Aza-Prilezhaev Aziridination-Enabled Multidimensional Analysis of Isomeric Lipids via High-Resolution U-Shaped Mobility Analyzer–Mass Spectrometry

Li, Yuling; Wang, Yiming; Guo, Kang; Tseng, Kuo-feng; Zhang, Xiaoqiang; Sun, Wenjian

doi:10.1021/acs.analchem.4c00481

Cited by 2 publications

(1 citation statement)

References 63 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…D 2 O labeling is particularly attractive for the isotope tracing of lipids as successfully demonstrated for Arabidopsis in this work and previously for duckweeds. While many isomers are still possible for the lipid species with the same molecular formulae depending on fatty acid chain length, sn-position, and double-bond position, many technical advancements are being made to resolve this issue including MS/MS imaging (Sun et al, 2023), MSI with ion mobility separation (Jiang et al, 2023), and ozone (Claes et al, 2021) or other chemical reactions (Li et al, 2024) to determine the double-bond position.…”

Section: Broad Implication and Limitation Of This Studymentioning

confidence: 99%

Mass spectrometry imaging of Arabidopsis thaliana with in vivo D2O labeling

Na,

Lee

2024

Front. Plant Sci.

View full text Add to dashboard Cite

The commonly used analytical tools for metabolomics cannot directly probe metabolic activities or distinguish metabolite differences between cells and suborgans in multicellular organisms. These issues can be addressed by in-vivo isotope labeling and mass spectrometry imaging (MSI), respectively, but the combination of the two, a newly emerging technology we call MSIi, has been rarely applied to plant systems. In this study, we explored MSIi of Arabidopsis thaliana with D2O labeling to study and visualize D-labeling in three classes of lipids: arabidopsides, chloroplast lipids, and epicuticular wax. Similar to other stress responses, D2O-induced stress increased arabidopsides in an hour, but it was relatively minor for matured plants and reverted to the normal level in a few hours. The D-labeling isotopologue patterns of arabidopsides matched with those of galactolipid precursors, supporting the currently accepted biosynthesis mechanism. Matrix-assisted laser desorption/ionization (MALDI)-MSI was used to visualize the spatiotemporal distribution of deuterated chloroplast lipids, pheophytin a, MGDGs, and DGDGs, after growing day-after-sowing (DAS) 28 plants in D2O condition for 3–12 days. There was a gradual change of deuteration amount along the leaf tissues and with a longer labeling time, which was attributed to slow respiration leading to low D2O concentration in the tissues. Finally, deuterium incorporation in epicuticular wax was visualized on the surfaces of the stem and flower. The conversion efficiency of newly synthesized C30 aldehyde to C29 ketone was very low in the lower stem but very high at the top of the stem near the flower or on the flower carpel. This study successfully demonstrated that MSIi can unveil spatiotemporal metabolic activities in various tissues of A. thaliana.

show abstract

Section: Broad Implication and Limitation Of This Studymentioning

confidence: 99%

Mass spectrometry imaging of Arabidopsis thaliana with in vivo D2O labeling

Na,

Lee

2024

Front. Plant Sci.

View full text Add to dashboard Cite

show abstract

Determination of double bond positions in unsaturated fatty acids by pre-column derivatization with dimethyl and dipyridyl disulfide followed by LC-SWATH-MS analysis

Olfert,

Knappe,

Sievers-Engler

et al. 2024

Anal Bioanal Chem

View full text Add to dashboard Cite

Comprehensive in-depth structural characterization of free mono-unsaturated and polyunsaturated fatty acids often requires the determination of carbon-carbon double bond positions due to their impact on physiological properties and relevance in biological samples or during impurity profiling of pharmaceuticals. In this research, we report on the evaluation of disulfides as suitable derivatization reagents for the determination of carbon-carbon double bond positions of unsaturated free fatty acids by UHPLC-ESI-QTOF-MS/MS analysis and SWATH (sequential windowed acquisition of all theoretical mass spectra) acquisition. Iodine-catalyzed derivatization of C = C double bonds with dimethyl disulfide (DMDS) enabled detection of characteristic carboxy-terminal MS2 fragments for various fatty acids in ESI negative mode. The determination of double bond positions of fatty acids with up to three double bonds, the transfer of the method to plasma samples, and its limitations have been shown. To achieve charge-switching for positive ion mode MS-detection, derivatization with 2,2′-dipyridyldisulfide (DPDS) was investigated. It enabled detection of both corresponding characteristic omega-end- and carboxy-end-fragments for fatty acids with up to two double bonds in positive ion mode. It provides a straightforward strategy for designing MRM transitions for targeted LC–MS/MS assays. Both derivatization techniques represent a simple and inexpensive way for the determination of double bond positions in fatty acids with low number of double bonds. No adaptation of MS hardware is required and the specific isotopic pattern of resulting sulfur-containing products provides additional structural confirmation. This reaction scheme opens up the avenue of structural tuning of disulfide reagents beyond DMDS and DPDS using reagents like cystine and analogs to achieve enhanced performance and sensitivity. Graphical Abstract

show abstract

Aza-Prilezhaev Aziridination-Enabled Multidimensional Analysis of Isomeric Lipids via High-Resolution U-Shaped Mobility Analyzer–Mass Spectrometry

Cited by 2 publications

References 63 publications

Mass spectrometry imaging of Arabidopsis thaliana with in vivo D2O labeling

Mass spectrometry imaging of Arabidopsis thaliana with in vivo D2O labeling

Determination of double bond positions in unsaturated fatty acids by pre-column derivatization with dimethyl and dipyridyl disulfide followed by LC-SWATH-MS analysis

Contact Info

Product

Resources

About