Structural Analysis of Triacylglycerols by Using a MALDI-TOF/TOF System with Monoisotopic Precursor Selection

Kubo, Ayumi; Satoh, Takaya; Itoh, Yoshiyuki; Hashimoto, Masahiro; Tamura, Jun; Cody, Robert B.

doi:10.1007/s13361-012-0513-9

Cited by 45 publications

(40 citation statements)

References 27 publications

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“…1C as examples, we observe that within the dual acyl group loss region there are two distinct peak groups: singlets (e.g., m/z 331.25) and paired doublets (e.g., m/z 345.26 and 347.24). High-energy CID experiments also yield similar fragments (7,8), confirming our assignments here. Each singlet peak (e.g., m/z 305.24 in Fig.…”

Section: Eieio Provides Characteristic Fragments For Tagssupporting

confidence: 87%

“…For brevity, we focused on the analyses of olive oils (8) in the main manuscript, of isomeric TAGs. Hence, we have listed double bond location patterns and their amount in percentages in the result tables (Table 2; supplemental Fig.…”

Section: Identifying Tags In Natural Lipid Samplesmentioning

confidence: 99%

“…This information is critical to understand the dynamic functions of TAGs, their digestion, and their metabolism. A conventional TAG characterization method in MS is based on low-energy (5, 6) or high-energy collision-induced dissociation (CID) (7,8). These methods provide TAG structural information, including acyl chain lengths and double bond number; however, the double bond positions and the acyl chain regioisomeric arrangement are not easily defined due to the limited information derived from the resultant fragments.…”

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confidence: 99%

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Structural identification of triacylglycerol isomers using electron impact excitation of ions from organics (EIEIO)

Baba

Campbell

Blanc

et al. 2016

Journal of Lipid Research

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approximate acyl chain composition (3), other critical information such as the exact regioisomerism of fatty acids along the glycerol backbone, the position(s) of the acyl chain double bonds, the stereochemistry of the double bonds, and so forth, cannot currently be obtained using conventional bioanalytical techniques. For example, a common method of TAG analysis is the chromatographic detection of FFAs or their derived methyl or ethyl esters, which are obtained by hydrolysis from TAGs (4). Although convenient, this method does not allow for consideration of the structural aspects of the intact TAG molecular species (i.e., regioisomeric structural information). This information is critical to understand the dynamic functions of TAGs, their digestion, and their metabolism. A conventional TAG characterization method in MS is based on low-energy (5, 6) or high-energy collision-induced dissociation (CID) (7,8). These methods provide TAG structural information, including acyl chain lengths and double bond number; however, the double bond positions and the acyl chain regioisomeric arrangement are not easily defined due to the limited information derived from the resultant fragments. HPLC has also been used to resolve regioisomers of TAGs (9), but it requires long analysis times, authentic standards as references, and extensive method development, potentially making this method unattractive to a high-throughput lab. A recent study of TAG regioisomers was reported using differential mobility spectrometry (DMS) without HPLC (10). Despite advances in the goal to characterize lipid molecular species, including using ozone-induced dissociation (OzID) (11, 12) or a Paternò-Büchi reaction (13, 14) to determine double bond positions, an efficient method to characterize lipid structural details has been lacking. Recently, a study using OzID found that TAG molecular species containing C18:1, n-7 versus C18:1, n-9 correlated with clinical variables of dyslipidemia and are proinflammatory (15). These results highlight the need for a method to fully characterize Abstract Electron-induced dissociation or electron impact excitation of ions from organics (EIEIO) was applied to triacylglycerols (TAGs) for in-depth molecular structure analysis using MS. In EIEIO, energetic electrons (10 eV) fragmented TAG ions to allow for regioisomeric assignment of identified acyl groups at the sn-2 or sn-1/3 positions of the glycerol backbone. In addition, carbon-carbon double bond locations within the acyl chains could also be assigned by EIEIO. Triacylglycerols (TAGs) are among the most abundant lipids in the human body, located primarily within adipose. TAGs are also found in plants and are concentrated in seeds as a source of energy during embryonic development. It is from these various seeds that a majority of edible oils are derived. The physiological role of TAGs is to serve as a reserve of fatty acids for energy generation via -oxidation. However, these same stored fatty acids may also serve as precursors, either directly or indirectly, to ...

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Section: Eieio Provides Characteristic Fragments For Tagssupporting

confidence: 87%

Section: Identifying Tags In Natural Lipid Samplesmentioning

confidence: 99%

mentioning

confidence: 99%

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Structural identification of triacylglycerol isomers using electron impact excitation of ions from organics (EIEIO)

Baba

Campbell

Blanc

et al. 2016

Journal of Lipid Research

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“…In our SpiralTOF-TOF, the HE-CID channels can be preferentially observed, because the electrostatic sector in rst SpiralTOF can eliminate PSD ions. [29][30][31][32] Here, we report the rst trial of MSI using a high performance SpiralTOF-TOF, and demonstrate advantages in an analysis of lipids directly on a tissue specimen. e variety of lipid structures in biological samples complicates mass spectra; however, the high mass resolution of SpiralTOF could resolve 0.1 u di erences in doublet peaks, of which the mass spectrometry images then indicated a complementary distribution.…”

Section: Introductionmentioning

confidence: 83%

Mass Spectrometry Imaging and Structural Analysis of Lipids Directly on Tissue Specimens by Using a Spiral Orbit Type Tandem Time-of-Flight Mass Spectrometer, SpiralTOF-TOF

