Unusual polymethylene-interrupted, Δ5 monounsaturated and omega-3 fatty acids in sea urchin (Arbacia punctulata) from the Gulf of Mexico identified by solvent mediated covalent adduct chemical ionization mass spectrometry

Wang, Dong Hao; Wang, Zhen; Li, Xu; Martinez, Secilia; James, Genevieve; Rahman, Saydur; Brenna, J. Thomas

doi:10.1016/j.foodchem.2021.131131

Cited by 11 publications

(23 citation statements)

References 31 publications

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“…Among the identified fatty acids, twelve are non-methylene interrupted fatty acids including sciadonic acid (FA 20:3 n -6,9,15 at 47 ± 8 nmol mL -1 ) and keteleeronic acid (FA 20:2 n -9,15 at 2.4 ± 0.4 nmol mL -1 ). Polyunsaturated fatty acids that exhibit a pattern of unsaturation other than the canonical methylene-interrupted or conjugated sequences of double bonds have not previously been reported in human plasma but have been observed in other biological systems including pine nuts, 45 sea urchins, 14 mangos, 46 marine food webs, 47 dairy 48 as well as human breast milk. 49 Prior identification of non-methylene interrupted fatty acids in foodstuffs may point to these being present in reference plasma as a result of dietary intake.…”

Section: Resultsmentioning

confidence: 98%

“…Examples of this approach in the context of GC-MS include off-line dimethyl disulfide derivatization, 12 and online gas-phase derivatization at the double bond via covalent-adduct chemical ionization mass spectrometry. 13,14 Analogous LC-MS approaches include derivatization at the site(s) of unsaturation via Paternò-Büchi reactions that are often conducted between the chromatograph and the mass spectrometer. 15,16 Once chemically activated by derivatization, carbon-carbon double bonds are cleaved by CID leading to two characteristic product ions demarking each double bond position.…”

Section: Introductionmentioning

confidence: 99%

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OzFAD: Ozone-enabled fatty acid discovery reveals unexpected diversity in the human lipidome

Menzel

Young

Benfield

et al. 2022

Preprint

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Fatty acid isomers are responsible for an under-reported lipidome diversity across all kingdoms of life. Isomers of unsaturated fatty acid are often masked in contemporary analysis by incomplete separation and the absence of sufficiently diagnostic methods for structure elucidation. Here, we introduce a comprehensive workflow to discover new unsaturated fatty acids through coupling liquid chromatography and mass spectrometry with gas-phase ozonolysis of double bonds. The workflow encompasses semi-automated data analysis and enables de novo identification in complex media including human plasma, cancer cell lines and human sebaceous wax (i.e., vernix caseosa). The targeted analysis including ozonolysis enables structural assignment over a dynamic range of five orders of magnitude, even in instances of incomplete chromatographic separation. Thereby we expand the number of identified plasma fatty acids two-fold, including non-methylene interrupted fatty acids. Detection, without prior knowledge, allows discovery of non-canonical double bond positions. Changes in relative isomer abundances reflect underlying perturbations in lipid metabolism.

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Section: Resultsmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

OzFAD: Ozone-enabled fatty acid discovery reveals unexpected diversity in the human lipidome

Menzel

Young

Benfield

et al. 2022

Preprint

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“…The fragmentation rules for various FAME varieties have been worked out in several publications, with monoenes, dienes, polyenes with ≥3 homoallylic double bonds, conjugated FAMEs and polyenes with non-methylene-interrupted double bonds having nuances in spectral interpretations. [5][6][7][23][24][25][26] SM-CACI enables de novo identification of common and unusual FAMEs without the need for authentic standards. For instance, Fig.…”

Section: Derivatization Methods For Gc-eims Analysismentioning

confidence: 99%

“…The SM-CACI-MS 2 spectra for the identification of polyunsaturated FAMEs and other unusual FAMEs by SM-CACI can be found in a series of previous publications. [5][6][7]23,24 The SM-CACI technique is currently the only online derivatization mass spectrometric method coupled with a GC system, eliminating fatty acid manual derivatization. Importantly, it is the only method which allows the separation of FAMEs on the GC column before making FAME derivatives, making it highly compatible with any analytical method established on a GC-FID, and thus requiring no further offline chemistry.…”

Section: Derivatization Methods For Gc-eims Analysismentioning

confidence: 99%

Section: Analytical Challenges Of Differentiating Fatty Acid Isomerismmentioning

confidence: 99%

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Fatty acid isomerism: analysis and selected biological functions

Wang,

Yang,

Brenna

et al. 2024

Food Funct.

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Skin derived branched‐chain fatty acids in fetal horse gut

Wang,

Qi,

Yang

et al. 2024

Euro J Lipid Sci & Tech

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Branched‐chain fatty acids (BCFAs) are mostly saturated fatty acids with a methyl branch at the penultimate or antepenultimate position to the CH3 end. Very‐long‐chain BCFAs (C ≥ 20) are uniquely found in surface lipids. Human and California sea lion (Zalophus californianus) are the only two species that possess vernix at birth, and vernix particles carry loads of BCFA to the gut, potentially influencing the establishment of the first microbiota. Horse (Equus caballus) contains high levels of BCFA in its surface lipids, and the current study aims to investigate if BCFA are components of a neonatal foal's gut. Electron ionization tandem mass spectrometry was used to distinguish iso‐ and anteiso‐form of BCFA from straight‐chain fatty acids. Abundant very‐long‐chain iso‐BCFA, mainly even‐numbered iso‐20:0, iso‐22:0, iso‐24:0, and iso‐26:0 were found in horse meconium but not in their manure collected a few months later. There are little differences in BCFA types and concentrations between foal manure and adult manure. Moderate to high levels of very‐long‐chain anteiso‐BCFA were also found. Comparisons of horse meconium BCFA to horse skin cholesterol ester BCFA content and to meconium from human and sea lion suggest its skin derived origin. The study expands our knowledge on the gut nutritional environment of a newborn horse, and further study is needed to establish the relationship between gut BCFA and microbiota composition in the first few hours of life.Practical Applications: Branched‐chain fatty acids (BCFA) are bioactive compounds found in vernix caseosa, the lipid‐laden material covering the surface of a newborn baby. BCFA also reaches high concentrations from the third trimester of gestation until birth. However, the exact functionality and mechanisms of BCFA in the surface and gut of a fetus remain unclear. The current study aims to clarify the lipid conditions in the gut of newborn foals and to identify the associations between BCFA in the gut and on the skin at a critical point when the horse's microbiota establishes itself. The findings of the current study lay a path for studying the physiological functions of BCFA in horse models, potentially accelerating research related to BCFA.

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Unusual polymethylene-interrupted, Δ5 monounsaturated and omega-3 fatty acids in sea urchin (Arbacia punctulata) from the Gulf of Mexico identified by solvent mediated covalent adduct chemical ionization mass spectrometry

Cited by 11 publications

References 31 publications

OzFAD: Ozone-enabled fatty acid discovery reveals unexpected diversity in the human lipidome

OzFAD: Ozone-enabled fatty acid discovery reveals unexpected diversity in the human lipidome

Fatty acid isomerism: analysis and selected biological functions

Skin derived branched‐chain fatty acids in fetal horse gut

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