We report herein the top–down lignomic analysis of virgin released lignin (VRL) extracted from the French oak wood using atmospheric pressure photoionization quadrupole orthogonal time‐of‐flight mass spectrometry (APPI‐QqTOF‐MS) (+ ion mode). Eight major protonated lignin oligomers were identified using the APPI‐QqTOF‐MS/MS of this complex VRL mixture without any kind of purification. This series of protonated oligomer ions were identified as neolignan cedrusin (1), five different aryltetralin lignans dimers (2–6), one lignan‐dehydroshikimic acid complex (7), and a lignan trimer (8). Similarly, electrospray ionization (ESI)‐QqTOF‐MS (+ ion mode) allowed us to identify three extra aryltetralin lignan derivatives (9–11). The Kendrick mass defect analysis was used for the simplification of this complex APPI‐QqTOF‐MS into a compositional map, which displayed clustering points of associated ions possessing analogous elemental composition. This series of novel protonated molecules were selected and subjected to low‐energy collision‐induced dissociation (CID)‐MS/MS analyses. The obtained gas‐phase fragmentation patterns helped to tentatively assign their most likely structures. Also, it was found that the use of different APPI and ESI ambient ionization techniques enhances the ionization of different types of lignin oligomers.

中文翻译：

---

通过大气压光电离和电喷雾电离四极杆飞行时间串联质谱法对法国橡木木质素进行自上而下的木质素分析：鉴定一系列新型木脂素

我们在此报告了使用大气压光电离四极杆正交飞行时间质谱（APPI-QqTOF-MS）（+离子模式）从法国橡木中提取的原始释放木质素（VRL）的自上而下的木质素分析。使用这种复杂的 VRL 混合物的 APPI-QqTOF-MS/MS 鉴定了八种主要的质子化木质素低聚物，无需任何形式的纯化。这一系列质子化低聚物离子被鉴定为新木脂素雪松素 ( 1 )、五种不同的芳基四氢化萘木脂素二聚体 ( 2-6 )、一种木脂素-脱氢莽草酸复合物 ( 7 ) 和木脂素三聚体 ( 8 )。同样，电喷雾电离 (ESI)-QqTOF-MS（+ 离子模式）使我们能够鉴定出三种额外的芳基四氢化萘木酚素衍生物 ( 9– 11）。Kendrick 质量缺陷分析用于将这种复杂的 APPI-QqTOF-MS 简化为组成图，该图显示了具有类似元素组成的相关离子的聚集点。选择这一系列新型质子化分子并进行低能碰撞诱导解离 (CID)-MS/MS 分析。获得的气相破碎模式有助于初步确定它们最可能的结构。此外，还发现使用不同的 APPI 和 ESI 环境电离技术增强了不同类型木质素低聚物的电离。