EIMS Fragmentation Pathways and MRM Quantification of 7α/β-Hydroxy-Dehydroabietic Acid TMS Derivatives

Rontani, Jean‐François; Aubert, Claude; Belt, Simon T.

doi:10.1007/s13361-015-1157-3

Cited by 9 publications

(17 citation statements)

References 23 publications

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“…These results highlighted the need for a set of tracers specific enough to pinpoint the origin of organic matter and with identified oxidation products specific to degradation processes we are looking at here. For this purpose, we previously studied and identified a number of tracers which, coupled with their degradation products, formed a specific set allowing us to unambiguously attribute a higher‐plant terrestrial origin to the suspended particulate matter we are studying [ Galeron et al ., , ; Rontani et al ., ].…”

Section: Methodsmentioning

confidence: 99%

“…Preliminary studies on the Rhône River [ Galeron et al ., ] highlighted the involvement of autoxidation in terrestrial organic matter during riverine transport but also evidenced the lack of unambiguous tracers allowing us to determine the origin of TPOM as well as to pinpoint the degradative processes it has undergone. With this challenge in mind, we developed a set of terrestrial tracers specific enough to distinguish between different types of higher‐plant organic matter sources (angiosperms versus gymnosperms) but also allowing us to identify the type of oxidative damages endured by POM [ Galeron et al ., , ; Rontani et al ., ].…”

Section: Introductionmentioning

confidence: 99%

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Autoxidation as a major player in the fate of terrestrial particulate organic matter in seawater

et al. 2017

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The Rhône River plays a major role in the Mediterranean Sea, being both its main freshwater source and its major particulate matter provider. This survey of the fate of terrestrial particulate organic matter (POM) was conducted along the salinity gradient of the Rhône River plume, between 2012 and 2014. It revealed that autoxidation acts rapidly and intensely upon the POM's arrival at sea, with α‐amyrin and β‐amyrin autoxidation rates going from 12.9 ± 2.9% to 45.0 ± 6.4% and 10.7 ± 4.0% to 50.3 ± 4.4%, respectively, between fresh water (salinity 0) and seawater (salinity 38). These compounds, being unambiguous markers of the terrestrial origin of POM, allow us to unequivocally characterize the POM as terrestrial. While it was originally believed that a desorption of redox‐active trace metal ions was the favoring factor that kick‐started this intense autoxidation, this study evidences no trace metal desorption in the Rhône River mixing zone and hence no correlation between high autoxidation rates and the presence of trace metal ions. Autoxidation rates however were very well correlated with salinity levels within the river plume, with r2 reaching 0.801, 0.962, and 0.943 for sitosterol, α‐amyrin, and β‐amyrin, respectively, in November 2014.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Autoxidation as a major player in the fate of terrestrial particulate organic matter in seawater

et al. 2017

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“…Further ions at m/z 191, 234, 237, 252, 299, 370, and 417 are also observed. The relative abundances of these fragments differ strongly between the two isomers, which allows for the unambiguous assignment of their structures [38]. The chromatographic elution order was also crucial together with the comparison between the obtained MS spectra and the ones found in the literature [38].…”

Section: Terpenic Compoundsmentioning

confidence: 96%

“…Compounds were identified by comparing their mass spectra (MS) with the equipment's mass spectral library (NIST Mass Spectral Library), with data from the literature [34][35][36][37][38][39][40][41][42][43], and by the co-injection of standards.…”

Section: The Gc-ms Analysismentioning

confidence: 99%

“…DHAA (5) was found to be the most abundant component in bark of the studied Pinus species, representing 49% and 57% w/w of the total content of abietane-type resin acids in the P. pinaster and P. pinea bark samples, respectively (Table 1). Interestingly, this compound is only a minor constituent of fresh conifer resin; however, its abundance increases with aging, which results from the oxidation pathways of the abietadiene-type precursors (Scheme 1) [6,38,44]. Furthermore, the formation of DHAA might result from exposure to light and oxygen from the air.…”

