Wootton Christopher A, Maillard Julien, Theisen Alina, Brabeck Gregory F, Schat Carlos L, Rüger Christopher P, Afonso Carlos, Giusti Pierre
Bruker Daltonics GmbH & Co. Kg, 28359 Bremen, Germany.
TotalEnergies One Tech, R&D, Downstream Processes & Polymers, TotalEnergies Research & Technology Gonfreville, BP 27, 76700 Harfleur, France.
Anal Chem. 2024 Jul 16;96(28):11343-11352. doi: 10.1021/acs.analchem.4c01370. Epub 2024 Jul 8.
Modern research faces increasingly complex materials with a constant need for new analytical strategies that can provide deeper levels of chemical insight. Ultrahigh resolution mass spectrometry (MS), particularly Fourier transform ion cyclotron resonance (FTICR) MS, has provided a robust analytical foundation. However, MS alone offers limited structural information. Here, we present the first implementation and results from an FTICR MS with fully integrated dual accumulation analysis with gated trapped ion mobility spectrometry (gTIMS) capability. The drastically extended charge capacity and parallel accumulation facilitate the analysis of complex mixtures. We achieved a high dynamic range of 4 orders of magnitude within a single FTICR acquisition event. Simultaneously, the valuable linear relationship between the TIMS elution voltage and reduced mobility was retained over a wide mobility range. Benchmarking the instrument performance with Suwannee River fulvic acid (SRFA) by variable ramp gTIMS analysis allowed separation and unambiguous assignment of different charge state distributions. Application to bio-oils has proven the capability to distinguish the isomeric diversity in these ultracomplex samples, while maintaining the expected FTICR MS resolving power and mass accuracy. Valuable information about the molecular distribution, isomeric diversity, and main molecular differences could directly be extracted within the analysis time of a classical "dilute and shoot" direct infusion experiment. The development of this fully integrated and flexible gTIMS with FTICR MS analysis possesses the potential to significantly change the current landscape of high-resolution mass spectrometric analysis of complex mixtures through the added insight of isomeric complexity afforded by TIMS. The exploration of the added IMS dimension promises transformative effects across diverse fields including energy transition, environmental studies, and biological research.
现代研究面临着日益复杂的材料，不断需要新的分析策略来提供更深入的化学见解。超高分辨率质谱（MS），特别是傅里叶变换离子回旋共振（FTICR）质谱，提供了一个强大的分析基础。然而，仅靠质谱提供的结构信息有限。在此，我们展示了具有门控捕获离子淌度光谱（gTIMS）功能的完全集成双累积分析的FTICR质谱的首次应用及结果。大幅扩展的电荷容量和平行累积有助于复杂混合物的分析。我们在单次FTICR采集事件中实现了4个数量级的高动态范围。同时，在很宽的淌度范围内保留了TIMS洗脱电压与折合淌度之间有价值的线性关系。通过可变斜率gTIMS分析用苏万尼河富里酸（SRFA）对仪器性能进行基准测试，实现了不同电荷态分布的分离和明确归属。应用于生物油已证明能够区分这些超复杂样品中的异构体多样性，同时保持预期的FTICR质谱分辨率和质量精度。在经典的“稀释进样”直接进样实验的分析时间内，可以直接提取有关分子分布、异构体多样性和主要分子差异的有价值信息。这种具有FTICR质谱分析功能的完全集成且灵活的gTIMS的开发，有可能通过TIMS提供的异构体复杂性的额外见解，显著改变当前复杂混合物高分辨率质谱分析的格局。对增加的离子淌度谱（IMS）维度的探索有望在包括能源转型、环境研究和生物学研究在内的多个领域产生变革性影响。
