Precise and accurate quantitative 13C NMR with reduced experimental time

Caytan, Elsa; Remaud, Gérald S.; Tenailleau, Eve; Akoka, Serge

doi:10.1016/j.talanta.2006.05.075

Cited by 90 publications

(73 citation statements)

References 28 publications

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“…The first study to examine natural position-specific isotopic variations in materials relevant to the Earth and life sciences measured the intramolecular carbon isotope variations of biosynthetic amino acids (Abelson and Hoering, 1961). This subject grew dramatically with the development of NMR techniques for measuring position-specific variations in D and 13 C abundances in organic molecules (Martin and Martin, 1981;Caytan et al, 2007). Such work has been applied to foodscience, plant physiology, paleoenvironment reconstruction and environmental contamination (Remaud et al, 1997;Gilbert et al, 2012;Ehler et al, 2015;Julien et al, 2015 and2016).…”

Section: Introductionmentioning

confidence: 99%

Position-specific hydrogen isotope equilibrium in propane

Xie

Ponton

Formolo

et al. 2018

Geochimica et Cosmochimica Acta

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Intramolecular isotope distributions can constrain source attribution, mechanisms of formation and destruction, and temperature-time histories of molecules. In this study, we explore the D/H fractionation between central (-CH 2 -) and terminal (-CH 3 ) positions of propane (C 3 H 8 ) -a percent level component of natural gases. The temperature dependence of position-specific D/H fractionation of propane could potentially work as a geo-thermometer for natural gas systems, and a forensic identifier of specific thermogenic sources of atmospheric or aquatic emissions. Moreover, kinetically controlled departures from temperature dependent equilibrium might constrain mechanisms of thermogenic production, or provide indicators of biological or photochemical destruction. We developed a method to measure position-specific D/H differences of propane with high-resolution gas source mass spectrometry. We performed laboratory exchange experiments to study the exchange rates for both terminal and central positions, and used catalysts to drive the hydrogen isotope distribution of propane to thermodynamic equilibrium. Experimental results demonstrate that D/H exchange between propane and water happens easily in the presence of either Pd catalyst or Ni catalyst. Exchange rates are similar between the two positions catalyzed by Pd. However, the central position exchanges 2.2 times faster than the terminal position in the presence of Ni catalyst. At 200°C in the presence of Pd catalyst, the e-folding time of propane-water exchange is 20 days and of homogeneous exchange (i.e., equilibrium between central and terminal positions) is 28 minutes. An equilibrated (bracketed and time-invariant) intramolecular hydrogen isotope distribution was attained for propane at three temperatures, 30°C, 100°C and 200°C; these data serve as an initial experimental calibration of a new position-specific thermometer with a temperature sensitivity of 0.25‰ per ˚C at 100 ˚C. We use this calibration to test the validity of prior published theoretical predictions. Comparison of data with models suggest the most sophisticated of these discrepant models (Webb and Miller, 2014) is most accurate; this conclusion implies that there is a combined experimental and theoretical foundation for an 'absolute reference frame' for positionspecific H isotope analysis of propane, following principles previously used for clumped isotope analysis of CO 2 , CH 4 and O 2 (Eiler and Schauble, 2004;Yeung et al., 2014;Stolper et al., 2014).

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Section: Introductionmentioning

confidence: 99%

Position-specific hydrogen isotope equilibrium in propane

Xie

Ponton

Formolo

et al. 2018

Geochimica et Cosmochimica Acta

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“…This is mainly due to the very substantial overlap of resonances characterizing 1D proton NMR spectra of complex metabolic mixtures. Quantitative 13 C NMR [4] provides an interesting alternative, as it leads to a better discrimination of resonances because of its much larger chemical shift range. However, its use in metabolomics is generally limited to 13 C-labeled metabolites [5] because of its inherent low sensitivity.…”

Section: Introductionmentioning

confidence: 99%

Fast and precise quantitative analysis of metabolic mixtures by 2D 1H INADEQUATE NMR

Martineau

Giraudeau

Téa

et al. 2011

Journal of Pharmaceutical and Biomedical Analysis

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140

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“…3−5 Separation of compounds by these techniques is not assured, and variation of chromatography columns can be resource-intensive (in both time and cost) and does not always lead to peak separation or reliable ratios. 7−9 13 C NMR spectroscopy can be used as a quantitative tool, 10−14 but quantitative 13 C NMR spectroscopy requires long relaxation delays, which can result in long acquisition times to achieve sufficient signal-to-noise ratios.…”

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confidence: 99%

¹³C NMR Spectroscopy for the Quantitative Determination of Compound Ratios and Polymer End Groups

et al. 2014

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13C NMR spectroscopic integration employing short relaxation delays was evaluated as a quantitative tool to obtain ratios of diastereomers, regioisomers, constitutional isomers, mixtures of unrelated compounds, peptoids, and sugars. The results were compared to established quantitative methods such as 1H NMR spectroscopic integration, gas chromatography, and high-performance liquid chromatography and were found to be within <3.4% of 1H NMR spectroscopic values (most examples give results within <2%). Acquisition of the spectra took 2–30 min on as little as 10 mg of sample, proving the general utility of the technique. The simple protocol was extended to include end group analysis of low molecular weight polymers, which afforded results in accordance with 1H NMR spectroscopy and matrix-assisted laser desorption-ionization time-of-flight spectrometry.

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Precise and accurate quantitative 13C NMR with reduced experimental time

Cited by 90 publications

References 28 publications

Position-specific hydrogen isotope equilibrium in propane

Position-specific hydrogen isotope equilibrium in propane

Fast and precise quantitative analysis of metabolic mixtures by 2D 1H INADEQUATE NMR

¹³C NMR Spectroscopy for the Quantitative Determination of Compound Ratios and Polymer End Groups

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Precise and accurate quantitative 13C NMR with reduced experimental time

Cited by 90 publications

References 28 publications

Position-specific hydrogen isotope equilibrium in propane

Position-specific hydrogen isotope equilibrium in propane

Fast and precise quantitative analysis of metabolic mixtures by 2D 1H INADEQUATE NMR

13C NMR Spectroscopy for the Quantitative Determination of Compound Ratios and Polymer End Groups

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Product

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¹³C NMR Spectroscopy for the Quantitative Determination of Compound Ratios and Polymer End Groups