On‐Demand Electrochemical Epoxidation in Nano‐Electrospray Ionization Mass Spectrometry to Locate Carbon–Carbon Double Bonds

Tang, Shuli; Cheng, Heyong; Yan, Xingru

doi:10.1002/ange.201911070

Cited by 20 publications

(7 citation statements)

References 56 publications

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“…The post-column epoxidation/peroxidation does not compromise the LC, so the chain length and number of double bonds in each FA in the mixture can be easily determined from the LC results 27 . Similar approach was reported recently, where FA epoxidation was facilitated by low voltage on nano-ESI sprayer 30 , although there are significant technical differences such as the existence of hydrochloric acid and the polarity of ESI capillary. The drawback of our method, presently, is its low sensitivity, mainly attributable to the poor epoxidation/ peroxidation efficiency.…”

Section: Discussionmentioning

confidence: 60%

Positional determination of the carbon–carbon double bonds in unsaturated fatty acids mediated by solvent plasmatization using LC–MS

Takashima

Toyoshi

Yamamoto

et al. 2020

Sci Rep

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fatty acids (fAs) are the central components of life: they constitute biological membranes in the form of lipid, act as signaling molecules, and are used as energy sources. FAs are classified according to their chain lengths and the number and position of carbon-carbon double bond, and their physiological character is largely defined by these structural properties. Determination of the precise structural properties is crucial for characterizing FAs, but pinpointing the exact position of carbon-carbon double bond in FA molecules is challenging. Herein, a new analytical method is reported for determining the double bond position of mono-and poly-unsaturated fAs using liquid chromatography-mass spectrometry (LC-MS) coupled with solvent plasmatization. With the aid of plasma on ESI capillary, epoxidation or peroxidation of carbon-carbon double bond in FAs is facilitated. Subsequently, molecular fragmentation occurs at or beside the epoxidized or peroxidized double bond via collisioninduced dissociation (CID), and the position of the double bond is elucidated. In this method, FAs are separated by LC, modified by plasma, fragmented via CID, and detected using a time-of-flight mass spectrometer in a seamless manner such that the FA composition in a mixture can be determined. Our method enables thorough characterization of FA species by distinguishing multiple isomers, and therefore can uncover the true diversity of FAs for their application in food, health, and medical sciences. Fatty acids (FAs) are the central components of living organisms as they are structural components of phospholipids and sphingolipids that constitute biological membranes, can be converted into physiologically active signal molecules (i.e. eicosanoids and lysophospholipids), and serve as energy sources 1-5. Their chemical characteristics are primarily determined by their carbon chain length as well as the number and position of carbon-carbon double bonds. Saturated fatty acids (SFAs) do not contain carbon-carbon double bonds and their chemical stability is suitable for cellular energy storage. In contrast, unsaturated FAs contain one or more carbon-carbon double bonds and are relatively unstable compared to SFAs, especially when multiple double bonds are present. Unsaturated FAs with a single carbon-carbon double bond are referred to as mono-unsaturated fatty acids (MUFAs), while those with multiple carbon-carbon double bonds are collectively called poly-unsaturated fatty acids (PUFAs). Unsaturated FAs can be further categorized into several groups, such as ω-3, ω-6, and ω-9 family FAs, where each family is distinguished by the position of the first double bond in relation to the omega carbon. The number and position of double bonds in FAs dictate their biological activities and are considered to be important subjects for human health 2,6,7. Gas chromatography-mass spectrometry (GC-MS) is traditionally used to analyze FAs. To determine the position of carbon-carbon double bonds, derivatization of unsaturated FAs at the double bonds, such as with...

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Section: Discussionmentioning

confidence: 60%

Positional determination of the carbon–carbon double bonds in unsaturated fatty acids mediated by solvent plasmatization using LC–MS

Takashima

Toyoshi

Yamamoto

et al. 2020

Sci Rep

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“…Isomeric structures of lipids, such as C=C bond positional isomers, could reveal information of diseases. C=C bond positions could be identified through fragmentations, such as ozone-induced dissociation [ 46 ], reaction-based dissociation [ 47 , 48 ], and ultraviolet photodissociation [ 49 ], and derivations, such as Paternò-Bǜchi [ 50 ], ozonolysis [ 51 ], epoxidation [ 52 ], and thiol-ene reactions [ 53 ]. Together with tandem MS and MSI, MS 2 I, it revealed the spatial localization of isomeric lipids in biological systems otherwise invisible with traditional MSI.…”

Section: Mass Spectrometry Imaging (Msi) Of Tissues Using Direct Samplingmentioning

confidence: 99%

Recent advances in on-site mass spectrometry analysis for clinical applications

Zhou¹,

Zhang²,

Ouyang³

2022

TrAC Trends in Analytical Chemistry

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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.

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“…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].…”

Section: Introductionmentioning

confidence: 99%

Site-Specific Photochemical Reaction for Improved C=C Location Analysis of Unsaturated Lipids by Ultraviolet Photodissociation

Zhao

Cao

et al. 2022

Research

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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.

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On‐Demand Electrochemical Epoxidation in Nano‐Electrospray Ionization Mass Spectrometry to Locate Carbon–Carbon Double Bonds

Cited by 20 publications

References 56 publications

Positional determination of the carbon–carbon double bonds in unsaturated fatty acids mediated by solvent plasmatization using LC–MS

Positional determination of the carbon–carbon double bonds in unsaturated fatty acids mediated by solvent plasmatization using LC–MS

Recent advances in on-site mass spectrometry analysis for clinical applications

Site-Specific Photochemical Reaction for Improved C=C Location Analysis of Unsaturated Lipids by Ultraviolet Photodissociation

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