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Isotopic Enrichment (isotopic + enrichment)
Selected AbstractsLiquid and gas chromatography coupled to isotope ratio mass spectrometry for the determination of 13C,valine isotopic ratios in complex biological samplesJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 10 2008Jean-Philippe Godin Abstract On-line gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) is commonly used to measure isotopic ratios at natural abundance as well as for tracer studies in nutritional and medical research. However, high-precision 13C isotopic enrichment can also be measured by liquid chromatography-isotope ratio mass spectrometry (LC-IRMS). Indeed, LC-IRMS can be used, as shown by the new method reported here, to obtain a baseline separation and to measure 13C isotopic enrichment of underivatised amino acids (Asp, Thr,Ser, Glu, Pro, Gly, Ala, Cys and Val). In case of Val, at natural abundance, the SD(,13C) reported with this method was found to be below 1, . Another key feature of the new LC-IRMS method reported in this paper is the comparison of the LC-IRMS approach with the conventional GC-C-IRMS determination. To perform this comparative study, isotopic enrichments were measured from underivatised Val and its N(O, S)-ethoxycarbonyl ethyl ester derivative. Between 0.0 and 1.0 molar percent excess (MPE) (,13C = , 12.3 to 150.8,), the calculated root-mean-square (rms) of SD was 0.38 and 0.46, and the calculated rms of accuracy was 0.023 and 0.005 MPE, respectively, for GC-C-IRMS and LC-IRMS. Both systems measured accurately low isotopic enrichments (0.002 atom percent excess (APE)) with an SD (APE) of 0.0004. To correlate the relative (,13C) and absolute (atom%, APE and MPE) isotopic enrichment of Val measured by the GC-C-IRMS and LC-IRMS devices, mathematical equations showing the slope and intercept of the curves were established and validated with experimental data between 0.0 to 2.3 MPE. Finally, both GC-C-IRMS and LC-IRMS instruments were also used to assess isotopic enrichment of protein-bound 13C,Val in tibial epiphysis in a tracer study performed in rats. Isotopic enrichments measured by LC-IRMS and GC-C-IRMS were not statistically different (p > 0.05). The results of this work indicate that the LC-IRMS was successful for high-precision 13C isotopic measurements in tracer studies giving 13C isotopic enrichment similar to the GC-C-IRMS but without the step of GC derivatisation. Therefore, for clinical studies requiring high-precision isotopic measurement, the LC-IRMS is the method of choice to measure the isotopic ratio. Copyright © 2008 John Wiley & Sons, Ltd. [source] Incorporating life histories and diet quality in stable isotope interpretations of crustacean zooplanktonFRESHWATER BIOLOGY, Issue 7 2008MARC VENTURA Summary 1. Stable isotope studies have been extremely useful for improving general food web descriptions due to their ability to simultaneously summarize complex trophic networks and track the energy flow through them. However, when considering trophic relationships involving only two or few species, application of general isotopic interpretations based on average fractionation values may easily lead to misleading conclusions. In these cases a more accurate consideration of the current processes involved in the isotopic fractionation should be considered. 2. We investigated the trophic relationships of the crustacean zooplankton assemblage in an alpine lake (Lake Redon, Pyrenees) by means of stable isotopes of carbon and nitrogen and applied information on their life history and biochemical composition in the interpretation. 3. The three species occurring in the lake had distinct isotopic signatures: the two copepod species (the cyclopoid Cyclops abyssorum and the calanoid Diaptomus cyaneus) had higher nitrogen isotopic composition than the cladoceran (Daphnia pulicaria), indicative of a higher trophic position of the two copepods. Most intra-specific isotopic variability was associated with growth, while the effect of metabolic turnover was negligible. The effects of changes in the proportion of lipids was restricted to the adults of the two copepods. 4. Daphnia Juveniles showed ontogenetic shifts in their carbon, and nitrogen isotopic composition. Cyclops copepodites only showed changes in carbon isotopic composition. These isotopic shifts with changes in size were the result of: (i) the prevalence of growth over metabolic turnover as the main factor for isotopic variability and (ii) feeding, during the growth period, on isotopically depleted food in the case of Daphnia, and on isotopically enriched food in the case of Cyclops. 