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Trace Analysis and Reaction Monitoring by Nanophotonic lonization Mass Spectrometry from Elevated Bowtie and Silicon Nanopost Arrays

机译:纳米领结和硅纳米柱阵列的纳米光子电离质谱法进行痕量分析和反应监测

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摘要

Silicon nanopost arrays (NAPA) are used in trace analysis by mass spectrometry (MS) because they enable highly efficient ion production from small molecules and thin tissue sections by UV laser desorption ionization (LDI). Such nanophotonic ionization of adsorbates relies on localized interactions between a nanostructured substrate and laser radiation. In LDI from NAPA, only the component of the oscillating electric field vector that is parallel with the posts couples the laser energy into the nanostructure. Enhancements in control over adsorbate ionization and fragmentation are expected if the surface-parallel component can also interact with the nanostructure. Here, an alternative nanophotonic ionization platform is introduced for LDI-MS, the elevated bowtie (EBT) array by adding triangular chromium features on top of silicon post pairs to form bowties. Compared to NAPA, the threshold fluence for ionization from EBT is lower, and at low laser fluences the ionization efficiency is increased by a factor of approximate to 17. The EBT platform with optimized apex angle exhibits a higher survival yield for molecular ions produced from biomolecules and xenobiotics and allows more control over fragmentation by adjusting the fluence. These unique nanophotonic ionization attributes are utilized for trace analysis and reaction monitoring in complex biological samples.
机译:硅纳米柱阵列(NAPA)用于通过质谱(MS)进行痕量分析,因为它们可以通过紫外线激光解吸电离(LDI)从小分子和薄组织切片中高效产生离子。吸附物的这种纳米光子电离依赖于纳米结构化基底与激光辐射之间的局部相互作用。在来自NAPA的LDI中,只有与柱平行的振荡电场矢量的分量才将激光能量耦合到纳米结构中。如果表面平行的组分也可以与纳米结构相互作用,则有望增强对吸附物离子化和断裂的控制。在这里,为LDI-MS引入了另一种纳米光子电离平台,即通过在硅柱对上添加三角铬特征以形成领结的高架领结(EBT)阵列。与NAPA相比,来自EBT的电离阈值通量更低,并且在低激光通量下,电离效率提高了约17倍。具有最佳顶角的EBT平台对生物分子产生的分子离子具有更高的存活率和异生物素,并通过调整注量来更好地控制碎片。这些独特的纳米光子电离属性可用于复杂生物样品中的痕量分析和反应监测。

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