A new method for improving LC/Time-of-flight mass spectrometry detection limits using simultaneous ion counting and waveform averaging.
A new method for improving LC/Time-of-flight mass spectrometry detection limits using simultaneous ion counting and waveform averaging.
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一种使用同步离子计数和波形平均来提高 LC/飞行时间质谱检测限的新方法。
DOI：
10.1021/acs.analchem.0c00301
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发表时间：
2019
影响因子：
7.4
通讯作者：
Michisato Toyoda
中科院分区：
文献类型：
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作者：
Yosuke Kawai ; Yumi Miyake ; Toshinobu Hondo ; Jean-Luc Lehmann ; Kentaro Terada ; Michisato Toyoda
采用高速数字转换器和现场可编程门阵列实现了离子计数和波形平均的同时进行，并将其应用于磺胺类药物的超高效液相色谱-飞行时间质谱分析。离子计数通过“峰值检测”（PKD）功能与信号平均（AVG）一起进行。测定了人血清（HS）模型样品基质中的磺胺二甲嘧啶（SDD）和磺胺二甲氧嘧啶（SDMX）。通过同时使用PKD和AVG采集，我们观察到超过3个数量级的样品量（0.010-100.0 pmol）的统一校准曲线。对于“实际”样品量，例如小于1 pmol，离子计数率低于30%，这适合于基于PKD的离子计数，以获得定量准确性和优异的峰识别性能。无法从AVG波形中识别含有200 fmol或更少的样品。加入经乙腈处理的HS后，SDMX离子被严重抑制到不足一半（58.1%）。然而，对于根据PKD波形计算的分析物，观察到色谱峰面积的线性响应。此外，从PKD波形上的峰计算的质量分辨能力比相应的AVG波形好24%，这也提高了分析物鉴定的性能。
Simultaneous ion counting and waveform averaging implemented on a field-programmable gate array compiled with a high-speed digitizer was applied to ultraperformance liquid chromatography-time-of-flight mass spectrometric analysis of sulfa drugs. Ion counting was carried out by a “Peak Detection” (PKD) function that works together with signal averaging (AVG). Sulfadimidine (SDD) and sulfadimethoxine (SDMX) were measured in human serum (HS) model sample matrix. By using simultaneous PKD and AVG acquisition, we observed a unified calibration curve for more than 3 orders of magnitude of sample amounts (0.010–100.0 pmol). The ion count rate for the “practical” sample amounts, such as less than 1 pmol, was below 30%, which is suitable for PKD-based ion counting for quantitative accuracy and excellent peak identification performance. Samples containing 200 fmol or less could not be identified from the AVG waveform. Adding HS treated with acetonitrile severely suppressed the SDMX ion to less than one-half (58.1%). However, a linear response was observed for chromatographic peak area for analytes calculated from PKD waveforms. Also, the mass-resolving power calculated from the peak on the PKD waveform was 24% better than the corresponding AVG waveform, which also improves performance for analyte identification.