Analysis of sesquiterpene pyridine alkaloids using ESI–MS/MS: The product ion at m / z 310 formed by an ion–dipole intermediate

Cai, Tian; Luo, Yinggang; Zhou, Min; Wu, Zhijun; Fang, Dong‐Mei; Zhang, Guolin

doi:10.1016/j.ijms.2014.11.014

Cited by 6 publications

(4 citation statements)

References 26 publications

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“…In the low mass range, the product ions at m / z 105 and 206 are the characteristic ions of the benzoic acid group linked to C1 and the pyridine part, respectively. The product ion at m / z 178 resulted from m / z 206 with the loss of CO. An interesting product ion at m / z 310 was detected and corresponding processes involve an intermediate formed by the McLafferty‐type rearrangement and an ion–neutral complex intermediate (Scheme (a)) . An interesting product ion was also detected at m / z 310 in the MS/MS spectrum of compound 2 .…”

Section: Resultsmentioning

confidence: 96%

“…The product ion at m/z 178 resulted from m/z 206 with the loss of CO. An interesting product ion at m/z 310 was detected and corresponding processes involve an intermediate formed by the McLafferty-type rearrangement and an ion-neutral complex intermediate (Scheme 1(a)). [27][28][29][30][31] An interesting product ion was also detected at m/z 310 in the MS/MS spectrum of compound 2. The major fragmentation pathways of compound 3 are similar to those of compounds 1 and 2.…”

Section: Esi-ms/ms Analysis Of Reference Compounds 1-15mentioning

confidence: 99%

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Untargeted analysis of sesquiterpene pyridine alkaloids from the dried roots of Tripterygium wilfordii using high‐performance liquid chromatography/electrospray ionization tandem mass spectrometry

Cai

Luo

Zhou

et al. 2015

Rapid Comm Mass Spectrometry

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Section: Resultsmentioning

confidence: 96%

Section: Esi-ms/ms Analysis Of Reference Compounds 1-15mentioning

confidence: 99%

Untargeted analysis of sesquiterpene pyridine alkaloids from the dried roots of Tripterygium wilfordii using high‐performance liquid chromatography/electrospray ionization tandem mass spectrometry

Cai

Luo

Zhou

et al. 2015

Rapid Comm Mass Spectrometry

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“…The processes do not occur in the [M + NH 4 ] + ions. Recently, Wu et al studied protonated sesquiterpene pyridine alkaloids using ESI‐QTOF (Cai et al, ). The product ions resulting from the internal residue loss of the dihydroagarofuran moiety could be detected (Fig.…”

Section: Characteristic Fragmentation Patternsmentioning

confidence: 99%

Recent (2000–2015) developments in the analysis of minor unknown natural products based on characteristic fragment information using LC–MS

Cai

Guo

et al. 2016

Mass Spectrometry Reviews

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Liquid chromatography-Mass Spectrometry (LC-MS) has been widely used in natural product analysis. Global detection and identification of nontargeted components are desirable in natural product research, for example, in quality control of Chinese herbal medicine. Nontargeted components analysis continues to expand to exciting life science application domains such as metabonomics. With this background, the present review summarizes recent developments in the analysis of minor unknown natural products using LC-MS and mainly focuses on the determination of the molecular formulae, selection of precursor ions, and characteristic fragmentation patterns of the known compounds. This review consists of three parts. Firstly, the methods used to determine unique molecular formula of unknown compounds such as accurate mass measurements, MS spectra, or relative isotopic abundance information, are introduced. Secondly, the methods improving signal-to-noise ratio of MS/MS spectra by manual-MS/MS or workflow targeting-only signals were elucidated; pure precursor ions can be selected by changing the precursor ion isolated window. Lastly, characteristic fragmentation patterns such as Retro-Diels-Alder (RDA), McLafferty rearrangements, "internal residue loss," and so on, occurring in the molecular ions of natural products are summarized. Classical application of characteristic fragmentation patterns in identifying unknown compounds in extracts and relevant fragmentation mechanisms are presented (RDA reactions occurring readily in the molecular ions of flavanones or isoflavanones, McLafferty-type fragmentation reactions of some natural products such as epipolythiodioxopiperazines; fragmentation by "internal residue loss" possibly involving ion-neutral complex intermediates). © 2016 Wiley Periodicals, Inc. Mass Spec Rev 37:202-216, 2018.

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“…[22][23][24] Both of these concepts remain important for the analytical interpretation of mass spectra generated by different ionisation techniques and, in fact, their ubiquitous occurrence is of utmost relevance to our mechanistic understanding of mass spectra. 25,26 In this contribution, we present the ion/neutral complexbased rational of an intriguing fragmentation behaviour observed during a systematic investigation into the constituents of agarwood. This natural material, also known as "chenxiang" in Chinese, is the fragrant resinous heartwood obtained from certain trees of the genus Aquilaria (Malvales: Thymelaeaceae).…”

Section: Introductionmentioning

confidence: 99%

Fragmentation of Protonated 2-(2-Phenylethyl)Chromones from Agarwood: The Diagnostic Role of Ion/Neutral Complexes as Reactive Intermediates

Yang

Xia

Jiang

et al. 2015

Eur J Mass Spectrom (Chichester)

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A positive-ion electrospray ionisation collision-induced dissociation mass spectrometric study on the fragmentation of the [M + H](+) ions of 2-(2-phenylethyl)chromone and a set of nine hydroxyl- and/or methoxy-substituted derivatives has revealed a highly prominent fragmentation channel, the loss of benzoquinomethanes or a benzaldehyde, respectively, as a diagnostic feature for 2-(2-phenylethyl)chromones that bear a hydroxyl group at the para- (4'-), ortho- (2'-) and/or benzylic (α-) position of the phenylethyl residue. Derivatives that bear only a meta- (3'-) hydroxyl group do not undergo this elimination. The intermediacy of ion/neutral complexes (INCs) is invoked to explain this fragmentation, which involves the remarkable intra-complex proton or hydrogen atom transfer from the remote 4'-OH (or the 2'- or α-OH) functionalities. Density functional theory (B3LYP/6-31G(d)) calculations confirm the energetic preference for these elimination channels and agree with the limited thermochemical data known for para- and ortho- benzoquinomethanes. The INC-mediated losses of the benzaldehydes from the [M + H](+) ions of the α-hydroxy-substituted 2-(2-phenylethyl)chromones correspond to a particularly facile (vinylogous) Grob fragmentation. The study may be viewed as a telling example of the diagnostic role of ion/neutral complexes as intermediates for the structural assignment of constitutional isomers by mass spectrometry.

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Analysis of sesquiterpene pyridine alkaloids using ESI–MS/MS: The product ion at m / z 310 formed by an ion–dipole intermediate

Cited by 6 publications

References 26 publications

Untargeted analysis of sesquiterpene pyridine alkaloids from the dried roots of Tripterygium wilfordii using high‐performance liquid chromatography/electrospray ionization tandem mass spectrometry

Untargeted analysis of sesquiterpene pyridine alkaloids from the dried roots of Tripterygium wilfordii using high‐performance liquid chromatography/electrospray ionization tandem mass spectrometry

Recent (2000–2015) developments in the analysis of minor unknown natural products based on characteristic fragment information using LC–MS

Fragmentation of Protonated 2-(2-Phenylethyl)Chromones from Agarwood: The Diagnostic Role of Ion/Neutral Complexes as Reactive Intermediates

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