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Correlation between Sweet Spots of Glycopeptides and Polymorphism of the Matrix Crystal in MALDI Samples

机译:MALDI样品中糖肽的甜点与基质晶体多态性的相关性

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摘要

A standard dried-droplet preparation using 2,5-dihydroxybenzoic acid (2,5-DHBA) as the matrix results in a large varia-tion in signal intensity and poor shot-to-shot reproducibility in matrix-assisted laser desorption/ionization (MALDI). We ex-pected that the differences can be attributed to the nature of the crystal structures in the region of the "sweet spot" within the MALDI samples. 2,5-DHBA crystals with and without analytes on a target plate obtained by means of a dried-droplet prepara-tion contain two polymorphs, which can be distinguished by Raman spectra. In comparing the Raman image with the MS im-age, a clear correlation between the signal distribution of glycopeptides and hydrophilic peptides and the specific crystal form of 2,5-DHBA could be made. The ionization of hydrophobic peptides appears to proceed in both types of polymorphic crystals. In addition, the derivatization of glycopeptides with a pyrene group enabled us to detect glycopeptides regardless the crystal form. As the result, the number of sweet spots increased and MS spectra with a high signal intensity were obtained. The results suggest that the introduction of a hydrophobic/aromatic moiety to glycopeptides results in a more successful MALDI analysis due to the effective incorporation of the analyte into matrix crystals.
机译:使用2,5-二羟基苯甲酸(2,5-DHBA)作为基质的标准干滴制剂会导致基质辅助激光解吸/电离中信号强度的大幅度变化和逐次再现性差( MALDI)。我们预计,差异可以归因于MALDI样品中“最佳点”区域中晶体结构的性质。通过干滴制备获得的在目标板上带有或不带有分析物的2,5-DHBA晶体包含两个多晶型物,可以通过拉曼光谱进行区分。通过将拉曼图像与MS图像进行比较,可以得出糖肽和亲水肽的信号分布与2,5-DHBA的特定晶型之间的明确相关性。疏水肽的离子化似乎在两种类型的多晶型晶体中进行。此外,带有a基的糖肽的衍生化使我们能够检测糖肽,无论其晶体形式如何。结果,最佳点数增加,并且获得了具有高信号强度的MS​​光谱。结果表明,由于将分析物有效地掺入基质晶体中,向糖肽中引入疏水/芳族部分导致更成功的MALDI分析。

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