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Ionisation Tandem Mass Spectrometry (ionisation + tandem_mass_spectrometry)

Distribution by Scientific Domains
Chemistry100%

Kinds of Ionisation Tandem Mass Spectrometry

  • electrospray ionisation tandem mass spectrometry
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    Selected Abstracts

    Identification of oleuropein oligomers in olive pulp and pomace

    JOURNAL OF THE SCIENCE OF FOOD AND AGRICULTURE, Issue 10 2006
    Susana M Cardoso
    Abstract Analysis of a purified fraction from acetone extracts of olive pulp and pomace by electrospray ionisation tandem mass spectrometry (ESI-MSn) showed the presence of oleuropein oligomers, whose occurrence has not been reported previously in the literature. The main ionic species (m/z 1613) in the ESI-MS spectrum was an oleuropein trimer containing three linkages through the hydroxytyrosol backbone. In both samples, oleuropein dimers (m/z 1075), trimers comprising two hydroxytyrosol linkages (m/z 1615), tetramers (m/z 2153) and pentamers (m/z 2691) were also detected by MS. The occurrence of oleuropein oligomers was also observed by nuclear magnetic resonance (NMR). 13C, 13C distortionless enhancement by polarisation transfer DEPT 90, 13C DEPT 135, gHSQC (heteronuclear single quantum coherence) and gHMBC (heteronuclear multiple bond coherence) spectra showed all carbon and proton resonances of oleuropein with the exception of the low-mobility and asymmetric signals of the aromatic rings. Since mature olives were used in this study, it is possible that the disappearance of oleuropein that has been described to occur with the olive fruit maturation, could be associated with the formation of phenolic oligomers together with lower-molecular-weight compounds resulting from its degradation. Copyright © 2006 Society of Chemical Industry [source]

    MS/MS profiling of taxoids from the needles of Taxus wallichiana,

    PHYTOCHEMICAL ANALYSIS, Issue 1 2002
    K. P. Madhusudanan
    Abstract Ammonium cationisation has been used for taxoid profiling of partially purified methanolic extracts of needles of Taxus wallichiana growing in different regions of the Himalayas (Kashmir, Himachal Pradesh, UP Hills, Darjeeling, Sikkim and Arunachal Pradesh) by electrospray ionisation tandem mass spectrometry (MS/MS). The MS/MS spectra of the [M,+,NH4]+ or [M,+,H]+ ions gave structurally diagnostic fragment ions which revealed information about the taxane skeleton as well as the number and nature of the substituents. The rearranged 11(15,,,1)- abeo -taxanes showed a characteristic elimination of the hydroxyisopropyl group with an acetoxy/benzoyloxy group from C-9. The identification of the taxoids was achieved by comparison of the MS/MS spectra with those of authentic taxoids or was based on biogenetic grounds. The results were corroborated by liquid chromatography,MS analysis. Out of the 50 taxoids identified, 21 belonged to the rearranged class. The presence of paclitaxel in the samples from four regions was confirmed: the study also revealed the occurrence of several basic taxoids in these samples. ­MS/MS profiling by electrospray ionisation was shown to be a fast and reliable technique for the analysis of taxoid samples. Copyright © 2001 John Wiley & Sons, Ltd. [source]

    Carbon starvation survival of Listeria monocytogenes in planktonic state and in biofilm: A proteomic study

    PROTEINS: STRUCTURE, FUNCTION AND BIOINFORMATICS, Issue 10 2003
    Emmanuelle Helloin
    Abstract The proteomes of Listeria monocytogenes expressed in suspension and biofilm state, in the presence and absence of a caron source, were analysed by two-dimensional electrophoresis with the help of computer software. The up-regulated proteins in each case were identified by peptide sequencing using electrospray ionisation tandem mass spectrometry and a database search against the Listeria genome was performed. Relevant functions could be attributed to a number of the induced proteins which contibute to the understanding of the mechanisms of starvation survival of L. monocytogenes in planktonic state and in biofilm. [source]

    Simultaneous determination of parabens, triclosan and triclocarban in water by liquid chromatography/electrospray ionisation tandem mass spectrometry

    RAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 12 2009
    Iria González-Mariño
    A method for the determination of several household biocides in water by liquid chromatography/electrospray ionisation tandem mass spectrometry (LC/ESI-MS/MS) is presented. It permits the simultaneous determination of triclosan (TCS), triclocarban (TCC) and seven parabens, including the distinction between branched and linear isomers of propyl (i -PrP and n -PrP) and butyl parabens (i -BuP and n -BuP). Prior to LC/MS/MS, analytes are preconcentrated by solid-phase extraction (SPE) on Oasis HLB (60,mg) cartridges at natural sample pH and subsequently eluted with 4,mL of methanol. This simple SPE procedure provides extraction recoveries above 85% except for raw wastewater, where it falls to 65% for TCC. The performance of the method was tested with two triple-quadrupole LC/MS instruments from a low/mid and mid/high market range: a Varian 1200L and an API-4000. The latter system provided between 3 and 80 times lower limits of quantification (LOQs) than the first one, in the 0.08,0.44,ng/L range for surface water. Moreover, a comparison of matrix effects on both instruments showed a very different behaviour, particularly in the case of parabens. For these compounds signal suppression was observed in the 1200L instrument and signal enhancement with the 4000 instrument. As a result, different calibration approaches were chosen for them and this pointed to the need of matrix effect re-evaluation in method transfer between different LC/MS systems. The application of the method to real samples showed the ubiquity of methyl paraben (MeP) and n -PrP (at the 1,6,µg/L in raw wastewater) and the coexistence of i -BuP and n -BuP at similar levels (ca. 100,200,ng/L in raw wastewater). Copyright © 2009 John Wiley & Sons, Ltd. [source]

    Simultaneous detection of five different 2-hydroxyethyl-DNA adducts formed by ethylene oxide exposure, using a high-performance liquid chromatography/electrospray ionisation tandem mass spectrometry assay

    RAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 1 2008
    Elaine M. Tompkins
    A method has been developed for the simultaneous detection and quantitation of five different 2-hydroxyethyl-DNA (HE-DNA) adducts that could be formed as a result of exposure to ethylene oxide (EO). In addition to the major N7-HE-guanine (N7-HEG) adducts this assay can also measure the less prevalent but potentially more biologically significant N1-HE-2,-deoxyadenosine (N1-HEdA), O6 -HE-2,-deoxyguanosine (O6 -HEdG), N6 -HE-2,-deoxyadenosine (N6 -HEdA) and N3-HE-2,-deoxyuridine adducts (N3-HEdU). The method involves the isolation of HE adducts from the unmodified nucleosides by either neutral thermal hydrolysis or enzymatic digestion, followed by high-performance liquid chromatographic (HPLC) purification, before detection and quantification by liquid chromatography tandem mass spectrometry (LC/MS/MS) using selective reaction monitoring (SRM). The limits of detection were in the range 0.5,25,fmol for each individual adduct, making this one of the most sensitive assays available for the detection of N7-HEG. To illustrate the possible applications of the assay, it has been employed in the measurement of endogenous/background and EO-induced HE adducts in a variety of DNA samples. Copyright © 2007 John Wiley & Sons, Ltd. [source]

    Development of a multi-residue method for the determination of 18 carbamates in tobacco by high-performance liquid chromatography/positive electrospray ionisation tandem mass spectrometry

    RAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 4 2006
    B. Mayer-Helm
    A multi-residue method for the determination of carbamates in tobacco was developed by high-performance liquid chromatography (HPLC) triple quadrupole mass spectrometry (MS). A rapid sample preparation consisted of an extraction step with methanol, centrifugation and 1:1 dilution with aqueous 10,mM ammonium acetate. After filtration these extracts were directly analysed by reversed-phase HPLC coupled to positive electrospray ionisation tandem mass spectrometry operated in the multiple reaction monitoring mode. Capillary voltage and dwell times were optimised to reduce matrix effects and to increase sensitivity. The method was validated for the determination of 18 carbamates in three main types of raw tobacco and three tobacco products. The interday accuracy ranged between 80 and 110% with a relative standard deviation (RSD) of <30%. The limits of quantification (LOQs) ranged between 0.01 and 0.04,ppm for almost all carbamates, except aldicarb sulfone, carbofuran, and pebulate, with LOQs between 0.10 and 0.20,ppm. These LOQs were clearly below the guidance residue levels defined by the Agrochemical Advisory Committee of CORESTA, an association of organisations having scientific research relative to tobacco. Copyright © 2006 John Wiley & Sons, Ltd. [source]

    Fragmentation of mycosporine-like amino acids by hydrogen/deuterium exchange and electrospray ionisation tandem mass spectrometry

    RAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 2 2006
    Karina H. M. Cardozo
    The determination and identification of mycosporine-like amino acids (MAAs) from algae remain a major challenge due to the low concentration. Mass spectrometry (MS) can make an invaluable contribution in the search and identification of MAAs because of its high sensitivity, possibility of coupling with liquid chromatography, and the availability of powerful tandem mass spectrometric techniques. However, the unequivocal determination of the presence and location of important functional groups present on the basic skeleton of the MAAs is often elusive due to their inherent instability under MS conditions. In this study, the use of hydrogen/deuterium (H/D) exchange and electrospray ionisation tandem mass spectrometry (ESI-MS/MS) for characterisation of four MAAs (palythine, asterina, palythinol and shinorine) isolated from the macroalgae Gracilaria tenuistipitata Chang et Xia was investigated. The accurate-mass confirmation of the protonated molecules was performed on a Q-TOF instrument. We demonstrate that employing deuterium labelling in ESI-MS/MS analysis provides a convenient tool for the determination of new MAAs. Although the fragmentation patterns of MAAs were discussed earlier, to our knowledge, this is the first time that mechanisms are proposed. Copyright © 2005 John Wiley & Sons, Ltd. [source]