Satoh

Kubo

Shimma³

et al. 2012

Mass Spectrometry

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In this paper, we report the use of mass spectrometry imaging and structural analysis of lipids directly on a tissue specimen, carried out by means of matrix-assisted laser desorption/ionization tandem time-of-ight mass spectrometry, using a combination of spiral orbit-type and re ectron-type time-of-ight mass spectrometers. e most intense peak observed in the mass spectrum from a brain tissue specimen was con rmed as phosphatidylcholine (34 : 1) [M+K] + , using tandem mass spectrometry. e charge remote fragmentation channels, which are characteristically observed using high-energy collisioninduced dissociation, contributed signi cantly to this con rmation. Accurate mass analysis was further facilitated by mass correction using the con rmed peak. In mass spectrometry imaging, the high resolving power of our system could separate doublet peak of less than 0.1 u di erence, which would otherwise be problematic when using a low-resolution re ectron type time-of-ight mass spectrometer. Two compounds, observed at m/z 848.56 and 848.65, were found to be located in complementary positions on a brain tissue specimen. ese results demonstrate the importance of a high-performance tandem timeof-ight mass spectrometer for mass spectrometry imaging and analysis of observed compounds, to allow distinction between biological molecules.

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“…This technique is based on the selection of stationary phases, mobile phases, detectors, column temperature program and an appropriate resolution of carbon chain. Several scientific instruments are used to develop rapid, reliable and cost effective techniques for the analysis of vegetable oils such as gas chromatography-mass spectroscopy (GC-MS), high performance liquid chromatography (HPLC), matrix assisted laser desorption/ionization mass spectrometry (MALDI) and others (Dugo et al, 2012;Mercy et al, 2016;Kubo et al, 2013). TOF-MS techniques are advanced, efficient, much faster, have high data acquisition rate and a small internal volume for mass analysis (Vaclavik et al, 2009).…”

Section: Introductionmentioning

confidence: 99%

Characterization of Leucaena (<em>Leucaena leucephala</em>) oil by direct analysis in real time (DART) ion source and gas chromatography

et al. 2017

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SUMMARY:For the first time, we report the characterization of triacylglycerols and fatty acids in Leucaena (Leucaena leucephala) oil [LUCO], an unexplored nontraditional non-medicinal plant belonging to the family Fabaceae. LUCO was converted to fatty acid methyl esters (FAMEs). We analyzed the triacylglycerols (TAGs) of pure LUCO and their FAMEs by time-of-flight mass spectrometry (TOF-MS) followed by multivariate analysis for discrimination among the FAMEs. Our investigations for the analysis of LUCO samples represent noble features of glycerides. A new type of ion source, coupled with high-resolution TOF-MS was applied for the comprehensive analysis of triacylglycerols. The composition of fatty acid based LUCO oil was studied using Gas Chromatography (GC-FID). The major fatty acid components of LUCO oil are linoleic acid (52.08%) oleic acid (21.26%), palmitic acid (7.91%) and stearic acid (6.01%). A metal analysis in LUCO was done by Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The structural elucidation and thermal stability of LUCO were studied by FT-IR, 1 H NMR, 13 C NMR spectroscopic techniques and TGA-DSC, respectively. We also measured the cytotoxicity of LUCO. KEYWORDS: Cytotoxicity; Gas Chromatography; Leucaena oil; Thermal analysis; TOF-MSRESUMEN: Caracterización del aceite de Leucaena (Leucaena leucocephala) por análisis directo en tiempo real (DART) y cromatografía de gases. Se presenta por primera vez la caracterización de triacilgliceroles y ácidos grasos del aceite de Leucaena (Leucaena leucephala) [LUCO], una planta no medicinal, no tradicional y no explorada, perteneciente a la familia Fabaceae. Se analizaron triacilgliceroles (TAGs) de LUCO y sus FAMEs por espectrometría de masas de tiempo de vuelo (TOF-MS) seguido de análisis multivariante para discriminación entre los FAME. Nuestras investigaciones para el análisis de muestras de LUCO presentaron características propias de los glicéridos. Un nuevo tipo de fuente de iones, junto con alta resolución TOF-MS se aplicó para el análisis exhaustivo de triacilgliceroles. La composición de aceite de LUCO basado en ácidos grasos se estudió usando Cromatografía de Gas (GC-FID). Los principales componentes de ácidos grasos del aceite LUCO fueron, linoleico (52,08%), oleico (21,26%), palmítico (7,91%) y esteárico 6,01%. El análisis de metales se realizó mediante Espectrometría de Plasma Acoplado Inductivamente a Masas (ICP-MS). La elucidación estructural y la estabilidad térmica de LUCO se estudiaron mediante FT-IR, 1 H NMR, técnicas espectroscópi-cas de 13 C NMR y TGA-DSC, respectivamente. También se midió la citotoxicidad de LUCO.

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Structural Analysis of Triacylglycerols by Using a MALDI-TOF/TOF System with Monoisotopic Precursor Selection

Cited by 45 publications

References 27 publications

Structural identification of triacylglycerol isomers using electron impact excitation of ions from organics (EIEIO)

Structural identification of triacylglycerol isomers using electron impact excitation of ions from organics (EIEIO)

Mass Spectrometry Imaging and Structural Analysis of Lipids Directly on Tissue Specimens by Using a Spiral Orbit Type Tandem Time-of-Flight Mass Spectrometer, SpiralTOF-TOF

Characterization of Leucaena (<em>Leucaena leucephala</em>) oil by direct analysis in real time (DART) ion source and gas chromatography

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