Quantitative Analysis of TAG in Oils Using Lithium Cationization and Direct‐Infusion ESI Tandem Mass Spectrometry

Ramaley, Louis; Herrera, Lisandra Cubero

doi:10.1007/s11746-015-2604-9

Cited by 10 publications

(8 citation statements)

References 39 publications

(81 reference statements)

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“…Using a similar approach, Ramaley and co-workers have demonstrated that the fragmentation profile of lithium adducts of TAGs from fish oil samples can provide both absolute and relative quantitative data with low average errors with the potential to be applied in routine analyses of complex oil samples. The present study demonstrates that the TAGs composition and their relative proportion can be directly accessed from soybean samples using a reagent pencil doped with a lithium salt.…”

Section: Resultsmentioning

confidence: 99%

“…54 In another investigation, lithiated TAG adducts were also generated via direct infusion ESI-MS, and their fragmentation profile was used to accurately perform positional analysis of complex TAG mixtures based on their fragmentation profile. 55 Using a similar approach, Ramaley and co-workers 56 have demonstrated that the fragmentation profile of lithium adducts of TAGs from fish oil samples can provide both absolute and relative quantitative data with low average errors with the potential to be applied in routine analyses of complex oil samples. The present study demonstrates that the TAGs composition and their relative proportion can be directly accessed from soybean samples using a reagent pencil doped with a lithium salt.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Reagent-Pencil and Paper Spray Mass Spectrometry: A Convenient Combination for Selective Analyses in Complex Matrixes

Aquino

Pereira

Dossi

et al. 2020

J. Am. Soc. Mass Spectrom.

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The recent developments on fieldable miniature mass spectrometers require efforts to produce easy-to-use and portable alternative tools to assist in point-of-care analysis. In this paper, the reagent-pencil (RP) technology, which has been used for solvent-free deposition of reagents in paper-based microfluidics, was combined with paper spray ionization mass spectrometry (PS-MS). In this approach, named RP-PS-MS, the PS triangular piece of paper was written with the reagent pencil, consisting of mixtures of graphite and bentonite (used as a support) and a reactive compound, and allowed to react with a given analyte from a sample matrix selectively. We conducted typical applications as proof-of-principles to verify the methodology’s general usefulness in detecting small organic molecules in distinct samples. Hence, various aldehydes (2-furaldehyde, valeraldehyde, and benzaldehyde) in spiked cachaça samples (an alcoholic drink produced from fermentation/distillation of sugarcane juice) were promptly detected using a reagent pencil doped with 4-aminophenol (the reactive compound). Similarly, we recognized typical ginsenosides and triacylglycerols (TAGs) in ginseng aqueous infusions and soybean oil samples, respectively, using lithium chloride as the reactive compound. The results indicate that the reagent-pencil methodology is compatible with PS-MS and provides an easy and fast way to detect target analytes in complex samples. The advantage over the usual solution-based deposition of reagents lies in the lack of preparation or carrying different specific solutions for special applications, which can simplify operation, especially in point-of-care analysis with fieldable mass spectrometers.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Reagent-Pencil and Paper Spray Mass Spectrometry: A Convenient Combination for Selective Analyses in Complex Matrixes

Aquino

Pereira

Dossi

et al. 2020

J. Am. Soc. Mass Spectrom.

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“…Formation of these product ions is typical of the MS 2 spectra of all cationized TAGs and has been well documented. 8,[10][11][12][13][14][15][16]20 Tandem mass spectral data for lithiated tripropanoylglycerol (m/z 267) acquired at different collision energies are shown in Figure 1 where breakdown curves are shown in (a) and a product-ion spectrum at a collision energy of 3 eV in (b). The product ions at m/z 193, [PrPrPr + Li − PrH] + , and m/z 187, [PrPrPr + Li − PrLi] + , have comparable intensities at low collision energy, but as this energy was increased, the intensity of [PrPrPr + Li − PrH] + dropped far more rapidly than that of [PrPrPr + Li − PrLi] + since secondary fragmentation pathways become important.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…Electrospray ionization (ESI-MS) from protic solvents (e.g., methanol) to which no cationizing reagents have been added provides primarily [TAG + Na] + ions. Cationized TAG signals useful for analysis using ESI-MS can be formed by adding Li + , Na + , or NH 4 + to lipid-containing samples. − Data on side chain identity and position can then be obtained by using double-stage tandem mass spectrometry (MS 2 ). The adducts of the alkali metal ions fragment by the loss of either a neutral side-chain acid or a neutral side-chain salt to form diacylglycerol-like ions. , Cationization by Na + gives [TAG + Na – RCOOH] + and [TAG + Na – RCOONa] + as product ions.…”

