Department of Fundamental Chemistry, Institute of Chemistry, University of São Paulo, Av. Prof. Lineu Prestes, 748, Cidade Universitária, São Paulo 05508-000, São Paulo, Brazil.
J Phys Chem A. 2023 Jun 22;127(24):5152-5161. doi: 10.1021/acs.jpca.3c01323. Epub 2023 Jun 7.
Cyclophosphamide (CP or CTX) is a widely used antineoplastic agent, and the evaluation of its efficacy and its impacts on the environment are dependent on mass spectrometry (MS) techniques. Because there is no dedicated experimental study to characterize the actual molecular nature of the CP fragments upon collision-induced dissociation, this work evaluated the chemical structure of the fragments of protonated and sodiated CP and CP protonation sites by infrared multiple photon dissociation spectroscopy supported by density functional theory calculations. This study allowed us to propose a new fragment structure and confirm the nature of multiple fragments, including those relevant for transitions used for CP quantitative and qualitative analyses. Our results also show that there is no spectroscopic evidence that can rule out the existence of aziridinium fragments, making it clear that further studies on the nature of iminium/aziridinium fragments in the gas phase are necessary.
环磷酰胺（CP 或 CTX）是一种广泛使用的抗肿瘤药物，其疗效的评估及其对环境的影响都依赖于质谱（MS）技术。由于没有专门的实验研究来描述在碰撞诱导解离时 CP 片段的实际分子性质，因此本工作通过红外多光子解离光谱结合密度泛函理论计算，评估了质子化和钠化 CP 以及 CP 质子化位点的碎片的化学结构。这项研究使我们能够提出新的碎片结构，并确认多个碎片的性质，包括用于 CP 定量和定性分析的相关片段。我们的结果还表明，没有光谱证据可以排除氮丙啶片段的存在，这清楚地表明有必要进一步研究气相中亚氨基/氮丙啶片段的性质。
