Abstract:Unraveling the complexity of the lipidome requires the development of novel approaches for the structural characterization of lipid species with isomer-level discrimination. Herein, we introduce an online photochemical approach for lipid isomer identification through selective derivatization of double bonds by reaction with singlet oxygen. Lipid hydroperoxide products are generated promptly after laser irradiation. Fragmentation of these species in a mass spectrometer produces diagnostic fragments revealing th… Show more
“…On the other hand, the combination of functional group specific derivatization and MS 2 CID greatly expands the capability of detailed structural analysis of lipids on commercial MS platforms. Notable methods include epoxidation (23,24), converting C=C to hydroperoxides via singlet oxygen (25), and the Paternò-Büchi (PB) reaction (26). The PB-MS/MS approach has been adopted by several groups and applied to common lipid analysis workflows, including shotgun (27), direct analysis (28), LC-MS (29), and MS-imaging (30).…”
This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
“…On the other hand, the combination of functional group specific derivatization and MS 2 CID greatly expands the capability of detailed structural analysis of lipids on commercial MS platforms. Notable methods include epoxidation (23,24), converting C=C to hydroperoxides via singlet oxygen (25), and the Paternò-Büchi (PB) reaction (26). The PB-MS/MS approach has been adopted by several groups and applied to common lipid analysis workflows, including shotgun (27), direct analysis (28), LC-MS (29), and MS-imaging (30).…”
This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
“…As shown in Fig. 2 e, MS image of lipid hydroperoxides (LOOH), indicated that PC 34:1(LOOH) was enhanced in the gray matter (case ii); however, MS 2 I indicated that more 9Δ isomer than the 11Δ isomer existed in the white matter (cases iii and iv) [ 54 ]. Fig.…”
Section: Mass Spectrometry Imaging (Msi) Of Tissues Using Direct Samplingmentioning
In recent years, mass spectrometry (MS) is increasingly attracting interests for clinical applications, which also calls for technical innovations to make a transfer of MS from conventional analytical laboratories to clinics. The system design and analysis procedure should be friendly for novice users and appliable for on-site clinical diagnosis. In addition, the analysis result should be auto-interpreted and reported in formats much simpler than mass spectra. This motivates new ideas for developments in all the aspects of MS. In this review, we report recent advances of direct sampling ionization and miniature MS system, which have been developed targeting clinical and even point-of-care analysis. We also discuss the trend of the development and provide perspective on the technical challenges raised by diseases such as coronavirus SARS-CoV-2.
“…However, the information regarding the C=C locations within the fatty acyl chains was hardly provided through CID MS/MS alone [11,12]. Thus, site-specific derivatization on C=C bonds, such as epoxidation [13][14][15][16], singlet oxygen ene reaction [17], and the Paternò-Büchi (PB) reaction [18,19], have been developed to enable double bond localization in conjunction with CID. Ultraviolet photodissociation (UVPD) as an alternative ion activation method has been utilized independently for providing detailed structural characterization of intact lipids [20][21][22].…”
Unraveling the complexity of the lipidome requires the development of novel approaches to facilitate structural identification and characterization of lipid species with isomer-level discrimination. Ultraviolet photodissociation tandem mass spectrometry (UVPD MS/MS) is a promising tool for structure determination of lipids. The sensitivity of UVPD for lipid analysis however is limited mainly due to weak absorption of UV photons by a C=C. Herein, a C=C site-specific derivatization, the Paternò-Büchi (PB) reaction, was used to incorporate a chromophore to the C=C moiety in fatty acyls, leading to significantly improved UVPD efficiency and sensitivity for pinpointing C=C locations. The wavelength-dependent photodissociation of the PB products demonstrated 4-CF3-benzophenone as the best reagent for UVPD in terms of the efficiency of generating C=C diagnostic fragments and simplicity for C=C location assignments. We demonstrated the effectiveness of this approach for the shotgun profiling of C=C location isomers in different lipid classes from complex lipid extracts, highlighting its potential to advancing the identification of the C=C bond locations in unsaturated lipids.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