5. The carbon isotopic variation in Cyclops juveniles could be explained by fitting an isotopic growth model that considered that they fed entirely on Daphnia. However this was not the case for nitrogen isotopic variability. Cyclops nitrogen isotopic composition variation and the Cyclops to Daphnia nitrogen isotopic enrichment were closely correlated to the quantity of Daphnia protein and to the dissimilarity in the essential amino acid composition between the two species, which can be interpreted as an indication of consumer nitrogen limitation. [source] Denitrification in a hyporheic riparian zone controlled by river regulation in the Seine river basin (France)HYDROLOGICAL PROCESSES, Issue 5 2009F. Curie Abstract The purpose of this paper is to study denitrification and the conditions for its development in a hyporheic zone. The study site is the riparian zone of a former branch of the Seine River, where the river stage is kept almost constant during the year by hydraulic regulation. Hydrological and geochemical surveys were performed by monitoring four wells, ten shorter piezometers and the river over a 15-month period. The water fluxes originating from the chalky hillsides and the river converge in a zone parallel to the river that acts as a drainage flow path through the floodplain. The riparian zone between this flow path and the river shows an important depletion of nitrate during the summer and autumn period, which cannot be explained by a simple mixing of waters coming from the river and the chalky hillsides. It can be attributed to denitrification as it occurs when oxygen concentration is below 2 mg l,1, and goes along with a consumption of dissolved organic carbon and a decrease of redox potential. The river completely controls these hydro-geochemical conditions. It also keeps the wetness of the riparian zone almost constant, which allowed us to isolate the high temperatures in summer and autumn as an important triggering factor for denitrification through its influence on the reaction rate and oxygen deficits. We also found a small isotopic enrichment of nitrate, suggesting that denitrification occurs after diffusion of nitrate through the sediment and riparian zone matrix, which is consistent with the hyporheic functioning of the study site. Copyright © 2008 John Wiley & Sons, Ltd. [source] Synthesis of deuterium labelled diclofenac with improved isotopic enrichmentJOURNAL OF LABELLED COMPOUNDS AND RADIOPHARMACEUTICALS, Issue 13 2009Keying Wu Abstract A five-step synthesis of deuterium-labelled diclofenac starting from 2-phenyl[2H5] acetic acid is described. The synthesis prevents deuterium from scrambling during the reaction. It offers the labelled compound with over 99% isotopic enrichment. It also provides a possible alternative route for the synthesis of deuterium-labelled 4,-hydroxydiclofenac, which is the principal human metabolite of diclofenac. Copyright © 2009 John Wiley & Sons, Ltd. [source] Synthesis of deuterium, tritium, and carbon-14 labeled BIRB 796, a p38 MAP kinase inhibitorJOURNAL OF LABELLED COMPOUNDS AND RADIOPHARMACEUTICALS, Issue 12 2004Bachir Latli Abstract 1-(5- tert -Butyl-2- p -tolyl-2H-pyrazol-3-yl)-3-[4-(2-morpholin-4-yl-ethoxy)naphthalen-1-yl]urea (BIRB 796), currently in clinical trials for the treatment of inflammatory diseases, is a potent inhibitor of p38 MAP kinase. Labeled BIRB 796 with stable and radioactive isotopes was required for metabolism, distribution, and absorption studies. We first report the synthesis of carbon-14 labeled BIRB 796 with a specific activity of 2 GBq/mmol (54.2 mCi/mmol), using [14C]-phosgene under modified Schotten,Baumann conditions; second the preparation of tritium-labeled BIRB 796 with a specific activity of 659 GBq/mmol (17.81 Ci/mmol) by reductive dehalogenation of iodo-BIRB 796 with tritium gas; and finally, the synthesis of 2H8 -BIRB 796 using morpholine-2,2,3,3,5,5,6,6- 2H8 with isotopic enrichment of 98.9 at% 2H. Copyright © 2004 John Wiley & Sons, Ltd. [source] Liquid and gas chromatography coupled to isotope ratio mass spectrometry for the determination of 13C,valine isotopic ratios in complex biological samplesJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 10 2008Jean-Philippe Godin Abstract On-line gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) is