Chemistry Department, The Pennsylvania State University, University Park, PA, 16802, USA.
Fakultät für Physik, Universität Duisburg - Essen, 47048, Duisburg, Germany.
J Am Soc Mass Spectrom. 2016 Dec;27(12):2014-2024. doi: 10.1007/s13361-016-1492-z. Epub 2016 Sep 22.
Dynamic reactive ionization (DRI) utilizes a reactive molecule, HCl, which is doped into an Ar cluster projectile and activated to produce protons at the bombardment site on the cold sample surface with the presence of water. The methodology has been shown to enhance the ionization of protonated molecular ions and to reduce salt suppression in complex biomatrices. In this study, we further examine the possibility of obtaining improved quantitation with DRI during depth profiling of thin films. Using a trehalose film as a model system, we are able to define optimal DRI conditions for depth profiling. Next, the strategy is applied to a multilayer system consisting of the polymer antioxidants Irganox 1098 and 1010. These binary mixtures have demonstrated large matrix effects, making quantitative SIMS measurement not feasible. Systematic comparisons of depth profiling of this multilayer film between directly using GCIB, and under DRI conditions, show that the latter enhances protonated ions for both components by 4- to ~15-fold, resulting in uniform depth profiling in positive ion mode and almost no matrix effect in negative ion mode. The methodology offers a new strategy to tackle the matrix effect and should lead to improved quantitative measurement using SIMS. Graphical Abstract ᅟ.
动态反应性离子化(DRI)利用反应性分子 HCl,将其掺杂到 Ar 团簇射弹中,并在水存在的情况下在冷样品表面的轰击部位激活以产生质子。该方法已被证明可以增强质子化分子离子的电离,并减少复杂生物基质中的盐抑制。在这项研究中,我们进一步研究了在薄膜深度剖析过程中使用 DRI 获得更好定量的可能性。使用海藻糖薄膜作为模型系统,我们能够为深度剖析定义最佳的 DRI 条件。接下来,该策略应用于由聚合物抗氧化剂 Irganox 1098 和 1010 组成的多层系统。这些二元混合物表现出较大的基质效应,使得定量 SIMS 测量不可行。对该多层膜在直接使用 GCIB 和 DRI 条件下的深度剖析进行系统比较表明,后者使两种成分的质子化离子增强了 4 到 15 倍,从而在正离子模式下实现均匀的深度剖析,并且负离子模式下几乎没有基质效应。该方法为解决基质效应提供了一种新策略,应能改善使用 SIMS 的定量测量。