Interfacial chemical reactions accompanying desorption ionization mass spectrometry

Detter, Lisa D.; Hand, Owen W.; Cooks, R. Graham; Walton, Richard A.

doi:10.1002/mas.1280070502

Cited by 88 publications

(33 citation statements)

References 258 publications

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“…7 Mechanisms of ion sputtering from frozen inorganic solids were discussed. 16,22,[59][60][61] More recently, some frozen gases were analyzed using highly charged megaelectronvolt heavy-ion bombardment. [62][63][64][65][66] A characteristic feature of the LT secondary emission mass spectra is the presence of relatively large cluster ions over the whole temperature range of the existence of solid inorganic sample.…”

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

confidence: 99%

“…The occurrence of beam-induced reactions leading to the production of clusters of unexpected composition has been reported. 60,61 Particular attention has been given to clusters of water [7][8][9][10][11]21,25,[66][67][68][69] as one of the favorite objects of study for properties of the hydrogen bond. The main feature of the response of frozen water to bombardment with accelerated particles is the production of a set of protonated hydrogen bonded clusters (H 2 O) n •H + in the positive-ion mode and (H 2 O) n •OH -clusters in the negative-ion mode.…”

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

confidence: 99%

“…[72][73][74][75][76] Voluminous mass spectrometric information on glycerol at both ambient and LT conditions is available. 21,24,26,33,60,91 A water-glycerol mixture gives a typical example of LT-FAB mass spectra of a two-component system whose phase diagram is of the same type as presented in Figure 4. In accord with the model for interpretation of the LT-FAB mass spectra, described in the previous section, it is necessary to determine the morphology of the samples formed during freezing (much studied for water-glycerol mixture by cryobiology [72][73][74] ).…”

Section: Water-cryoprotector Mixturesmentioning

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: 99%

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

confidence: 99%

Section: Water-cryoprotector Mixturesmentioning

confidence: 99%

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Low temperature secondary emission mass spectrometry. Cryobiological applications

Kosevich

1998

Eur. J. Mass Spectrom.

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“…Compound 7 exhibited the molecular formula C 16 , respectively. 17,18) The isolated proton (d 7.19) was assigned to the C-4 position on the basis of its chemical shift and HMBC spectral analysis (Fig.…”

Section: Iridoids and Anthraquinones From The Malaysian Medicinal Plamentioning

confidence: 99%

Iridoids and Anthraquinones from the Malaysian Medicinal Plant, Saprosma scortechinii (Rubiaceae).

et al. 2003

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Saprosma scortechinii BL. KING & GAMBLE, a rubiaceous plant endemic in the Malay Peninsula, 1) is also known as 'sekentut', a local name associated with the unpleasant and fetid odor emitted by the bruised plant tissues. In the traditional medicinal system of Malaysia, the roots are employed in decoctions to treat fever by the native communities, while the young leaves are also eaten as a vegetable.2) Our previous studies on the plant have resulted in the isolation of six sulfur-containing bis-iridoid glucosides (saprosmosides A-F) and 13 iridoid glucosides.3) On-going studies on the same plant materials have resulted in the isolation of two new bisiridoid glucosides, a new iridoid glucoside, and seven new anthraquinones, in addition to three known compounds. We wish to report herein the isolation and structural elucidation of these compounds. Results and DiscussionDried leaves and stems were separately extracted with methanol, and the resulting extracts were subjected to solvent-solvent partitioning. A combination of column chromatography followed by further purification led to the isolation of two new bis-iridoid glucosides (1 and 2) and a new iridoid glucoside (3) from the leaves, and seven new anthraquinones (4-10) from the stems, in addition to three known compounds identified as 6-O-acetylscandoside, The 1 H-and 13 C-NMR spectra ( ; 8-19-1 Nanakuma, Jyounanku, Fukuoka 814-0180, Japan. Received February 18, 2002; accepted May 8, 2002 A further investigation of the leaves and stems of Saprosma scortechinii afforded 13 compounds, of which 10 are new compounds. These were elucidated as the bis-iridoid glucosides, saprosmosides G (1) and H (2), the iridoid glucoside, 6-O-epi-acetylscandoside (3), and the anthraquinones, 1-methoxy-3-hydroxy-2-carbomethoxy-9,10-anthraquinone (4), 1-methoxy-3-hydroxy-2-carbomethoxy-9,10-anthraquinone 3-O-b b-primeveroside (5), 1,3-dihydroxy-2-carbomethoxy-9,10-anthraquinone 3-O-b b-primeveroside (6), 1,3,6-trihydroxy-2-methoxymethyl-9,10-anthraquinone (7), 1-methoxy-3,6-dihydroxy-2-hydroxymethyl-9,10-anthraquinone (8), 1,3,6-trihydroxy-2-hydroxymethyl-9,10-anthraquinone 3-O-b b-primeveroside (9), and 3,6-dihydroxy-2-hydroxymethyl-9,10-anthraquinone (10). Structure assignments for all compounds were established by means of mass and NMR spectroscopies, chemical methods, and comparison with published data. The new anthraquinones were derivatives of munjistin and lucidin.

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“…It is here that the relative proton affinity or gas-phase basicity of a molecule could be all-important. One of the chemical reactions identified by Detter et al that occur at the vacuum and condensed phase interface are Brönsted acid-base reactionsö [31],öandötheögas-phaseöbasicitiesöoföcompoundsöin mixtures have already been shown to be important in fastöatomöbombardmentö(FAB)ö [32].öIfötheösameöisötrue within SIMS, then within binary mixtures, the probability that a molecule is detected as a [M ϩ H] ϩ or [M Ϫ H] Ϫ ion should be linked to these properties. By creating mixtures of compounds of known gas-phase basicities and studying the ions that are detected we aim to determine the role that these chemical properties play in the outcome of a SIMS experiment.…”

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confidence: 99%

Suppression and enhancement of secondary ion formation due to the chemical environment in static-secondary ion mass spectrometry

Jones

Lockyer

Kordys

et al. 2007

J. Am. Soc. Mass Spectrom.

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Through analyzing mixtures of compounds of known gas-phase basicities, the importance of this property on the secondary ions emitted from a surface under primary ion bombardment is investigated. The aim is to obtain a greater understanding of the ionization mechanisms that occur in secondary ion mass spectrometry (SIMS). The commonly used matrix assisted laser desorption/ionization (MALDI) matrix 2,4,6-trihydroxyacetophenone (THAP) and a range of low molecular weight biomolecules were used to investigate whether analyte/matrix suppression effects that have been observed in analogous MALDI experiments were also present in static-SIMS. The outcome of the experiments demonstrates that strong suppression of the quasi-molecular signal of one molecule in a mixture can occur due to the presence of the other, with the gas-phase basicity of the compounds being a good indicator of the secondary ions detected. It is also demonstrated that the suppression of the quasi-molecular ion signal of a compound in a two-component mixture can be minimized by the inclusion of a third compound of suitable gas-phase basicity. (J Am Soc Mass Spectrom 2007, 18, 1559 -1567

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Interfacial chemical reactions accompanying desorption ionization mass spectrometry

Cited by 88 publications

References 258 publications

Low temperature secondary emission mass spectrometry. Cryobiological applications

Low temperature secondary emission mass spectrometry. Cryobiological applications

Iridoids and Anthraquinones from the Malaysian Medicinal Plant, Saprosma scortechinii (Rubiaceae).

Suppression and enhancement of secondary ion formation due to the chemical environment in static-secondary ion mass spectrometry

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