commonly used to measure isotopic ratios at natural abundance as well as for tracer studies in nutritional and medical research. However, high-precision 13C isotopic enrichment can also be measured by liquid chromatography-isotope ratio mass spectrometry (LC-IRMS). Indeed, LC-IRMS can be used, as shown by the new method reported here, to obtain a baseline separation and to measure 13C isotopic enrichment of underivatised amino acids (Asp, Thr,Ser, Glu, Pro, Gly, Ala, Cys and Val). In case of Val, at natural abundance, the SD(,13C) reported with this method was found to be below 1, . Another key feature of the new LC-IRMS method reported in this paper is the comparison of the LC-IRMS approach with the conventional GC-C-IRMS determination. To perform this comparative study, isotopic enrichments were measured from underivatised Val and its N(O, S)-ethoxycarbonyl ethyl ester derivative. Between 0.0 and 1.0 molar percent excess (MPE) (,13C = , 12.3 to 150.8,), the calculated root-mean-square (rms) of SD was 0.38 and 0.46, and the calculated rms of accuracy was 0.023 and 0.005 MPE, respectively, for GC-C-IRMS and LC-IRMS. Both systems measured accurately low isotopic enrichments (0.002 atom percent excess (APE)) with an SD (APE) of 0.0004. To correlate the relative (,13C) and absolute (atom%, APE and MPE) isotopic enrichment of Val measured by the GC-C-IRMS and LC-IRMS devices, mathematical equations showing the slope and intercept of the curves were established and validated with experimental data between 0.0 to 2.3 MPE. Finally, both GC-C-IRMS and LC-IRMS instruments were also used to assess isotopic enrichment of protein-bound 13C,Val in tibial epiphysis in a tracer study performed in rats. Isotopic enrichments measured by LC-IRMS and GC-C-IRMS were not statistically different (p > 0.05). The results of this work indicate that the LC-IRMS was successful for high-precision 13C isotopic measurements in tracer studies giving 13C isotopic enrichment similar to the GC-C-IRMS but without the step of GC derivatisation. Therefore, for clinical studies requiring high-precision isotopic measurement, the LC-IRMS is the method of choice to measure the isotopic ratio. Copyright © 2008 John Wiley & Sons, Ltd. [source] Continuous flow isotope ratio mass spectrometry for the measurement of nanomole amounts of 13CO2 by a reverse isotope dilution methodJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 1 2002J. Guitton Abstract A simple method for the determination of nanomole amounts of 13CO2 generated from an in vitro reaction is reported. The incubation medium contains a known amount of unlabeled sodium bicarbonate and the gaseous 13CO2 enriches the atmosphere upon which a measurement of the isotopic enrichment (13CO2/12CO2) is made corresponding to a reverse isotope dilution. The quantification of the 13CO2 was performed by gas chromatography/isotope ratio mass spectrometry. This assay was validated in terms of linearity, accuracy and precision using three different substrates which produce 13CO2 either by enzymatic reaction [13C]urea, sodium [13C]formate) or by chemical reaction (sodium [13C]bicarbonate). Four calibration curves were tested for each 13C-labeled substrate, allowing the quantification of 13CO2 from 25 pmol to 150 nmol. The dynamics of the assay were obtained as a function of the quantity of unlabeled sodium bicarbonate added to each sample. Copyright © 2001 John Wiley & Sons, Ltd. [source] DIET-TISSUE FRACTIONATION OF STABLE CARBON AND NITROGEN ISOTOPES IN PHOCID SEALSMARINE MAMMAL SCIENCE, Issue 1 2002VÉRONIQUE Lesage Diet-tissue isotopic fractionation of carbon (C) and nitrogen (N) isotopes in short- and longer-term diet integrators of diet (i. e., blood serum and red cells), that involve non-invasive sampling techniques was examined using three species of phocid seals (harbor seals, gray seals, and harp seals) fed a known diet. Variability in diet-tissue fractionation values within and between species was also scrutinized to determine the legitimacy of using values obtained from one species to explore trophic positions and diets of other related species. All captive seals raised on a constant diet had tissues enriched in 13C and 15N relative to their diet. Diet-tissue isotopic fractionation values were generally consistent among conspecifics and among phocid species for a given tissue. Trophic isotopic enrichment in 13C was significantly higher in red blood cells (+1.5%±) than in blood