Physical Chemistry, University of Potsdam, Karl-Liebknecht-Straße 24-25, 14476, Potsdam, Germany.
BAM Federal Institute for Materials Research and Testing, Richard-Willstätter-Straße 11, 12489, Berlin, Germany.
Anal Bioanal Chem. 2016 Sep;408(23):6259-68. doi: 10.1007/s00216-016-9739-x. Epub 2016 Jul 2.
The novel combination of infrared matrix-assisted laser dispersion and ionization (IR-MALDI) with ion mobility (IM) spectrometry makes it possible to investigate biomolecules in their natural environment, liquid water. As an alternative to an ESI source, the IR-MALDI source was implemented in an in-house-developed ion mobility (IM) spectrometer. The release of ions directly from an aqueous solution is based on a phase explosion, induced by the absorption of an IR laser pulse (λ = 2.94 μm, 6 ns pulse width), which disperses the liquid as nano- and micro-droplets. The prerequisites for the application of IR-MALDI-IM spectrometry as an analytical method are narrow analyte ion signal peaks for a high spectrometer resolution. This can only be achieved by improving the desolvation of ions. One way to full desolvation is to give the cluster ions sufficient time to desolvate. Two methods for achieving this are studied: the implementation of an additional drift tube, as in ESI-IM-spectrometry, and the delayed extraction of the ions. As a result of this optimization procedure, limits of detection between 5 nM and 2.5 μM as well as linear dynamic ranges of 2-3 orders of magnitude were obtained for a number of substances. The ability of this method to analyze simple mixtures is illustrated by the separation of two different surfactant mixtures.
新型红外基质辅助激光解吸电离(IR-MALDI)与离子淌度(IM)谱联用技术使我们能够在液态水环境中研究处于天然状态的生物分子。IR-MALDI 源替代了 ESI 源,被应用于我们自主研发的离子淌度(IM)谱仪中。通过吸收一个红外激光脉冲(λ=2.94 μm,6 ns 脉冲宽度),引发相爆炸,将溶液分散成纳米和微液滴,从而实现了直接从水溶液中释放离子。将 IR-MALDI-IM 谱作为分析方法的应用前提是为了实现高分辨率的质谱仪,要求得到狭窄的分析物离子信号峰。这只能通过改善离子去溶剂化作用来实现。完全去溶剂化的一种方法是让簇离子有足够的时间去溶剂化。为了实现这一点,研究了两种方法:一是像 ESI-IM 谱仪一样,在谱仪中添加一个额外的漂移管;二是延迟离子提取。通过这种优化过程,对于许多物质,检测限达到 5 nM 至 2.5 μM 之间,线性动态范围为 2-3 个数量级。该方法还可用于分析简单混合物,通过对两种不同表面活性剂混合物的分离,即可证明这一点。