Picoelectrospray ionization mass spectrometry using narrow-bore chemically etched emitters.

Picoelectrospray ionization mass spectrometry using narrow-bore chemically etched emitters.
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使用窄孔化学蚀刻的发射器,picoelectrospray电离质谱法。

DOI:
10.1007/s13361-013-0749-z
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发表时间:
2014-01
影响因子:
3.2
通讯作者:
Kelly, Ryan T.
Kelly, Ryan T.
中科院分区:
化学3区
文献类型:
--
作者:
Marginean, Ioan;Tang, Keqi;Smith, Richard D.;Kelly, Ryan T.

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在流量低于~10nL/min的情况下,电喷雾电离质谱仪(ESI-MS)由于难以重复制造能够在较低流量下工作的发射器而仅被零星地探索。在这里,我们展示了窄孔化学刻蚀发射器,用于在低至400pl/min的流速下进行稳定的电喷雾。根据分析物浓度的不同,我们观察到两种类型的MS信号响应作为流速的函数。在低浓度时,最佳流速略高于1nL/min,而在高浓度时,信号随着流速的降低而单调减小。例如,消耗500zmoL的样品,对某些多肽产生约10的信噪比。尽管MS信号较低,但在所有情况下,离子利用效率都随着流速的降低而呈指数增加。对于等摩尔的多肽混合物,在这一流速范围内观察到电离效率的显著变化,表明在目前的实验条件下,电离效率是分析物相关的特性。使用低流速和避免不必要的样品稀释,使质量受限的样品受益匪浅。这些发现对痕量生物样品的分析具有重要意义。
Electrospray ionization mass spectrometry (ESI-MS) at flow rates below ~10 nL/min has been only sporadically explored due to difficulty in reproducibly fabricating emitters that can operate at lower flow rates. Here we demonstrate narrow orifice chemically etched emitters for stable electrospray at flow rates as low as 400 pL/min. Depending on the analyte concentration, we observe two types of MS signal response as a function of flow rate. At low concentrations, an optimum flow rate is observed slightly above 1 nL/min, while the signal decreases monotonically with decreasing flow rates at higher concentrations. For example, consumption of 500 zmol of sample yielded signal-to-noise ratios ~10 for some peptides. In spite of lower MS signal, the ion utilization efficiency increases exponentially with decreasing flow rate in all cases. Significant variations in ionization efficiency were observed within this flow rate range for an equimolar mixture of peptides, indicating that ionization efficiency is an analyte-dependent characteristic for the present experimental conditions. Mass-limited samples benefit strongly from the use of low flow rates and avoiding unnecessary sample dilution. These findings have important implications for the analysis of trace biological samples.
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