serum (+0.8%±), whereas the reverse was observed for nitrogen isotopes (+1.7%± in red cells vs. +3.1%± in serum). However, 13C-depleted lipids were not extracted from blood tissues in this study. This results in a downward bias in the diet-tissue fractionation factors for carbon for both red cells and blood serum, particularly the latter because of their significantly higher lipid contents (x,± SD = 14.6 ± 2.3%; n= 20; red blood cells 3.8 ± 0.9%±; n= 50, muscle 7.7 ± 2.0; n= 21) in marine mammals. [source] Interfacial spin structure in epitaxial Fe/FeSn2 bilayers with exchange biasPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 12 2004F. Stromberg Abstract Fe/FeSn2 structures with epitaxial FeSn2 layers have been grown by MBE (Molecular Beam Epitaxy). Exchange bias and pinning phenomena were proved by SQUID magnetometry. In order to elucidate the spin structure at the Fe/FeSn2 interface and in some depth of the FeSn2 layer with CEMS (Conversion Electron Mössbauer Spectroscopy), 57FeSn2 tracer layers of approx. 50 Å thickness have been incorpo- rated in the base structure, the only difference being the isotopic enrichment with 57Fe. An ellipsoidal model was applied to represent the spin structure. A strong out-of-plane component of the spin structure at the interface was observed. (© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Modelling advection and diffusion of water isotopologues in leavesPLANT CELL & ENVIRONMENT, Issue 8 2007MATTHIAS CUNTZ ABSTRACT We described advection and diffusion of water isotopologues in leaves in the non-steady state, applied specifically to amphistomatous leaves. This explains the isotopic enrichment of leaf water from the xylem to the mesophyll, and we showed how it relates to earlier models of leaf water enrichment in non-steady state. The effective length or tortuosity factor of isotopologue movement in leaves is unknown and, therefore, is a fitted parameter in the model. We compared the advection,diffusion model to previously published data sets for Lupinus angustifolius and Eucalyptus globulus. Night-time stomatal conductance was not measured in either data set and is therefore another fitted parameter. The model compared very well with the observations of bulk mesophyll water during the whole diel cycle. It compared well with the enrichment at the evaporative sites during the day but showed some deviations at night for E. globulus. It became clear from our analysis that night-time stomatal conductance should be measured in the future and that the temperature dependence of the tracer diffusivities should be accounted for. However, varying mesophyll water volume did not seem critical for obtaining a good prediction of leaf water enrichment, at least in our data sets. In addition, observations of single diurnal cycles do not seem to constrain the effective length that relates to the tortuosity of the water path in the mesophyll. Finally, we showed when simpler models of leaf water enrichment were suitable for applications of leaf water isotopes once weighted with the appropriate gas exchange flux. We showed that taking an unsuitable leaf water enrichment model could lead to large biases when cumulated over only 1 day. [source] Brief communication: Tissue isotopic enrichment associated with growth depression in a pig: Implications for archaeology and ecologyAMERICAN JOURNAL OF PHYSICAL ANTHROPOLOGY, Issue 3 2010Christina Warinner Abstract Stressors such as fasting or poor diet quality are thought to potentially alter the nitrogen and carbon isotopic values of animal tissues. In this study, we demonstrate an inverse correlation between growth rate and multiple tissue enrichment of ,15N, ,13C, and, to a lesser degree, ,18O in a juvenile pig. A more complex pattern is observed with respect to tissue ,D and growth rate. The observed association between growth rate and tissue isotopic fractionation has important implications for paleodietary and migratory reconstructions of archaeological populations that may have been affected by famine, malnutrition, seasonal variation in food availability, and/or other factors that can affect childhood growth rates. Am J Phys Anthropol 2010. © 2010 Wiley-Liss, Inc. [source] Simultaneous measurement of 13C- and 15N-isotopic enrichments of threonine by mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 8 2009Jean-Philippe Godin Under conditions of high isotopic dilution, e.g. in a tracer study, the ability to determine accurately and