A comprehensive study of oleuropein aglycone isomers in olive oil by enzymatic/chemical processes and liquid chromatography-Fourier transform mass spectrometry integrated by H/D exchange

Abbattista, Ramona; Losito, Ilario; Ceglie, Cristina De; Castellaneta, A.; Calvano, Cosima Damiana; Palmisano, Francesco; Cataldi, Tommaso R. I.

doi:10.1016/j.talanta.2019.07.002

Cited by 18 publications

(54 citation statements)

References 37 publications

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“…The open enolic/aldehydic form resulting from the opening of the initial, unstable hemiacetalic moiety of this aglycone is reported in the inset of Figure S2 (supporting information). Other product ions, detected at nominal m/z values 345, 307 and 275, can be explained by considering neutral losses, from OA, of methanol (−32 Da), 2‐butenal (−70 Da) and 2‐butenal and methanol (−102 Da), respectively, in accordance with a pattern recently described by Abbattista et al for OA examined under HCD‐MS/MS conditions. Finally, the peak at m/z 179.06 was assigned to the monohexose moiety in its deprotonated form.…”

Section: Resultssupporting

confidence: 84%

“…According to the accurate mass values, the peak at m/z 241.072 was assigned to deprotonated EA [C 11 H 13 O 6 ] − ; the one at m/z 361.129 corresponds to deprotonated ligstroside aglycone (LA, [C 19 H 21 O 7 ] − ), whereas the peak at m/z 377.124 ([C 19 H 21 O 8 ] − ) can be tentatively assigned to oleuropein aglycone and/or to the oxidized form of ligstroside aglycone. Although these isobaric species cannot be distinguished in MS mode, the identification was possible through MS/MS experiments ( vide infra ), suggesting that the signal at m/z 377.124 was mainly due to OA (i.e., compound n. 1 in Table ), in agreement with a recent LC/FTMS/MS study on VOO extracts . The occurrence of additional VOO secoiridoids, i.e., oleocanthal and oleacein, was ascertained by the detection of peaks at m/z 303.124 and 319.118, respectively.…”

Section: Resultssupporting

confidence: 82%

“…When the precursor ion of decarboxymethyl‐elenoic acid (EDA) at m/z 183 was fragmented (Figure F), the main peaks were due to acetate ion ( m/z 59, [C 2 H 3 O 2 ] − ) and to an ion with nominal m/z 69, compatible with the empirical formula [C 4 H 5 O] − , recently detected also in the HCD‐MS/MS spectrum of oleuropein aglycone and identified as buta‐1,3‐dien‐1‐olate . A fragmentation scheme explaining the generation of this product ion is reported in Figure S6 (supporting information).…”

Section: Resultsmentioning

confidence: 86%

“…The subsequent loss of CO 2 gives rise to the product ion detected at m/z 165. Moreover, a specific fragmentation pathway, already proposed, was invoked to explain the generation of the product ion at nominal m/z 139 from EA deprotonated on the COOH group (see Figure S5, supporting information). As suggested by a comparison of Figures A, B and E, the remaining product ions detected in the MS/MS spectra of the aglycones of oleuropein and ligstroside are related to the fragmentation of deprotonated EA, whose signal is indeed visible in the MS/MS spectrum of OA, along with one of its decarboxylated derivatives at m/z 197.…”

Section: Resultsmentioning

confidence: 87%

“…The same product ion was included, though not interpreted, in the fragmentation pattern reported for deprotonated EA by Kanakis et al using ESI‐FTMS with an orbitrap MS analyzer. More recently, the structural interpretation of that ion as a fragment of the enolic/aldehydic open‐structure isomer of EA deprotonated on the enolic OH group has been provided by Abbattista et al The resulting structure can be found in Figure S5 (supporting information). As emphasized in the same figure, deprotonated EA on the enolic moiety underwent a neutral loss of methanol from the carboxymethyl group, with formation of a product ion at m/z 209.…”

Section: Resultsmentioning

confidence: 98%

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Characterization of bioactive and nutraceutical compounds occurring in olive oil processing wastes