Section: Terpenic Compoundsmentioning

confidence: 99%

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Chemical Composition of Lipophilic Bark Extracts from Pinus pinaster and Pinus pinea Cultivated in Portugal

et al. 2018

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The chemical composition of lipophilic bark extracts from Pinus pinaster and Pinus pinea cultivated in Portugal was evaluated using gas chromatography-mass spectrometry. Diterpenic resin acids were found to be the main components of these lipophilic extracts, ranging from 0.96 g kg −1 dw in P. pinea bark to 2.35 g kg −1 dw in P. pinaster bark. In particular, dehydroabietic acid (DHAA) is the major constituent of both P. pinea and P. pinaster lipophilic fractions, accounting for 0.45 g kg −1 dw and 0.95 g kg −1 dw, respectively. Interestingly, many oxidized compounds were identified in the studied lipophilic extracts, including DHAA-oxidized derivatives (7-oxo-DHAA, 7α/β-hydroxy-DHAA, and 15-hydroxy-DHAA, among others) and also terpin (an oxidized monoterpene). These compounds are not naturally occurring compounds, and their formation might occur by the exposure of the bark to light and oxygen from the air, and the action of micro-organisms. Some of these compounds have not been previously reported as lipophilic constituents of the bark of the referred pine species. Other constituents, such as aromatic compounds, fatty acids, fatty alcohols, and sterols, are also present in the studied extracts. These results can represent an opportunity to valorize P. pinaster and P. pinea by-products as a primary source of the bioactive resin acids that are integrated into the current uses of these species.Resin acids (mainly abietane-type resin acids, including the abietic, neoabietic, palustric, and levopimaric acids, and minor amounts of pimarane-type resin acids, including the pimaric, isopimaric, and sandaracopimaric acids) are the major components of Pinus spp. wood resin [5]. Small amounts of dehydroabietic acid (DHAA), obtained by dehydrogenation of abietane-type resin acids, can also be found in wood resins. These compounds have been exploited as important commodities for the chemical industry [5]. In addition, they play an important role in the chemical defense of conifers. Many examples show a relationship between conifer diterpenic acid content and a tree's resistance to potential herbivores and pathogens [6]. Furthermore, resin acids display important beneficial properties for human health, being the antimicrobial, antiulcer, and cardiovascular activities the most representative ones [7,8].Due to the mentioned significant biological properties, the search for new natural and synthetic resin acid derivatives has been an active research field. Most of these compounds have been tested for their cytotoxicity against cancer cells [9][10][11][12][13][14], and their antioxidant [9,15], antiviral [10,11,16], antimycotic [10], and gastroprotective [12] activities. Resin acids can also be found in the lipophilic extracts of different morphological parts of several Pinus spp. [17-25], including the bark of Pinus nigra [21], the Turkish P. pinea L. [23], and the Pakistani Pinus wallichiana, Pinus roxburghii, and Pinus gerardiana [25]. Among the resin acids that have been identified in bark lipophilic extracts are the pimaric, s...

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Mass Spectrometric Fragmentation of Trimethylsilyl and Related Alkylsilyl Derivatives

Harvey

Vouros

2019

Mass Spectrometry Reviews

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This review describes the mass spectral fragmentation of trimethylsilyl (TMS) and related alkylsilyl derivatives used for preparing samples for analysis, mainly by combined gas chromatography and mass spectrometry (GC/MS). The review is divided into three sections. The first section is concerned with the TMS derivatives themselves and describes fragmentation of derivatized alcohols, thiols, amines, ketones, carboxylic acids and bifunctional compounds such as hydroxy‐ and amino‐acids, halo acids and hydroxy ethers. More complex compounds such as glycerides, sphingolipids, carbohydrates, organic phosphates, phosphonates, steroids, vitamin D, cannabinoids, and prostaglandins are discussed next. The second section describes intermolecular reactions of siliconium ions such as the TMS cation and the third section discusses other alkylsilyl derivatives. Among these latter compounds are di‐ and trialkyl‐silyl derivatives, various substituted‐alkyldimethylsilyl derivatives such as the tert‐butyldimethylsilyl ethers, cyclic silyl derivatives, alkoxysilyl derivatives, and 3‐pyridylmethyldimethylsilyl esters used for double bond location in fatty acid spectra. © 2019 Wiley Periodicals, Inc. Mass Spec Rev 0000:1–107, 2019

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EIMS Fragmentation Pathways and MRM Quantification of 7α/β-Hydroxy-Dehydroabietic Acid TMS Derivatives

Cited by 9 publications

References 23 publications

Autoxidation as a major player in the fate of terrestrial particulate organic matter in seawater

Autoxidation as a major player in the fate of terrestrial particulate organic matter in seawater

Chemical Composition of Lipophilic Bark Extracts from Pinus pinaster and Pinus pinea Cultivated in Portugal

Mass Spectrometric Fragmentation of Trimethylsilyl and Related Alkylsilyl Derivatives

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