当前位置:
X-MOL 学术
›
Inorg. Chem.
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
Undervalued N3 Coordination Revealed in the Cisplatin Complex with 2′-Deoxyadenosine-5′-monophosphate by a Combined IRMPD and Theoretical Study
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2017-07-18 00:00:00 , DOI: 10.1021/acs.inorgchem.7b00570
Barbara Chiavarino 1 , Maria Elisa Crestoni 1 , Simonetta Fornarini 1 , Debora Scuderi 2 , Jean-Yves Salpin 3, 4
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2017-07-18 00:00:00 , DOI: 10.1021/acs.inorgchem.7b00570
Barbara Chiavarino 1 , Maria Elisa Crestoni 1 , Simonetta Fornarini 1 , Debora Scuderi 2 , Jean-Yves Salpin 3, 4
Affiliation
![]() |
The complex obtained by the reaction of cisplatin and 2′-deoxyadenosine-5′-monophosphate (5′-dAMP) in water has been isolated and detected by electrospray ionization mass spectrometry. The so-formed cis-[PtCl(NH3)2(5′-dAMP)]+ complex has been studied in detail by infrared multiple photon dissociation (IRMPD) spectroscopy in two spectral ranges, namely, 700–1900 and 2800–3800 cm–1, backed by quantum-chemical calculations at the B3LYP/LACV3P/6-311G** level of theory. In agreement with the computational results, the vibrational spectroscopic characterization of cis-[PtCl(NH3)2(5′-dAMP)]+ shows that the sampled ionic population comprises two major isomers, differentiated in the X–H stretching region by their distinct fragmentation patterns. One of these species presents coordination of the platinum moiety at the N3 position of adenine, whereas in the second one, platinum is bound at the N1 position of adenine. IRMPD kinetics have allowed an estimation of their relative proportions. Surprisingly, the most abundant component of cis-[PtCl(NH3)2(5′-dAMP)]+ is the N3 isomer, although it is slightly less stable than the other potential isomers in the gas phase. In contrast, the lowest-energy species, namely, the one showing cisplatin binding to the N7 position of adenine, seems to be the one less represented in the sampled ionic population. These findings suggest that the reaction of cisplatin with 5′-dAMP is governed by the kinetics of the process occurring in solution rather than by the thermodynamic factors.
中文翻译:
结合IRMPD和理论研究,发现在2'-脱氧腺苷-5'-单磷酸顺铂配合物中低估的N3配位
分离出了顺铂与2'-脱氧腺苷-5'-单磷酸酯(5'-dAMP)在水中反应得到的配合物,并通过电喷雾电离质谱法对其进行了检测。如此形成的顺式-[PtCl(NH 3)2(5'-dAMP)] +络合物已通过红外多光子离解(IRMPD)光谱在两个光谱范围(即700–1900和2800–3800)中进行了详细研究。 cm –1,以B3LYP / LACV3P / 6-311G **理论水平的量子化学计算为后盾。与计算结果一致,顺式-[PtCl(NH 3)2(5'-dAMP)] +的振动光谱表征结果表明,所采样的离子群包括两个主要的异构体,它们在X–H拉伸区域通过其独特的片段化模式进行区分。这些物质中的一种呈现出在腺嘌呤的N 3位置处的铂部分的配位,而在第二种中,铂结合在腺嘌呤的N 1位置处。IRMPD动力学可以估算其相对比例。令人惊讶的是,顺式-[PtCl(NH 3)2(5'-dAMP)] +的最丰富成分N 3是N 3异构体,尽管它在气相中的稳定性略低于其他潜在的异构体。相反,最低能量的物质,即显示顺铂结合到腺嘌呤的N7位置的物质,似乎是在所采样的离子种群中代表较少的物质。这些发现表明,顺铂与5'-dAMP的反应受溶液中发生的动力学的控制,而不是受热力学因素的控制。
更新日期:2017-07-18
中文翻译:

结合IRMPD和理论研究,发现在2'-脱氧腺苷-5'-单磷酸顺铂配合物中低估的N3配位
分离出了顺铂与2'-脱氧腺苷-5'-单磷酸酯(5'-dAMP)在水中反应得到的配合物,并通过电喷雾电离质谱法对其进行了检测。如此形成的顺式-[PtCl(NH 3)2(5'-dAMP)] +络合物已通过红外多光子离解(IRMPD)光谱在两个光谱范围(即700–1900和2800–3800)中进行了详细研究。 cm –1,以B3LYP / LACV3P / 6-311G **理论水平的量子化学计算为后盾。与计算结果一致,顺式-[PtCl(NH 3)2(5'-dAMP)] +的振动光谱表征结果表明,所采样的离子群包括两个主要的异构体,它们在X–H拉伸区域通过其独特的片段化模式进行区分。这些物质中的一种呈现出在腺嘌呤的N 3位置处的铂部分的配位,而在第二种中,铂结合在腺嘌呤的N 1位置处。IRMPD动力学可以估算其相对比例。令人惊讶的是,顺式-[PtCl(NH 3)2(5'-dAMP)] +的最丰富成分N 3是N 3异构体,尽管它在气相中的稳定性略低于其他潜在的异构体。相反,最低能量的物质,即显示顺铂结合到腺嘌呤的N7位置的物质,似乎是在所采样的离子种群中代表较少的物质。这些发现表明,顺铂与5'-dAMP的反应受溶液中发生的动力学的控制,而不是受热力学因素的控制。