Statistical evaluation of internal and external mass calibration laws utilized in Fourier transform ion cyclotron resonance mass spectrometry
Statistical evaluation of internal and external mass calibration laws utilized in Fourier transform ion cyclotron resonance mass spectrometry
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DOI：
10.1021/ac048258l
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发表时间：
2005-04-15
影响因子：
7.4
通讯作者：
Oberg, AL
中科院分区：
文献类型：
--
作者：
Muddiman, DC;Oberg, AL
提出了傅里叶变换离子回旋共振质谱中使用的两种常见校准定律和三种新校准定律的统计评估。采用电喷雾电离制备了平均分子量为 1000 Da 的铵加合聚丙二醇 (PPG) 的一系列质谱图。单电荷 PPG-1000 低聚物可以描述每个质谱内的广泛 m/z 和丰度值。改变六极杆累积时间以提供大约一个数量级的总离子丰度值范围。为了检查每个校准定律，我们分别对内部和外部校准数据使用“谱内”和“谱间”交叉验证。此外，我们使用 t 统计量来确保每个校准系数具有统计显着性，并且对于准确描述数据的变化是必要的。与常用的内部校准校准定律相比，我们基于多元线性回归的新校准定律将质量测量精度 (MMA) 提高了 2 倍。与没有自动增益控制的外部校准法相比，我们使用多元回归的新校准法将 MMA 提高了 10 倍以上；随着测量动态范围的增加（例如生物系统），这种改进将进一步增加。对于我们的内部和外部校准定律，MMA 中值均小于百万分之一。此外，我们还研究了校准离子的数量及其所需的 m/z 范围，以成功实现高 MMA。
The statistical evaluation of two common and three new calibration laws utilized in Fourier transform ion cyclotron resonance mass spectrometry are presented. Electrospray ionization was used to prepare a series of mass spectra of ammonium-adducted polypropylene glycol (PPG) with an average molecular weight of 1000 Da. The singly charged PPG-1000 oligomers allowed for the description of a broad range of m/z and abundance values within each mass spectrum. The hexapole accumulation time was varied to afford a range of total ion abundance values of about an order of magnitude. To examine each of the calibration laws, we utilized cross-validation both "within-spectrum" and "between-spectra" for internally and externally calibrated data, respectively. In addition, we used t-statistics to ensure that each calibration coefficient was statistically significant and necessary to accurately describe the variation in the data. In comparison to commonly used calibration laws for internal calibration, our new calibration law based on multiple linear regression offered a 2-fold improvement in mass measurement accuracy (MMA). In comparison to external calibration laws without automatic gain control, our new calibration law using multiple regression improved the MMA by > 10-fold; this improvement would increase further as the dynamic range of the measurement increases (e.g., a biological system). For both our internal and external calibration laws, the median MMA was less than 1 part-per-million. Furthermore, we investigate the number of calibrant ions as well as their required m/z range in order to successfully achieve high MMA.