Direct infusion electrospray ionization–ion mobility–mass spectrometry for comparative profiling of fatty acids based on stable isotope labeling

A rapid method for fatty acids (FAs) comparative profiling based on carboxyl-specific stable isotope labeling (SIL) and direct infusion electrospray ionization–ion mobility–mass spectrometry (ESI–IM–MS) is established. The design of the method takes advantage of the three-dimensional characteristics...

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Bibliographic Details
Published in:Analytica chimica acta 2015-08, Vol.887, p.148-154
Main Authors: Leng, Jiapeng, Guan, Qing, Sun, Tuanqi, Wang, Haoyang, Cui, Jianlan, Liu, Qinghao, Zhang, Zhixu, Zhang, Manyu, Guo, Yinlong
Format: Article
Language:English
Subjects:
Electrospray ionization
Fatty acids
Fatty Acids - analysis
Humans
Ion mobility–mass spectrometry
Isotope Labeling - methods
Limit of Detection
Spectrometry, Mass, Electrospray Ionization - methods
Stable isotope labeling
Thyroid Gland - pathology
Thyroid Neoplasms - pathology
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Summary:A rapid method for fatty acids (FAs) comparative profiling based on carboxyl-specific stable isotope labeling (SIL) and direct infusion electrospray ionization–ion mobility–mass spectrometry (ESI–IM–MS) is established. The design of the method takes advantage of the three-dimensional characteristics of IM–MS including drift time, m/z and ion intensity, for comparison of d0-/d6-2,4-dimethoxy-6-piperazin-1-yl pyrimidine (DMPP)-labeled FAs. In particular, without chromatographic separation, the method allowed direct FAs profiling in complex samples due to the advantageous priority of DMPP in signal enhancement as well as the extra resolution that IM–MS offered. Additionally, the d0-/d6-DMPP-labeled FAs showed expected features, including very similar drift times, 6 Da mass deviations, specific reporter ions, similar MS responses, and adherence to the drift time rule regarding the influence of carbon chain length and unsaturation on relative drift times. Therefore, the introduction of isotope analogs minimized the matrix effect and variations in quantification and ensured accurate identification of non-targeted FAs by those typical features. Peak intensity ratios between d0-/d6-DMPP-labeled ions were subsequently used in relative quantification for the detected FAs. The established strategy has been applied successfully in the rapid profiling of trace free FAs between normal and cancerous human thyroid tissues. Sixteen free FAs were found with the increased level with a statistically significant difference (p 
ISSN:0003-2670
1873-4324
DOI:10.1016/j.aca.2015.06.029