其振动特征。将实验红外离子光谱与不同可能的同分异构体家族的计算红外吸收进行比较，发现CysGly优先通过去质子的硫醇基与铂（II）结合形成单价复合物顺-[PtCl（NH3）2（CysGly）]+，并通过半胱氨酸残基的SH和NH2官能团，进一步发展为S，N-结合的螯合物顺-[PtCl（NH3）（CysGly）]+。此外，我们的研究结果表明铂化反应不影响CysGly肽键的构型，其仍保持反式构型。这些结果为参与细胞顺铂耐药性的谷胱甘肽与Pt（II）复合物的反应性提供了额外的洞察。版权所有©2023 The Authors。由Elsevier Inc.发表，保留所有权利。

The inorganic antineoplastic drug cisplatin was made to react in solution with the dipeptide cysteinylglycine (CysGly), chosen as a functional model of glutathione, and the reaction products were analyzed using electrospray ionization mass spectrometry (ESI-MS). Selected complexes, i.e., the primary substitution product cis-[PtCl(NH3)2(CysGly)]+ and the chelate cis-[PtCl(NH3)(CysGly)]+, were submitted to IR multiple photon dissociation (IRMPD) spectroscopy obtaining their vibrational features. The experimental IR ion spectra were compared with the calculated IR absorptions of different plausible isomeric families, finding CysGly to bind preferentially platinum(II) via its deprotonated thiolic group in the monovalent complex, cis-[PtCl(NH3)2(CysGly)]+, and to evolve in the S,N-bound chelate structure cis-[PtCl(NH3)(CysGly)]+ through the SH and NH2 functionality of the cysteine residue. Moreover, our findings indicate that the platination reaction does not affect the CysGly peptide bond, which remains in its trans configuration. These results provide additional insights into the reactivity of Pt(II)-complexes with glutathione which is involved in cellular cisplatin resistance.Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.