Ventura

Calvano

Abbattista

et al. 2019

Rapid Comm Mass Spectrometry

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Rationale Several bioactive compounds, including phenolic acids and secoiridoids, are transferred from olive drupes to olive oil during the first stage of production. Here, the characterization of these low molecular weight (LMW) compounds in olive oil and in closely related processing materials, like olive leaves (OL) and olive mill wastewaters (OMW), was faced up, for the first time, by matrix‐assisted laser desorption/ionization (MALDI) time‐of‐flight mass spectrometry (TOF MS). Methods A novel binary matrix composed of 1,8‐bis(tetramethylguanidino)naphthalene (TMGN) and 9‐aminoacridine (9AA) (1:1 molar ratio), displaying excellent ionization properties at low levels of laser energy, was employed in reflectron negative ion mode by a MALDI TOF/TOF system equipped with a neodymium‐doped yttrium lithium fluoride (Nd:YLF) laser (345 nm). MS/MS experiments were performed by using ambient air as the collision gas. Results Four major secoiridoids typically present in olive oil, i.e., the aglycones of oleuropein and ligstroside, and oleacein and olecanthal at m/z 377.1, 361.1, 319.1 and 303.1, respectively, were detected in virgin olive oil (VOO) extracts, along with some of their chemical/enzymatic hydrolysis by‐products, such as elenolic (m/z 241.1), decarboxymethyl‐elenolic acids (m/z 183.1) and hydroxytyrosol (m/z 153.1). Besides oleuropein aglycone and oleacein, hydroxylated derivatives of decarboxymethyl‐elenolic acid and hydroxytyrosol were evidenced in OMW. Conclusions While oleuropein was confirmed in OL extracts, several interesting phenolic compounds, including hydroxytyrosol, were recognized in OMW. The proposed approach based on the use of a novel binary matrix for MALDI MS/MS analyses of LMW bioactive compounds can be considered a promising analytical tool for a rapid screening of the phenolic fraction in olive oils and related processing wastes.

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Section: Resultssupporting

confidence: 84%

Section: Resultssupporting

confidence: 82%

Section: Resultsmentioning

confidence: 86%

Section: Resultsmentioning

confidence: 87%

Section: Resultsmentioning

confidence: 98%

See 3 more Smart Citations

Characterization of bioactive and nutraceutical compounds occurring in olive oil processing wastes

Ventura

Calvano

Abbattista

et al. 2019

Rapid Comm Mass Spectrometry

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Structural characterization of the ligstroside aglycone isoforms in virgin olive oils by liquid chromatography–high‐resolution Fourier‐transform mass spectrometry and H/Dexchange

et al. 2019

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A systematic structural characterization of the isomeric forms related to ligstroside aglycone (LA), one of the most relevant secoiridoids contained in virgin olive oils, was performed using reverse phase liquid chromatography with electrospray ionization Fourier‐transform single and tandem mass spectrometry, operated in negative ion mode (RPLC‐ESI(−)‐FTMS and FTMS/MS). The high mass resolution and accuracy provided by the adopted orbital trap mass analyzer enabled the recognition of more than 10 different isomeric forms of LA in virgin olive oil extracts. They were related to four different types of molecular structure, two of which including a dihydropyranic ring bearing one or two aldehydic groups, whereas the others corresponded to dialdehydic open‐structure forms, differing just for the position of a C═C bond. The contemporary presence of enolic or dienolic tautomers associated to most of these compounds, stable at room temperature (23°C), was also assessed through RPLC‐ESI‐FTMS analyses operated under H/D exchange conditions, ie, by using D2O instead of H2O as co‐solvent of acetonitrile in the RPLC mobile phase. As discussed in the paper, the results obtained for LA indicated a remarkable structural similarity with oleuropein aglycone (OA), the most abundant secoiridoid of olive oil, whose isoforms had been previously characterized using the same analytical approach.

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Bio‐phenols determination in olive oils: Recent mass spectrometry approaches

Bongiorno

Stefano

Indelicato

et al. 2021

Mass Spectrometry Reviews

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Extra virgin olive oil (EVOO) is largely used in Mediterranean diet, and it is also worldwide apprised not only for its organoleptic properties but also for its healthy effects mainly attributed to the presence of several naturally occurring phenolic and polyphenolic compounds (bio-phenols). These compounds are characterized by the presence of multiple phenolic groups in more or less complex structures.Their content is fundamental in defining the healthy qualities of EVOO and consequently the analytical methods for their characterization and quantification are of current interest. Traditionally their determination has been conducted using a colorimetric assay based on the reaction of Folin-Ciocalteu (FC) reagent with the functional hydroxy groups of phenolic compounds. Identification and quantification of the bio-phenols in olive oils requires certainly more performing analytical methods. Chromatographic separation is now commonly achieved by HPLC, coupled with spectrometric devices as UV, FID, and MS. This last approach constitutes an actual cutting-edge application for bio-phenol determination in complex matrices as olive oils, mostly on the light of the development of mass analyzers and the achievement of high resolution and accurate mass measurement in more affordable instrument configurations. After a short survey of some rugged techniques used for bio-phenols determination, in this review have been described the most recent mass spectrometry-based methods, adopted for the analysis of the bio-phenols in EVOOs. In particular, the sample handling and the results of HPLC coupled with low-and high-resolution MS and MS/MS Mass Spec Rev.

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A comprehensive study of oleuropein aglycone isomers in olive oil by enzymatic/chemical processes and liquid chromatography-Fourier transform mass spectrometry integrated by H/D exchange

Cited by 18 publications

References 37 publications

Characterization of bioactive and nutraceutical compounds occurring in olive oil processing wastes

Characterization of bioactive and nutraceutical compounds occurring in olive oil processing wastes

Structural characterization of the ligstroside aglycone isoforms in virgin olive oils by liquid chromatography–high‐resolution Fourier‐transform mass spectrometry and H/Dexchange

Bio‐phenols determination in olive oils: Recent mass spectrometry approaches

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