State Key Laboratory of Component-based Chinese Medicine, Tianjin Key Laboratory of TCM Chemistry and Analysis, Tianjin University of Traditional Chinese Medicine, 10 Poyanghu Road, Jinghai, Tianjin 301617, China.
State Key Laboratory of Component-based Chinese Medicine, Tianjin Key Laboratory of TCM Chemistry and Analysis, Tianjin University of Traditional Chinese Medicine, 10 Poyanghu Road, Jinghai, Tianjin 301617, China.
J Chromatogr A. 2022 Mar 29;1667:462904. doi: 10.1016/j.chroma.2022.462904. Epub 2022 Feb 13.
Liquid chromatography/mass spectrometry (LC/MS) is extensively applied for the untargeted/targeted analyses of the herbal components, utilizing data-dependent acquisition (DDA) or data-independent acquisition (DIA) to record the fragmentation information useful for the structural elucidation. A new trend recently has emerged by integrating DDA and DIA to render the hybrid scan, which, unfortunately, has rarely been reported. Herein, by using the Vion™ ion-mobility quadrupole time-of-flight mass spectrometer, a hybrid scan strategy (HDMS-HDDDA) was presented and validated by the untargeted characterization of the multicomponents from Carthamus tinctorius (safflower), in combination with reversed-phase ultra-high performance liquid chromatography (RP-UHPLC). Good chromatographic separation was achieved on an HSS T3 column within 26 min, while HDMS-MS/MS was used to acquire the collision-induced dissociation MS data in the negative mode. Automatic workflows (e.g., data correction, precursors/product ions matching, and peak annotation) were well established on UNIFI™ (incorporating an in-house library recording 261 known compounds) to process the obtained MS data. Compared with single DDA or DIA, the hybrid approach of HDMS-HDDDA better balanced between the coverage and reliability, led to high-definition MS spectra, offered useful collision cross section (CCS) information, and showed satisfactory identification performance comparable to MS. A total of 141 components (involving 41 quinochalcones, 66 flavanols/flavones, 11 flavanones, 6 organic acids, 1 polyacetylene, and 16 others) were characterized from safflower. Moreover, CCS prediction could assist isomers characterization, to some extent. Conclusively, this hybrid scan approach enables a dimension-enhanced MS data acquisition strategy providing the complementary structural information, which more suits the chemical characterization of complex samples.
液相色谱/质谱联用 (LC/MS) 广泛应用于草药成分的非靶向/靶向分析，利用数据依赖采集 (DDA) 或数据非依赖采集 (DIA) 记录有助于结构阐明的碎片信息。最近出现了一种新趋势，即将 DDA 和 DIA 集成以实现混合扫描，但遗憾的是，这种方法很少有报道。本文采用 Vion™ 离子迁移四极杆飞行时间质谱仪，提出了一种混合扫描策略 (HDMS-HDDDA)，并通过红花中多组分的非靶向特征分析进行了验证，同时结合反相超高效液相色谱 (RP-UHPLC)。在 HSS T3 柱上，在 26 分钟内实现了良好的色谱分离，而 HDMS-MS/MS 则用于在负离子模式下获取碰撞诱导解离 MS 数据。在 UNIFI™（包含一个记录 261 种已知化合物的内部库）上建立了良好的自动工作流程（例如，数据校正、前体/产物离子匹配和峰注释），以处理获得的 MS 数据。与单一 DDA 或 DIA 相比，HDMS-HDDDA 的混合方法在覆盖度和可靠性之间更好地平衡，获得了高清晰度的 MS 谱图，提供了有用的碰撞截面 (CCS) 信息，并显示出与 MS 相当的令人满意的鉴定性能。从红花中鉴定出 141 种成分（涉及 41 种查尔酮、66 种黄烷醇/黄酮、11 种黄烷酮、6 种有机酸、1 种聚乙炔和 16 种其他成分）。此外，CCS 预测在一定程度上可以辅助异构体的鉴定。总之，这种混合扫描方法可实现增强维度的 MS 数据采集策略，提供互补的结构信息，更适合复杂样品的化学特征分析。
