Willner Jakob, Brunnbauer Lukas, Podsednik Maximilian, Gibbs David K, Kriechbaum Ricarda, Spadiut Oliver, Limbeck Andreas
Institute of Chemical Technologies and Analytics, Research Group for Surface Analytics, Trace Analytics and Chemometry, TU Wien, Getreidemarkt 9/164-I2AC, Vienna 1060, Austria.
Institute of Chemical, Environmental and Bioscience Engineering, Research Division Integrated Bioprocess Development, TU Wien, Gumpendorferstraße 1a, Vienna 1060, Austria.
Anal Chem. 2025 Jul 15;97(27):14521-14530. doi: 10.1021/acs.analchem.5c01870. Epub 2025 Jul 1.
Recent instrumental developments in LA-ICP-MS, such as rapid response cells that significantly reduce the washout and the introduction of high-repetition rate lasers, have greatly impacted the field. To fully take advantage of these developments, improvements on the ICP-MS side were necessary. This was achieved by establishing ICP-TOF-MS instruments enabling simultaneous multielement detection suitable for recording the short transient signals generated by modern rapid response cells. These developments enabled a new operational mode for imaging called the single-pulse response (SPR). Nevertheless, quadrupole-based ICP-MS (ICP-Q-MS) instruments are still the most prevalent instrument type nowadays. Even though it provides many benefits, SPR-based imaging has not yet been applied to ICP-Q-MS due to the sequential / detection. However, recent developments enabling shorter dwell times and settling times of ICP-Q-MS systems make a SPR-based imaging approach feasible. In this work, we investigate the potential and limitations of SPR-based imaging using ICP-Q-MS. Therefore, we investigate the relationship between the cycle time and the signal stability by evaluating Ag/Ag while ablating NIST SRM 612. With the results derived, theoretical considerations about the relationship between the peak width, laser repetition rate, and dwell times can be confirmed. In the next step, the effects of different dwell times on image quality and image artifacts are evaluated by imaging a test structure. Finally, the applicability of the SPR-based LA-ICP-Q-MS imaging approach is demonstrated for life science applications by showing SPR multielement measurements of cell samples, detecting 4 elements with a pixel acquisition rate of 100 Hz.
激光烧蚀电感耦合等离子体质谱（LA-ICP-MS）最近在仪器方面取得了进展，例如能显著减少冲洗时间的快速响应池以及高重复频率激光器的引入，这些都对该领域产生了重大影响。为了充分利用这些进展，有必要在电感耦合等离子体质谱（ICP-MS）方面进行改进。通过建立电感耦合等离子体飞行时间质谱（ICP-TOF-MS）仪器实现了这一点，该仪器能够进行同时多元素检测，适用于记录现代快速响应池产生的短瞬态信号。这些进展促成了一种名为单脉冲响应（SPR）的成像新操作模式。然而，基于四极杆的ICP-MS（ICP-Q-MS）仪器仍是目前最普遍的仪器类型。尽管它有诸多优点，但由于其顺序检测方式，基于SPR的成像尚未应用于ICP-Q-MS。不过，最近ICP-Q-MS系统实现了更短的驻留时间和稳定时间，使得基于SPR的成像方法变得可行。在这项工作中，我们研究了使用ICP-Q-MS进行基于SPR成像的潜力和局限性。因此，我们在烧蚀美国国家标准与技术研究院（NIST）标准参考物质612时，通过评估Ag/Ag来研究循环时间与信号稳定性之间的关系。根据得出的结果，可以证实关于峰宽、激光重复频率和驻留时间之间关系的理论考量。下一步，通过对一个测试结构进行成像，评估不同驻留时间对图像质量和图像伪影的影响。最后，通过展示细胞样品的SPR多元素测量，以100 Hz的像素采集速率检测4种元素，证明了基于SPR的LA-ICP-Q-MS成像方法在生命科学应用中的适用性。