Section: Introductionmentioning

confidence: 99%

Fragmentation Pathways of Cationized, Saturated, Short-Chain Triacylglycerols: Lithiated and Sodiated Tripropanoyl- and Trihexanoylglycerol

Grossert

Ramaley

2019

J. Am. Soc. Mass Spectrom.

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Many methods, often depending on tandem mass spectrometry, have been developed for analysis of complex mixtures of triacylglycerols (TAGs), especially in clinical diagnostics and food authentication. Understanding the fragmentation mechanisms of cationized TAGs has proved problematic. To obtain a better understanding of viable mechanisms, detailed studies including double- and triple-stage tandem mass spectrometry were made using electrospray ionization on lithiated and sodiated tripropanoyl- and trihexanoylglycerols. Density functional theory computations, including a functional parameterized for van der Waals interactions, were used to correlate computed energies with mass spectra. Losses of both a neutral salt and a neutral acid corresponding to a glycerol side chain were observed as major product ions in MS2 experiments. Signal intensities at low collision energies correlated well with computed energies. However, an important difference between the lithiated and sodiated ions was the appearance of the sodium cation as a major fragmentation product. Computations on the product ions resulting from the loss of a neutral acid indicated multiple structures for the lithiated ions but mainly a single structure for the sodiated ions. The lithiated product ions could be fragmented further (pseudo-MS3) to give additional structural information, whereas the sodiated ions gave only m/z 23. The longer chain TAG, while giving a much less intense mass spectrum than the shorter chain TAG, gave comparable MS2 and MS3 product ion spectra. Taken together, the spectral and computational work described herein offer a new and detailed pathway for collision-induced fragmentation of lithiated and sodiated saturated TAGs.

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“…The alkali-metal ions will form a chelate or complex with the oxygen groups in the molecule. This approach has been described for somewhat larger molecules in various application fields such as the analysis of polysaccharides, polymers, and oils [29,30,31].…”

Section: Introductionmentioning

confidence: 99%

A Sensitive LC-MS/MS Method for Palytoxin Using Lithium Cationization

Klijnstra

Gerssen

2018

Toxins

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Palytoxin (PlTX) and analogues are produced by certain dinoflagellates, sea anemones, corals and cyanobacteria. PlTX can accumulate in the food chain and when consumed it may cause intoxication with symptoms like myalgia, weakness, fever, nausea, and vomiting. The analysis of PlTXs is challenging, and because of the large molecular structure, it is difficult to develop a sensitive and selective liquid chromatography-mass spectrometry (LC-MS/MS) method. In this work, an LC-MS/MS method was developed to analyse PlTXs with use of lithium iodine and formic acid as additives in the mobile phase. For method development, initially, LC-hrMS was used to accurately determine the elemental composition of the precursor and product ions. The main adduct formed was [M + H + 2Li]3+. Fragments were identified with LC-hrMS and these were incorporated in the LC-MS/MS method. A method of 10 min was developed and a solid phase extraction clean-up procedure was optimised for shellfish matrix. The determined limits of detection were respectively 8 and 22 µg PlTX kg−1 for mussel and oyster matrix. Oysters gave a low recovery of approximately 50% for PlTX during extraction. The method was successfully in-house validated, repeatability had a relative standard deviation less than 20% (n = 5) at 30 µg PlTX kg−1 in mussel, cockle, and ensis, and at 60 µg PlTX kg−1 in oyster.

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Quantitative Analysis of TAG in Oils Using Lithium Cationization and Direct‐Infusion ESI Tandem Mass Spectrometry

Cited by 10 publications

References 39 publications

Reagent-Pencil and Paper Spray Mass Spectrometry: A Convenient Combination for Selective Analyses in Complex Matrixes

Reagent-Pencil and Paper Spray Mass Spectrometry: A Convenient Combination for Selective Analyses in Complex Matrixes

Fragmentation Pathways of Cationized, Saturated, Short-Chain Triacylglycerols: Lithiated and Sodiated Tripropanoyl- and Trihexanoylglycerol

A Sensitive LC-MS/MS Method for Palytoxin Using Lithium Cationization

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