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激光诱导声学解吸与傅里叶变换离子回旋共振质谱仪联用的表征

Characterization of laser-induced acoustic desorption coupled with a Fourier transform ion cyclotron resonance mass spectrometer.

作者信息

Shea Ryan C, Petzold Christopher J, Campbell J Larry, Li Sen, Aaserud David J, Kenttämaa Hilkka I

机构信息

Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IN 47907-2084, USA.

出版信息

Anal Chem. 2006 Sep 1;78(17):6133-9. doi: 10.1021/ac0602827.

DOI:10.1021/ac0602827
PMID:16944895
Abstract

Several experimental factors have been investigated that influence the efficiency of desorption and subsequent chemical ionization of nonvolatile, thermally labile molecules during laser-induced acoustic desorption/Fourier transform ion cyclotron resonance mass spectrometry (LIAD/FT-ICR) experiments. The experiments were performed by using two specially designed LIAD probes of different outer diameters (1/2 and 7/8 in.) and designs. Several improvements to the design of the "first generation" (1/2 in.) LIAD probe are presented. The larger diameter (7/8 in.) probe provides a larger surface area for desorption than the smaller diameter probe. Further, it was designed to desorb molecules on-axis with the magnetic field of the instrument. This is in contrast to the smaller probe for which desorption occurs 1.3 mm off-axis. This improved alignment, which provides better overlap between the desorbed molecules and trapped reagent ions, results in a substantial increase in the sensitivity of LIAD analyses. The thickness of the sample layer deposited on the irradiated metal foil and the number of laser shots fired on the backside of the foil were found to have a significant effect on the overall signal and the relative abundances of the ions formed in the experiment. Evaporation of a tetrapeptide, Val-Ala-Ala-Phe (VAAF), from Ag, Al, Au, Cu, Fe, and Ti foils, followed by protonation by protonated pyridine, revealed that the titanium foil provides the greatest signal. The importance of the laser power density was examined by desorbing a low MW polymer, polyisobutenyl succinic anhydride, at power densities ranging from 5.40 x 10(8) to 9.00 x 10(8) W/cm(2) at the backside of the foil. Higher laser power densities resulted in greater signals and an improved distribution for the higher molecular weight oligomers.

摘要

在激光诱导声解吸/傅里叶变换离子回旋共振质谱(LIAD/FT-ICR)实验中,研究了几个影响非挥发性、热不稳定分子解吸效率及后续化学电离的实验因素。实验使用了两种外径不同(1/2英寸和7/8英寸)且设计各异的特制LIAD探头来进行。文中给出了对“第一代”(1/2英寸)LIAD探头设计的若干改进。较大直径(7/8英寸)的探头比小直径探头提供了更大的解吸表面积。此外,它被设计成能在仪器磁场的轴上解吸分子。这与较小的探头不同,较小探头的解吸发生在离轴1.3毫米处。这种改进的对准方式使解吸分子与捕获的试剂离子之间有更好的重叠,从而导致LIAD分析灵敏度大幅提高。发现沉积在辐照金属箔上的样品层厚度以及在箔背面发射的激光脉冲数对实验中形成的离子的整体信号和相对丰度有显著影响。从Ag、Al、Au、Cu、Fe和Ti箔上蒸发四肽Val-Ala-Ala-Phe(VAAF),然后用质子化吡啶进行质子化,结果表明钛箔提供的信号最强。通过在箔背面以5.40×10⁸至9.00×10⁸W/cm²的功率密度解吸低分子量聚合物聚异丁烯基琥珀酸酐,研究了激光功率密度的重要性。更高的激光功率密度导致更大的信号以及更高分子量低聚物的分布得到改善。

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