Deciphering Isotopic Fine Structures of Silylated Compounds in Gas Chromatography-Vacuum Photoionization Orbitrap Mass Spectrometry of Bio-Oils

被引:1
作者
Vesga Martinez, Silvia Juliana [1 ,2 ]
Rueger, Christopher P. [1 ,2 ]
Koesling, Paul [1 ,2 ]
Schade, Julian [1 ,2 ]
Ehlert, Sven [3 ]
Tsybin, Yury O. [4 ]
Zimmermann, Ralf [1 ,2 ,5 ]
机构
[1] Univ Rostock, Chair Analyt Chem, Joint Mass Spectrometry Ctr JMSC, D-18059 Rostock, Germany
[2] Univ Rostock, Dept Life Light & Matter LLM, D-18059 Rostock, Germany
[3] Photonion GmbH, D-19061 Schwerin, Germany
[4] Spectroswiss, CH-1015 Lausanne, Switzerland
[5] Helmholtz Zentrum Muenchen, Cooperat Grp Comprehens Mol Analyt, Joint Mass Spectrometry Ctr, D-85764 Neuherberg, Germany
关键词
photoionization; high-resolutionmass spectrometry; fine isotopic structure; silicon; derivatization; bio-oil; CYCLOTRON RESONANCE CELL; FAST PYROLYSIS; IONIZATION; COMPONENTS; PRODUCTS; ELEMENTS; SILICON; BIOMASS; 1ST;
D O I
10.1021/jasms.4c00383
中图分类号
Q5 [生物化学];
学科分类号
071010 ; 081704 ;
摘要
We introduce vacuum resonance-enhanced multiphoton ionization (REMPI) with high-resolution Orbitrap Fourier transform mass spectrometry (FTMS) for analyzing silylated polar compounds. UV laser radiation at 248 nm sensitively and selectively targets aromatic constituents, while high-resolution mass spectrometry (HRMS) enables high-performance mass spectrometric detection. This workflow enhances the detection confidence of polar constituents by identifying unique isotopologue patterns, including at the isotopic fine structure (IFS) level, in analytical standards and complex bio-oils. A direct and derivatized gas chromatography (GC) procedure on a polar standard component mixture allowed us to explore the general ionization and detection characteristics of REMPI FTMS. HRMS enabled the examination of the complex isotopologue profiles, revealing distinct patterns for the CHO x Si y -class compounds. Particularly in complex mixtures, this isobaric/isonucleonic complexity exceeded the classical mass resolution capabilities of the employed Orbitrap D30 series and prompted the usage of prolonged transients via an external data acquisition system. This procedure substantially improved mass spectrometric results by recording the unreduced time-domain transient data for up to 2 s. Notably, the ability to distinguish diagnostic isotopic pairs, such as 12C/29Si vs 13C/28Si with a mass split of similar to 3.79 mDa and 13C12C/28Si29Si vs 13C2/28Si2, with an approximate mass difference of similar to 3.32 mDa, demonstrates a significant and expected performance improvement. Finally, we benchmark the GC HRMS methodology to identify silylated oxygenated and nitrogen-containing constituents in ultracomplex bio-oil samples. The presented approach of utilizing the silicon isotope pattern and unique isotopologue mass splits for increasing attribution confidence can be applied beyond bio-oils toward the general GC analyses of polar oxygenates.
引用
收藏
页码:3242 / 3255
页数:14
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