Kaufmann Anton, Walker Stephan
Official Food Control Authority, Fehrenstrasse 15, 8032, Zürich, Switzerland.
Rapid Commun Mass Spectrom. 2017 Nov 30;31(22):1915-1926. doi: 10.1002/rcm.7981.
The linear intrascan and interscan dynamic ranges of mass spectrometers are important in metabolome and residue analysis. A large linear dynamic range is mandatory if both low- and high-abundance ions have to be detected and quantitated in heavy matrix samples. These performance criteria, as provided by modern high-resolution mass spectrometry (HRMS), were systematically investigated.
The comparison included two generations of Orbitraps, and an ion mobility quadrupole time-of-flight (QTOF) system In addition, different scan modes, as provided by the utilized instruments, were investigated. Calibration curves of different compounds covering a concentration range of five orders of magnitude were measured to evaluate the linear interscan dynamic range. The linear intrascan dynamic range and the resulting mass accuracy were evaluated by repeating these measurements in the presence of a very intense background.
Modern HRMS instruments can show linear dynamic ranges of five orders of magnitude. Often, however, the linear dynamic range is limited by the detection capability (sensitivity and selectivity) and by the electrospray ionization. Orbitraps, as opposed to TOF instruments, show a reduced intrascan dynamic range. This is due to the limited C-trap and Orbitrap capacity. The tested TOF instrument shows poorer mass accuracies than the Orbitraps. In contrast, hyphenation with an ion-mobility device seems not to affect the linear dynamic range.
The linear dynamic range of modern HRMS instrumentation has been significantly improved. This also refers to the virtual absence of systematic mass shifts at high ion abundances. The intrascan dynamic range of the current Orbitrap technology may still be a limitation when analyzing complex matrix extracts. On the other hand, the linear dynamic range is not only limited by the detector technology, but can also be shortened by peripheral devices, where the ionization and transfer of ions take place.
质谱仪的线性扫描内和扫描间动态范围在代谢组学和残留分析中很重要。如果要在高背景基质样品中同时检测和定量低丰度和高丰度离子,大的线性动态范围是必不可少的。对现代高分辨率质谱(HRMS)提供的这些性能标准进行了系统研究。
比较包括两代轨道阱,以及一台离子淌度四极杆飞行时间(QTOF)系统。此外,还研究了所用仪器提供的不同扫描模式。测量了覆盖五个数量级浓度范围的不同化合物的校准曲线,以评估线性扫描间动态范围。通过在非常强的背景存在下重复这些测量来评估线性扫描内动态范围和由此产生的质量准确度。
现代HRMS仪器可显示五个数量级的线性动态范围。然而,线性动态范围通常受检测能力(灵敏度和选择性)以及电喷雾电离的限制。与飞行时间仪器相反,轨道阱的扫描内动态范围较小。这是由于C阱和轨道阱容量有限。测试的飞行时间仪器的质量准确度比轨道阱差。相比之下,与离子淌度装置联用似乎不会影响线性动态范围。
现代HRMS仪器的线性动态范围有了显著提高。这也意味着在高离子丰度下几乎不存在系统质量偏移。在分析复杂基质提取物时,当前轨道阱技术的扫描内动态范围可能仍然是一个限制。另一方面,线性动态范围不仅受检测器技术限制,还可能因离子发生电离和转移的外围设备而缩短。