quantitatively small variations in isotopic enrichments of differently labelled chemical compounds (e.g. 13C and 15N in threonine) in a single run by gas chromatography/mass spectrometry (GC/MS) is desirable but remains a technological challenge. Here, we report a new, rapid and simple GC/MS method for simultaneously measuring the isotopic enrichments of doubly labelled threonine ([U13C] and 15N) with isotopic enrichment lower than 1.5 Molar Percent Excess (MPE). The long-term reproducibility measured was around 0.09 MPE for both tracers (throughout a 6 week period). The intra-day repeatability was lower than 0.05 and 0.06 MPE for [U13C]-Thr and 15N-Thr, respectively. To calculate both isotopic enrichments, two modes of calculations were used: one based on work by Rosenblatt et al. in 1992 and the other one using a matrix approach. Both methods gave similar results (ANOVA, P >0.05) with close precision for each mode of calculation. The GC/MS method was then used to investigate the differential utilization of threonine in different organs according to its route of administration in minipigs after administration of both tracers. In plasma samples, the lowest isotopic enrichment measured between two successive time points was at 0.01 and 0.02 MPE for [U13C]-Thr and 15N-Thr, respectively. Moreover, the accuracy of GC/MS 13C-isotopic enrichment measured was validated by analyzing the same plasma samples by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Statistical analysis showed that both techniques gave the same results (ANOVA, P >0.05). This new GC/MS method offers the possibility to measure 13C- and 15N-isotopic enrichments with higher throughput, and using a lower amount of sample, than using GC/C/IRMS. Copyright © 2009 John Wiley & Sons, Ltd. [source] Effects of temperature on isotopic enrichment in Daphnia magna: implications for aquatic food-web studiesRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 14 2003M. Power Laboratory experiments were conducted with Daphnia magna and Hyalella sp. grown on a single food source of known isotopic composition at a range of temperatures spanning the physiological optima for each species. Daphnia raised at 26.5°C were enriched in ,13C and ,15N by 3.1 and 2.8,, respectively, relative to diet. Daphnia raised at 12.8°C were enriched 1.7 and 5.0, in ,13C and ,15N, respectively. Results imply a significant negative relationship between the ,13C and ,15N of primary consumers when a temperature gradient exists. Similar responses were observed for Hyalella. Results indicate a general increase in ,13C enrichment and decrease in ,15N enrichment as temperature rises. Deviations from the commonly applied isotopic enrichment values used in aquatic ecology were attributed to changes in temperature-mediated physiological rates. Field data from a variety of sources also showed a general trend toward ,13C enrichment with increasing temperature in marine and lacustrine zooplankton. Multivariate regression models demonstrated that, in oligotrophic and mesotrophic lakes, zooplankton ,13C was related to lake-specific POM ,13C, lake surface temperature and latitude. Temperature-dependent isotopic separation (enrichment) between predator and prey should be taken into consideration when interpreting the significance of isotopic differences within and among aquatic organisms and ecosystems, and when assigning organisms to food-web positions on the basis of observed isotope values. Copyright © 2003 John Wiley & Sons, Ltd. [source] Liquid and gas chromatography coupled to isotope ratio mass spectrometry for the determination of 13C,valine isotopic ratios in complex biological samplesJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 10 2008Jean-Philippe Godin Abstract On-line gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) is commonly used to measure isotopic ratios at natural abundance as well as for tracer studies in nutritional and medical research. However, high-precision 13C isotopic enrichment can also be measured by liquid chromatography-isotope ratio mass spectrometry (LC-IRMS). Indeed, LC-IRMS can be used, as shown by the new method reported here, to obtain a baseline separation and to measure 13C isotopic enrichment of underivatised amino acids (Asp, Thr,Ser, Glu, Pro, Gly, Ala, Cys and Val). In case of Val, at natural abundance, the SD(,13C) reported with this method was found to be below 1, . Another key feature of the new LC-IRMS method reported in this paper is the