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Deprotonated Molecules (deprotonated + molecule)
Selected AbstractsAnimal urine as painting materials in African rock art revealed by cluster ToF-SIMS mass spectrometry imagingJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 8 2010Vincent Mazel Abstract The rock art site at the village of Songo in Mali is a very important Dogon ritual place where, since the end of the nineteenth century until today, takes place the ceremony of circumcision. During these ceremonies, paintings are performed on the walls of the shelter with mainly three colors: red, black and white. Ethnological literature mentions the use of animal urine of different species such as birds, lizards or snakes as a white pigment. Urine of these animals is mainly composed of uric acid or urate salts. In this article, time-of-flight secondary ion mass spectrometry (ToF-SIMS) is used to compare uric acid, snake urine and a sample of a white pigment of a Dogon painting coming from the rock art site of Songo. ToF-SIMS measurements in both positive and negative ion modes on reference compounds and snake urine proved useful for the study of uric acid and urate salts. This method enables to identify unambiguously these compounds owing to the detection in negative ion mode of the ion corresponding to the deprotonated molecule ([M , H], at m/z 167.01) and its fragment ions. Moreover, the mass spectra obtained in positive ion mode permit to differentiate uric acid and urate salts on the basis of specific ions. Applying this method to the Dogon white pigments sample, we show that the sample is entirely composed of uric acid. This proves for the first time, that animal urine was used as a pigment by the Dogon. The presence of uric acid instead of urate salts as normally expected in animal urine could be explained by the preparation of the pigment for its application on the stone. Copyright © 2010 John Wiley & Sons, Ltd. [source] High-speed separation and characterization of major constituents in Radix Paeoniae Rubra by fast high-performance liquid chromatography coupled with diode-array detection and time-of-flight mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 1 2009E-Hu Liu A fast high-performance liquid chromatography (HPLC) method coupled with diode-array detection (DAD) and electrospray ionization time-of-flight mass spectrometry (ESI-TOFMS) has been developed for rapid separation and sensitive identification of major constituents in Radix Paeoniae Rubra (RPR). The total analysis time on a short column packed with 1.8-µm porous particles was about 20,min without a loss in resolution, six times faster than the performance of a conventional column analysis (115,min). The MS fragmentation behavior and structural characterization of major compounds in RPR were investigated here for the first time. The targets were rapidly screened from RPR matrix using a narrow mass window of 0.01,Da to restructure extracted ion chromatograms. Accurate mass measurements (less than 5,ppm error) for both the deprotonated molecule and characteristic fragment ions represent reliable identification criteria for these compounds in complex matrices with similar if not even better performance compared with tandem mass spectrometry. A total of 26 components were screened and identified in RPR including 11 monoterpene glycosides, 11 galloyl glucoses and 4 other phenolic compounds. From the point of time savings, resolving power, accurate mass measurement capability and full spectral sensitivity, the established fast HPLC/DAD/TOFMS method turns out to be a highly useful technique to identify constituents in complex herbal medicines. Copyright © 2008 John Wiley & Sons, Ltd. [source] Measurement of serum salicylate levels by solid-phase extraction and desorption/ionization on silicon mass spectrometryJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 8 2005Shoji Okuno Abstract The applicability of the matrix-free laser desorption/ionization on silicon mass spectrometry (DIOS-MS) to measuring serum drug levels was examined by analyzing serum salicylic acid. The optimized and simple solid-phase extraction (SPE) allowed good recovery, 88.9 ± 5.8%, for 1.4 mM (200 mg/L) of salicylic acid in serum. The negative ion MS allowed measurements of deprotonated molecules without interference from other signals. Using a deuterium-labeled internal standard, good linearity was obtained in the 0.14 to 4.2 mM (20,600 mg/L) range, which was sufficient for monitoring the therapeutic anti-inflammatory dose. SPE followed by DIOS-MS is