Identification and Mapping of Phosphocholine in Animal Tissue by Static Secondary Ion Mass Spectrometry and Tandem Mass Spectrometry

McMahon, John M.; Short, R.T.; McCandlish, Carl A.; Brenna, J. Thomas; Todd, Peter J.

doi:10.1002/(sici)1097-0231(199602)10:3<335::aid-rcm516>3.0.co;2-w

Cited by 38 publications

(34 citation statements)

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“…In the lowest temperature range no meaningful spectrum can be obtained from the frozen organic sample in the solid state; usually there is no ion production at all or only a featureless, noisy or low abundance, so-called "peak at every mass", degraded spectrum is recorded. [20][21][22]24,26,28 For many compounds, a rather sharp temperature threshold for ion production is observed, which is reproducible with temperature cycling. 20,21,24 Above the threshold, good-quality cluster-type spectra are recorded in some temperature range up to exhaustion (mainly due to evaporation) of a given sample.…”

Section: Applications Of Lt-fab/sims In Chemistry and Physicsmentioning

confidence: 82%

“…48 The investigation of cluster sputtering from ice is of interest for space, atmospheric and ecological research. 53,70,71 LT-FAB/SIMS studies were extended to organic compounds (mainly volatile solvents): glycerol, 21,[24][25][26]28 primary alcohols, 7,20,24,25 glycols 21 and some others. [22][23][24]27 The main observation with organic compounds was the existence of a strong dependence of the LT mass spectrum pattern and quality on the temperature of the sample.…”

Section: Applications Of Lt-fab/sims In Chemistry and Physicsmentioning

confidence: 99%

“…The main achievements of the techniques were connected with the production and investigation of relatively large clusters of inorganic gases [7][8][9][10][11][12][13][14][15][16][17][18][19] and volatile organic compounds. 11,[20][21][22][23][24][25][26][27][28][29] Attempts to produce LT-FAB/SIMS spectra of frozen water solutions of organic and biologically active compounds were few in number. [30][31][32][33] More recently, progress in other types of desorption techniques such as 252-Cf plasma desorption, laser desorption and matrix-assisted laser desorption/ionisation (MALDI), has brought about a series of reports on sputtering of biomolecules from frozen water-containing matrices.…”

Section: Introductionmentioning

confidence: 99%

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Low temperature secondary emission mass spectrometry. Cryobiological applications

Kosevich

1998

Eur. J. Mass Spectrom.

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Recent achievements of low temperature secondary emission mass spectrometry in exotic fields of life sciences such as cryobiology are surveyed. Specific problems of molecular cryobiology and cryobiophysics accessible to mass spectrometric investigation are defined and the potential of low temperature fast-atom bombardment and secondary ion mass spectrometry in studies of frozen water and cryoprotector solutions of biologically active compounds are demonstrated. Emphasis is placed on the elucidation of changes in intermolecular interactions, the binding of metal ions, water and cryoprotectors with biomolecules at reduced temperatures in comparison with ambient conditions. A model for interpretation of the low temperature secondary emission mass spectra, based on details of phase diagrams of the system under study, the heterogeneous structure of the sample resulting from phase separation during freezing and phase transitions in the sample with temperature variation is discussed.

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Section: Applications Of Lt-fab/sims In Chemistry and Physicsmentioning

confidence: 82%

Section: Applications Of Lt-fab/sims In Chemistry and Physicsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Low temperature secondary emission mass spectrometry. Cryobiological applications

Kosevich

1998

Eur. J. Mass Spectrom.

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“…For example, the major peak in the secondary ion mass spectrum of almost any collection of animal cells is m/z 184, phosphocholine. Phosphocholine is unique among secondary ions emitted from tissue in that its structure has been verified by MS/MS [2], a method permitting distinction of phosphocholine from other sources of m/z 184 such as epinephrine. The secondary phosphocholine ion derives from the head group of phosphatidylcholine, (PC in the shorthand of biochemists) a major constituent of the animal cell membrane.…”

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confidence: 99%

Secondary ion images of the developing rat brain

Todd

McMahon

McCandlish

2004

J. Am. Soc. Mass Spectrom.

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Secondary ion images were obtained from sections of rat brain over a 21 day postnatal period, using the intensity of m/z 184, phosphocholine. When compared with corresponding optical images of similar, but stained sections from the same animal, the secondary ion images appear to reflect less developed brains. During development, myelination occurs after axon extension. Apparently, myelination obscures the source of secondary m/z 184, phosphatidylcholine, from the analyzing ion probe; absenting myelination, secondary ion images show no physiological features. (J Am Soc Mass Spectrom 2004, 15, 1116 -1122) © 2004 American Society for Mass Spectrometry I mages obtained by a variety of methods-optical, secondary electron, nuclear magnetic resonance, etc., are integral to the philosophy of all branches of medicine. Among mass spectral methods, secondary ion mass spectrometry (SIMS) and imaging matrix assisted laser desorption (iMALDI) mass spectrometry are the major players in this arena [1]. These are both emerging methods, and as such, it is necessary to establish that not only are results consistent with known mass spectrometry, but also with known biomedicine.Secondary ions are emitted from tissue at virtually every m/z. We identify secondary ions by tandem mass spectrometry (MS/MS), and map the emission of ions whose structure we know. We then try to interpret the images in the context of known anatomy physiology. For example, the major peak in the secondary ion mass spectrum of almost any collection of animal cells is m/z 184, phosphocholine. Phosphocholine is unique among secondary ions emitted from tissue in that its structure has been verified by MS/MS [2], a method permitting distinction of phosphocholine from other sources of m/z 184 such as epinephrine. The secondary phosphocholine ion derives from the head group of phosphatidylcholine, (PC in the shorthand of biochemists) a major constituent of the animal cell membrane. Most of the outer layer of cell membranes in the brain is either phosphatidylcholine or sphingomyelin [3][4][5], and both compounds yield abundant m/z 184. Thus, detection of phosphocholine is consistent with the chemistry of low dose or static SIMS [6], a surface analytical method, and the fact that most of the surface of a tissue sample is comprised of compounds yielding phosphocholine secondary ions, m/z 184.The utility of SIMS for mapping phoshocholine is based on the observation that emission of phosphocholine secondary ions is heterogeneous across the tissue section surface [7]. Moreover, secondary m/z 184 images of adult rat brain show a direct correlation with optical images of stained tissue sections [8]. Regions of the brain containing a high density of cells such as cerebral cortex or the caudate/putamen yield an intense m/z 184 secondary ion signal, whereas acellular regions such as the corpus callosum or external capsule yield little or no m/z 184 secondary emission. In the adult, these acellular regions of the brain are very dense in cell projections (axons), many of which ar...

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“…Although there are usually a few abundant peaks, the assumption can be made that at least a small component of even large peaks is chemical noise. Consequently, we have found tandem mass spectrometry (MS/MS) to be virtually essential for (1) determination of ion structure [7] and (2) exclusive selection of the ion structure of interest from chemical background noise [4]. To this end, we constructed an imaging secondary ion microprobe using a triple quadrupole mass filter [4].…”

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confidence: 99%