comparison of the LC-IRMS approach with the conventional GC-C-IRMS determination. To perform this comparative study, isotopic enrichments were measured from underivatised Val and its N(O, S)-ethoxycarbonyl ethyl ester derivative. Between 0.0 and 1.0 molar percent excess (MPE) (,13C = , 12.3 to 150.8,), the calculated root-mean-square (rms) of SD was 0.38 and 0.46, and the calculated rms of accuracy was 0.023 and 0.005 MPE, respectively, for GC-C-IRMS and LC-IRMS. Both systems measured accurately low isotopic enrichments (0.002 atom percent excess (APE)) with an SD (APE) of 0.0004. To correlate the relative (,13C) and absolute (atom%, APE and MPE) isotopic enrichment of Val measured by the GC-C-IRMS and LC-IRMS devices, mathematical equations showing the slope and intercept of the curves were established and validated with experimental data between 0.0 to 2.3 MPE. Finally, both GC-C-IRMS and LC-IRMS instruments were also used to assess isotopic enrichment of protein-bound 13C,Val in tibial epiphysis in a tracer study performed in rats. Isotopic enrichments measured by LC-IRMS and GC-C-IRMS were not statistically different (p > 0.05). The results of this work indicate that the LC-IRMS was successful for high-precision 13C isotopic measurements in tracer studies giving 13C isotopic enrichment similar to the GC-C-IRMS but without the step of GC derivatisation. Therefore, for clinical studies requiring high-precision isotopic measurement, the LC-IRMS is the method of choice to measure the isotopic ratio. Copyright © 2008 John Wiley & Sons, Ltd. [source] Liquid chromatography combined with mass spectrometry for 13C isotopic analysis in life science researchMASS SPECTROMETRY REVIEWS, Issue 6 2007Jean-Philippe Godin Abstract Among the different disciplines covered by mass spectrometry, measurement of 13C/12C isotopic ratio crosses a large section of disciplines from a tool revealing the origin of compounds to more recent approaches such as metabolomics and proteomics. Isotope ratio mass spectrometry (IRMS) and molecular mass spectrometry (MS) are the two most mature techniques for 13C isotopic analysis of compounds, respectively, for high and low-isotopic precision. For the sample introduction, the coupling of gas chromatography (GC) to either IRMS or MS is state of the art technique for targeted isotopic analysis of volatile analytes. However, liquid chromatography (LC) also needs to be considered as a tool for the sample introduction into IRMS or MS for 13C isotopic analyses of non-volatile analytes at natural abundance as well as for 13C-labeled compounds. This review presents the past and the current processes used to perform 13C isotopic analysis in combination with LC. It gives particular attention to the combination of LC with IRMS which started in the 1990's with the moving wire transport, then subsequently moved to the chemical reaction interface (CRI) and was made commercially available in 2004 with the wet chemical oxidation interface (LC-IRMS). The LC-IRMS method development is also discussed in this review, including the possible approaches for increasing selectivity and efficiency, for example, using a 100% aqueous mobile phase for the LC separation. In addition, applications for measuring 13C isotopic enrichments using atmospheric pressure LC-MS instruments with a quadrupole, a time-of-flight, and an ion trap analyzer are also discussed as well as a LC-ICPMS using a prototype instrument with two quadrupoles. © 2007 Wiley Periodicals, Inc., Mass Spec Rev 26:751,774, 2007 [source] Neutron capture effects on samarium, europium, and gadolinium in Apollo 15 deep drill-core samplesMETEORITICS & PLANETARY SCIENCE, Issue 3 2000Hiroshi HIDAKA Large isotopic deviations of 150Sm/149Sm, 156Gd/155Gd, and 158Gd/157Gd derived from neutron capture effects were observed in all samples. Although neutron capture products in lunar samples were investigated extensively in the 1970s, our precise isotopic measurements resulted in several new findings. The neutron fluence in the Apollo 15 drill core is a function of depth with a symmetric peak at 190 g/cm2 depth from the surface, confirming the results of earlier investigations. Neutron fluence values calculated from the isotopic shifts by comparison to artificially irradiated standard reagents were (5.16,7.49) × 1016 n/cm2. These values are 1.3 to 1.4x larger than those previously reported. Variations of ,Sm/,Gd with depth are interpreted as being due to variations in the neutron