Investigation of two common explosives such as cyclonite (RDX) and cyclotetramethylenetetranitramine (HMX) using a mass spectrometer with ultrahigh resolution and accuracy has not been comprehensively performed. Here, ultrahigh mass accuracy 15‐T Fourier transform–ion cyclotron resonance mass spectrometry (FT‐ICR MS) spectra were utilized to comprehensively characterize the adduct ions of RDX and HMX. Two different ionization sources such as a conventional electrospray ionization (ESI) source and a chip‐based static nano‐ESI source were used to investigate the adduct ions of RDX and HMX. The ESI‐MS analyses of two explosives in negative ion mode provide some adduct ions of RDX and HMX even without prior addition of their corresponding anions. A total of six types of adduct ion were characterized: [M + Cl]⁻, [M + HCOO]⁻, [M + NO₂]⁻, [M + CH₃COO]⁻, [M + NO₃]⁻, and [M + C₃H₅O₃]⁻, where M is either RDX or HMX. The ultrahigh accuracy of the 15‐T FT‐ICR MS was utilized to distinguish two closely spaced peaks representing the monoisotopic [M + NO₂]⁻ and second isotopic [M + HCOO]⁻ ions, thereby enabling the discovery of a [M + NO₂]⁻ adduct ion in the ESI analysis of RDX or HMX. [M + NO₂]⁻ and [M + CH₃COO]⁻ adduct ions were only observed when using a static nano‐ESI source. It is the first report explaining the discovery of [M + NO₂]⁻ adduct ion in the ESI‐MS analyses of RDX and HMX.

中文翻译：

---

使用 ESI FT-ICR MS 表征 RDX 和 HMX 爆炸性加合离子


使用具有超高分辨率和精度的质谱仪对旋风石（RDX）和环四亚甲基四硝胺（HMX）等两种常见爆炸物进行调查尚未全面进行。在这里，利用超高质量精度 15-T 傅里叶变换离子回旋共振质谱 (FT-ICR MS) 谱来全面表征 RDX 和 HMX 的加合离子。使用两种不同的电离源（例如传统的电喷雾电离 (ESI) 源和基于芯片的静态纳米 ESI 源）来研究 RDX 和 HMX 的加合离子。即使没有事先添加相应的阴离子，两种炸药在负离子模式下的 ESI-MS 分析也提供了 RDX 和 HMX 的一些加合离子。总共表征了六种类型的加合离子：[M + Cl] ⁻ 、[M + HCOO] ⁻ 、[M + NO ₂ ] ⁻ 、[M + CH ₃ COO] ⁻ 、[M + NO ₃ ] ⁻ 、和 [M + C ₃ H ₅ O ₃ ] ^- ，其中 M 是 RDX 或 HMX。 15-T FT-ICR MS 的超高精度用于区分代表单一同位素 [M + NO ₂ ] ^-和第二同位素 [M + HCOO] ^-离子的两个间隔很近的峰，从而能够发现 [M + RDX 或 HMX 的 ESI 分析中的 NO ₂ ] ^-加合离子。 [M + NO ₂ ] ^-和 [M + CH ₃ COO] ^-加合物离子仅在使用静态纳米 ESI 源时观察到。这是第一份解释在 RDX 和 HMX 的 ESI-MS 分析中发现 [M + NO ₂ ] ^-加合离子的报告。