Hydrogen Isotopic Profile in the Characterization of Sugars. Influence of the Metabolic Pathway

Zhang, Ben‐Li; Billault, Isabelle; Li, Xiaobao; Mabon, Françoise; Remaud, Gérald S.; Martin, Maryvonne L.

doi:10.1021/jf010776z

Cited by 48 publications

(51 citation statements)

References 20 publications

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“…Although photorespiration leads to C loss, 3-phosphoglycerate (3-PGA) is formed after both carboxylation and oxygenation, but with differing stoichiometries and along differing paths. