Analysis of Lipids Using 2,4,6-Trihydroxyacetophenone as a Matrix for MALDI Mass Spectrometry

Stübiger, Gerald; Belgacem, Omar

doi:10.1021/ac062236c

Cited by 105 publications

(118 citation statements)

References 62 publications

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“…W ith the advent of electrospray ionization (ESI) [1,2] and matrix-assisted laser desorption ionization (MALDI) [3,4], the analysis of lipids using tandem mass spectrometry (MS) has been greatly facilitated since these techniques can generate the intact gaseous pseudo-molecular ions for most lipids ranging from simple fatty acids to complex lipids [5][6][7][8][9][10]. Among the various complex lipids, glycerophospholipids (GPLs) perform two important biological functions: one is making up most of the membranes of mammalian cells, and the other is acting as secondary messengers in metabolism [11,12].…”

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confidence: 99%

Electron transfer dissociation of doubly sodiated glycerophosphocholine lipids

Liang

Liu

LeBlanc³

et al. 2007

J. Am. Soc. Mass Spectrom.

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The ability to generate gaseous doubly charged cations of glycerophosphocholine (GPC) lipids via electrospray ionization has made possible the evaluation of electron-transfer dissociation (ETD) for their structural characterization. Doubly sodiated GPC cations have been reacted with azobenzene radical anions in a linear ion trap mass spectrometer. The ion/ion reactions proceed through sodium transfer, electron-transfer, and complex formation. Electron-transfer reactions are shown to give rise to cleavage at each ester linkage with the subsequent loss of a neutral quaternary nitrogen moiety. Electron-transfer without dissociation produces [M ϩ 2Na] ϩ· radical cations, which undergo collision-induced dissociation (CID) to give products that arise from bond cleavage of each fatty acid chain. The CID of the complex ions yields products similar to those produced directly from the electron-transfer reactions of doubly sodiated GPC, although with different relative abundances. These findings indicate that the analysis of GPC lipids by ETD in conjunction with CID can provide some structural information, such as the number of carbons, degree of unsaturation for each fatty acid substituent, and the positions of the fatty acid substituents; some information about the location of the double bonds may be present in low intensity CID product ions. [3,4], the analysis of lipids using tandem mass spectrometry (MS) has been greatly facilitated since these techniques can generate the intact gaseous pseudo-molecular ions for most lipids ranging from simple fatty acids to complex lipids [5][6][7][8][9][10]. Among the various complex lipids, glycerophospholipids (GPLs) perform two important biological functions: one is making up most of the membranes of mammalian cells, and the other is acting as secondary messengers in metabolism [11,12]. The structural determination (identities and positions of the fatty acid substituents) of GPLs for all five subclasses has been made via CID of negative ions formed by either ESI, fast atom bombardment (FAB), or MALDI [5,13,14]. Among the five main subclasses of GPLs, which are differentiated by the head-group (e.g., ethanolamine, choline, serine, glycerol, or inositol), glycerophosphocholine (GPC) species generally give stronger signals in positive ion mode than in negative mode due to the fixed charge on the quaternary nitrogen. The structural information mentioned above can be obtained by CID of alkali adducts of GPC species generated in positive ion ESI-MS [15]. Little or no information regarding the location of the double bonds in GPCs has been reported by these methods.Both electron capture dissociation (ECD) [16 -19] and electron-transfer dissociation (ETD) [20 -23] have been shown to be particularly useful in the structural determination of proteins and peptides [24 -27]. This is mainly because more extensive sequence information can often be obtained via ECD or ETD than via CID and because, unlike CID, labile post-translational modifications are often retained, which is particularly va...

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confidence: 99%

Electron transfer dissociation of doubly sodiated glycerophosphocholine lipids

Liang

Liu

LeBlanc³

et al. 2007

J. Am. Soc. Mass Spectrom.

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“…Matrix-assisted laser desorption/ionisation-time of flight mass spectrometry (MALDI-TOF MS) analysis of lipids has 35 been conducted using both commonly-used matrices such as isomers of 2,5-dihydroxybenzoic and 2,4,6-trihydroxyacetophenone, 2,3 as well as more novel species such as ionic liquids. 4 The identification of product ion peaks following fragmentation of lipids by MSMS in the presence of 40 metal cations is a good method for lipid analysis.…”

Section: Introductionmentioning

confidence: 99%

“…5 Similar studies have been carried out on the effect of adding lithium salts. Stübiger and Belgacem studied lipids from 50 several classes, 3 containing product ions separated by 6 Da. Both of these observations are advantageous for lipid identification and have been put to good use for techniques such as MALDI imaging.…”

Section: Introductionmentioning

confidence: 99%

The reproducibility of phospholipid analyses by MALDI-MSMS

Pridmore

Mosely

Sanderson

2011

Analyst

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(2011) 'The reproducibility of phospholipid analyses by MALDI-MSMS. ', Analyst., 136 (12). pp. 2598-2605. Further information on publisher's website:http://dx.doi.org/10.1039/C0AN00436GPublisher's copyright statement:Additional information: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. The identification of phosphocholine and phosphoethanolamine lipids by MALDI TOF/TOF, including characterisation of the headgroup and delineation of the acyl chain at each position of the glycerol backbone, has been explored using lipids representative of each type. The relative intensities of fragments involving the neutral loss of one or other of the acyl chains of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine (POPE), 1-palmitoyl-2-oleoyl-sn-glycero-3-10 phosphocholine (POPC) and 1-oleoyl-2-palmitoyl-sn-glycero-3-phosphocholine (OPPC) were compared. For POPC and POPE, a statistical preference for the loss of the chain from the sn-1 position was observed in the presence of lithium. For OPPC this selectivity was reversed for one of the fragments. In the absence of lithium, fragmentation was favoured at the sn-2 position for all lipids. In all cases, spectra obtained in the presence of lithium yielded more intense product ion 15 peaks. Although Collision Induced Dissociation (CID) could be used for complete lipid characterisation, LIFT™ was found to be a better method due to the presence of a greater number of distinguishing product ion peaks and a better shot-to-shot reproducibility of peak intensities.

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“…In addition, the method has been applied to measurements of polynucleotides [11][12][13][14] as well as a large number of smaller molecules, including lipids [15][16][17], fatty acids, bile acids, and steroids [18][19][20].…”

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confidence: 99%

“…Complicating any fundamental aspects of ion formation are the well known and rather subjective issues of the "right" matrix for any analyte [1,11,13,15,18,[24][25][26][27][28], including the use of ionic liquid matrices [29,30]. In addition, there have been efforts directed towards the "proper" method for sample preparation [8,21].…”

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confidence: 99%

Production of Reliable MALDI Spectra with Quality Threshold Clustering of Replicates

Olson

Epstein

Sackett

et al. 2011

J. Am. Soc. Mass Spectrom.

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We present the first application of the quality threshold (QT) clustering algorithm to mass spectrometry (MS) data. The unique abilities of QT clustering to yield precision nodes that are commensurate with the mass measurement precision of the instrument are exploited to generate a consensus spectrum out of multiple replicate spectra. The spectral dot product and confidence intervals are used as a tool for evaluating the similarity and reproducibility between the consensus and replicates. The method is equally applicable to high and low resolution measurements. This paper demonstrates applications to linear spectra from a matrix assisted laser desorption ionization (MALDI) time of flight (TOF) instrument as well as peptide fragmentation data obtained from a TOF/TOF after unimolecular decomposition. The advantages of clustering to mitigate the inherent precision the shortcomings of MALDI data are discussed.

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Analysis of Lipids Using 2,4,6-Trihydroxyacetophenone as a Matrix for MALDI Mass Spectrometry

Cited by 105 publications

References 62 publications

Electron transfer dissociation of doubly sodiated glycerophosphocholine lipids

Electron transfer dissociation of doubly sodiated glycerophosphocholine lipids

The reproducibility of phospholipid analyses by MALDI-MSMS

Production of Reliable MALDI Spectra with Quality Threshold Clustering of Replicates

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