energy spectrum. Here ,Sm and ,Gd are defined as in previous studies of lunar neutron stratigraphy. Our data suggest that the neutron is more thermalized at the lower layers than it is at the upper layers. In addition to large isotopic shifts for 149Sm, 150Sm, 155Gd, 156Gd, 157Gd, and 158Gd, isotopic enrichments of 152Gd and 154Gd derived from neutron capture for 151Eu and 153Eu, respectively, were also observed in all samples. [source] Simultaneous measurement of 13C- and 15N-isotopic enrichments of threonine by mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 8 2009Jean-Philippe Godin Under conditions of high isotopic dilution, e.g. in a tracer study, the ability to determine accurately and quantitatively small variations in isotopic enrichments of differently labelled chemical compounds (e.g. 13C and 15N in threonine) in a single run by gas chromatography/mass spectrometry (GC/MS) is desirable but remains a technological challenge. Here, we report a new, rapid and simple GC/MS method for simultaneously measuring the isotopic enrichments of doubly labelled threonine ([U13C] and 15N) with isotopic enrichment lower than 1.5 Molar Percent Excess (MPE). The long-term reproducibility measured was around 0.09 MPE for both tracers (throughout a 6 week period). The intra-day repeatability was lower than 0.05 and 0.06 MPE for [U13C]-Thr and 15N-Thr, respectively. To calculate both isotopic enrichments, two modes of calculations were used: one based on work by Rosenblatt et al. in 1992 and the other one using a matrix approach. Both methods gave similar results (ANOVA, P >0.05) with close precision for each mode of calculation. The GC/MS method was then used to investigate the differential utilization of threonine in different organs according to its route of administration in minipigs after administration of both tracers. In plasma samples, the lowest isotopic enrichment measured between two successive time points was at 0.01 and 0.02 MPE for [U13C]-Thr and 15N-Thr, respectively. Moreover, the accuracy of GC/MS 13C-isotopic enrichment measured was validated by analyzing the same plasma samples by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Statistical analysis showed that both techniques gave the same results (ANOVA, P >0.05). This new GC/MS method offers the possibility to measure 13C- and 15N-isotopic enrichments with higher throughput, and using a lower amount of sample, than using GC/C/IRMS. Copyright © 2009 John Wiley & Sons, Ltd. [source] High-precision isotopic analysis of palmitoylcarnitine by liquid chromatography/electrospray ionization ion-trap tandem mass spectrometryRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 22 2006ZengKui Guo Single quadrupole gas chromatography/mass spectrometry (GC/MS) has been widely used for isotopic analysis in metabolic investigations using stable isotopes as tracers. However, its inherent shortcomings prohibit it from broader use, including low isotopic precision and the need for chemical derivatization of the analyte. In order to improve isotopic detection power, liquid chromatography/electrospray ionization ion-trap tandem mass spectrometry (LC/ESI-itMS2) has been evaluated for its isotopic precision and chemical sensitivity for the analysis of [13C]palmitoylcarnitine. Over the enrichment range of 0.4,10 MPE (molar % excess), the isotopic response of LC/ESI-itMS2 to [13C]palmitoylcarnitine was linear (r,=,1.00) and the average isotopic precision (standard deviation, SD) was 0.11 MPE with an average coefficient of variation (CV) of 5.6%. At the lower end of isotopic enrichments (0.4,0.9 MPE), the isotopic precision was 0.05 MPE (CV,=,8%). Routine analysis of rat skeletal muscle [13C4]palmitoylcarnitine demonstrated an isotopic precision of 0.03 MPE for gastrocnemius (n,=,16) and of 0.02 MPE for tibialis anterior (n,=,16). The high precision enabled the detection of a small (0.08 MPE) but significant (P,=,0.01) difference in [13C4]palmitoylcarnitine enrichments between the two muscles, 0.51 MPE (CV,=,5.8%) and 0.43 MPE (CV,=,4.6%), respectively. Therefore, the system demonstrated an isotopic lower detection limit (LDL) of ,0.1 MPE (2 × SD) that has been impossible previously with other organic mass spectrometry instruments. LC/ESI-itMS2 systems have the potential to advance metabolic investigations using stable isotopes to a new level by significantly increasing the isotopic solving power. Copyright © 2006 John Wiley & Sons, Ltd. [source] | ||||||||||||||||