anticipated to be a method of measuring drug levels in blood and may allow high throughput analysis. Copyright © 2005 John Wiley & Sons, Ltd. [source] New features on the fragmentation patterns of homoisoflavonoids in Ophiopogon japonicus by high-performance liquid chromatography/diode-array detection/electrospray ionization with multi-stage tandem mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 15 2010Jin Qi Homoisoflavonoids, a special class of flavonoids, are mainly distributed in the Liliaceae family and have various biological activities. Previously, very little research has been reported on the gas-phase fragmentation patterns of homoisoflavonoids by electrospray ionization mass spectrometry. In this paper, we report the use of high-performance liquid chromatography with a diode-array detector (HPLC-DAD) and electrospray ionization multi-stage tandem mass spectrometry (ESI-MSn) to study the fragmentation behavior of 11 homoisoflavonoid standards and to analyze homoisoflavonoids in Ophiopogon japonicus. In total, 28 homoisoflavonoids (including seven novel constituents) were characterized. The deprotonated [MH], molecules of the homoisoflavonoids containing a saturated C2C3 bond afforded the A or B product ion (base peak) according to whether the B-ring was substituted with a hydroxyl group. For the homoisoflavonoids containing a C-2C-3 double bond, the product ions (A or C ion) were created from the precursor [MH], ion as the base peak when the B-ring was substituted with a hydroxyl group. The homoisoflavonoids carrying a formyl group in the A-ring readily eliminated one molecule of CO to form the product ion [M,+,HCO], (base peak) irrespective whether the C-2C-3 bond was saturated or not. This product ion afforded the [MHCOB-ringCH2,+,H], ion by cleavage of the C3C9 bond. This latter product ion always appeared in tandem mass (MS/MS) spectra of type I homoisoflavonoids. The common features of flavonoids observed during the gas-phase fragmentation mechanisms were the loss of the following groups: 15,Da (CH3), 18,Da (H2O), 28,Da (CO), 44,Da (CO2) and 46,Da (CH2O2). A retro-Diels-Alder (RDA)-like cleavage was also observed for the homoisoflavonoids. The different gas-phase fragmentation routes were characterized for the deprotonated molecules obtained from the various homoisoflavonoids and collision-induced dissociation (CID) fragmentation differences were noted for the different locations of the various substituents. In conclusion, we can say that this study allowed us to structurally elucidate and identify homoisoflavonoids distributed in related plants and their complex prescriptions. Copyright © 2010 John Wiley & Sons, Ltd. [source] Assigning glucose or galactose as the primary glycosidic sugar in 3- O -mono-, di- and triglycosides of kaempferol using negative ion electrospray and serial mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 19 2009Geoffrey C. Kite Kaempferol 3- O - , -glucopyranoside, kaempferol 3- O - , -galactopyranoside and higher glycosides of these two flavonoids with , -rhamnose at C-2 and/or C-6 of the primary sugar were studied by negative ion electrospray ionisation and serial mass spectrometry in a three-dimensional (3D) ion trap mass spectrometer. Kaempferol 3- O - , -glucopyranoside and kaempferol 3- O - , -rhamnopyranosyl(1,6)- , -glucopyranoside could be distinguished from their respective galactose analogues by differences in the ratio of the radical aglycone ion [Y0 , H],, to the rearrangement aglycone ion Y following MS/MS of the deprotonated molecules. Kaempferol 3- O -rhamnopyranosyl(1,2)- , -glucopyranoside and kaempferol 3- O - , -rhamnopyranosyl(1,2)[, -rhamnopyranosyl(1,6)]- , -glucopyranoside could be distinguished from their respective galactose analogues by differences in the product ion spectra of the [(M , H) , rhamnose], ion following serial mass spectrometry. In the triglycoside, it was deduced that this ion resulted from the loss of the rhamnose substituted at 2-OH of the primary sugar by observing that MS/MS of deprotonated kaempferol 3- O - , -glucopyranosyl(1,2)[, -rhamnopyranosyl(1,6)]- , -glucopyranoside showed the loss of glucose and not rhamnose. Thus the class of sugar (hexose, deoxyhexose, pentose) at C-2 and C-6 of the primary sugar can be determined. These observations aid the assignment of kaempferol 3- O -glycosides, having glucose or galactose as the primary glycosidic sugar, in LC/MS analyses of plant extracts, and this can be done with reference to only a few standards. Copyright © 2009 John Wiley & Sons, Ltd. [source] | ||||||||||