Enhanced Fourier transform for Orbitrap mass spectrometry

Enhanced Fourier transform for Orbitrap mass spectrometry
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DOI:
10.1016/j.ijms.2014.05.019
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发表时间:
2014-08-15
影响因子:
1.8
通讯作者:
Makarov, Alexander
Makarov, Alexander
中科院分区:
化学4区
文献类型:
--
作者:
Lange, Oliver;Damoc, Eugen;Makarov, Alexander

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一种处理周期信号的新方法,将吸收光谱呈现与幅度谱和有限脉冲响应滤波相结合,应用于 Orbitrap 质谱中采集的图像电流瞬变。 Orbitrap 分析仪中形成相干离子包的注入激发机制促进了吸收光谱信号的定相。结合 Orbitrap 分析仪的陷阱和电子设计的广泛改进,该方法允许在离子从外部存储设备喷射到 Orbitrap 分析仪后不到一毫秒内完成激发过程并启动检测,从而避免基线滚动和大的非线性相位校正。对于大多数在采集时间内信号衰减有限的现实分析物,该方法相对于传统的傅里叶变换处理方法实现了 2 倍的分辨率提高。对于快速衰减的完整蛋白质信号,分辨能力的相对增加降低至约 1.4,这符合理论。采用新方法获得的 LC/MS 测量中的峰形和质量精度似乎与传统震级模式 FT 谱中观察到的峰形和质量精度相似。使用校准混合物优化了方法的性能,并在不同的实际样品上进行了测试,包括以输注和 LC/MS 模式提供给质谱仪的复杂肽混合物和蛋白质。 (C) 2014 Elsevier B.V. 保留所有权利。
A novel method for processing of periodic signals, which combines absorption spectra presentation with magnitude spectra and finite-impulse-response filtering, is applied to image current transients acquired in Orbitrap mass spectrometry. Phasing of signal for absorption spectra is facilitated by the excitation-by-injection mechanism of forming coherent ion packets in the Orbitrap analyzer. In conjunction with extensive refinement of the trap and electronics design of the Orbitrap analyzer, this method allows completion of the excitation process and initiation of detection within a fraction of a millisecond after ejection of ions from an external storage device into the Orbitrap analyzer, thus avoiding baseline roll and large non-linear phase corrections. For most real-life analytes with limited signal decay over acquisition time, the method achieves a 2-fold increase of resolving power relative to the traditional Fourier transform processing method. For rapidly decaying signals of intact proteins, the relative increase in resolving power is reduced to about 1.4, which accords with theory. Peak shape and mass accuracy in LC/MS measurements obtained employing the novel method appear to be similar to those observed in traditional magnitude-mode FT spectra. Performance of the method was optimized using calibration mixtures and tested on different real-life samples, including complex peptide mixtures and proteins supplied to the mass spectrometer in infusion and LC/MS modes. (C) 2014 Elsevier B.V. All rights reserved.