    In-house validation of a liquid chromatography/electrospray tandem mass spectrometry method for confirmation of chloramphenicol residues in muscle according to Decision 2002/657/EC

    RAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 22 2005
    Floriana Vinci
    In this work we present an in-house validation study for the confirmatory analysis of chloramphenicol (CAP) in muscle according to the Commission Decision 2002/657/EC requirements. CAP is extracted in acetonitrile and after liquid-liquid partitioning with n -hexane is identified and quantitatively determined by ion trap liquid chromatography/electrospray ionisation tandem mass spectrometry (LC/ESI-MS/MS) analysis in the negative ion mode. CAP was identified using the precursor ion and at least two product ions, meeting the qualitative and quantitative criteria set by the European Commission in the Decision 2002/657/EC for confirmation of prohibited veterinary drug residues. We calculated mean drug recoveries, CC, and CC, of the method, and reported data on specificity, ruggedness and within-laboratory reproducibility. Finally, we point out and discuss some problems and questions arising from controversy about the application of Decision 2002/657/EC. Copyright © 2005 John Wiley & Sons, Ltd. [source]

    Characterisation of sulphoxides by atmospheric pressure ionisation mass spectrometry

    RAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 14 2005
    Patricia Wright
    An observation that a series of proprietary compounds containing a methyl thiophenyl group all underwent metabolic S-oxidation, and that the product ion spectra of the resulting S-oxides showed methyl radical loss under low-energy atmospheric pressure ionisation tandem mass spectrometry (API-MS/MS) conditions, has led to an investigation of the fragmentation of commercially available sulphoxides. The phenyl methyl sulphoxides studied do lose methyl radicals under MS/MS conditions on triple quadrupole mass spectrometers. In addition, the phenyl sulphoxides, with simple substituents other than a methyl group, also showed a tendency to lose the substituent as a radical. It was concluded that radical loss from these simple sulphoxides was characteristic of S-oxidation of these molecules. Radical losses, such as those reported here, are used in-house to distinguish S-oxidation from N- and C-oxidation in metabolism studies. Copyright © 2005 John Wiley & Sons, Ltd. [source]

    Sensitive determination of acidic drugs and triclosan in surface and wastewater by ion-pair reverse-phase liquid chromatography/tandem mass spectrometry

    RAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 7 2004
    José Benito Quintana
    A new method is presented for the determination of 12 acidic pharmaceuticals (non-steroidal anti-inflammatory drugs and bezafibrate), including two metabolites from aqueous samples, together with triclosan as a personal care product. Ion-pair liquid chromatography (IP-LC) with electrospray ionisation tandem mass spectrometry (ESI-MS) in the negative ion mode was employed. The ion-pairing agent (tri- n -butylamine) increased the signal intensity for all acidic analytes and detection limits of 6,200,ng/L were obtained by multiple reaction monitoring. This allows analysis of wastewater samples by direct injection into the LC/MS system without the need for a preceding enrichment step. When combined with a solid-phase extraction (SPE) step, limits of quantification between 0.15 and 11,ng/L were obtained from 100-mL sample volumes, which is adequate for most applications. The occurrence of matrix effects was studied and standard addition was required for reliable quantification after SPE from wastewater. The method was finally applied to surface and wastewaters, with analyte concentrations ranging from below the detection limit up to 5.5,,g/L. Copyright © 2004 John Wiley & Sons, Ltd. [source]

    Determination of phenolic compounds in rose hip (Rosa canina) using liquid chromatography coupled to electrospray ionisation tandem mass spectrometry and diode-array detection

    RAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 7 2002
    Erlend Hvattum
    Liquid chromatography coupled with negative and positive electrospray ionisation (ESI) tandem mass spectrometry (MS/MS) and diode-array detection (DAD) was used for determination of phenols in rose hip (Rosa canina) extract. ESI mass spectra of the chromatographically separated phenols gave the molecular weight of the compounds through prominent [M,,,H], ions for most of the compounds and M+ ions for the anthocyanins. Collision induced dissociation (CID) of the [M,,,H], (or M+) precursor ions yielded product ions which determined the molecular weight of the aglycones. In-source fragmentation followed by CID of the resulting deprotonated aglycone ([A,,,H],) provided product ions for the identification of the unconjugated phenols. The identification was based on comparison with product ion spectra of commercial standards. UV-diode-array spectra were used for identity confirmation. This combined approach allowed the identification in rose hip extract of an anthocyanin, i.e. cyanidin-3- O -glucoside, several glycosides of quercetin and glycosides of taxifolin and eriodictyol. Phloridzin was identified, and several conjugates of methyl gallate were also found, one of which was tentatively identified as methyl gallate-rutinoside. Catechin and quercetin were found as the aglycones in the extract. Copyright © 2002 John Wiley & Sons, Ltd. [source]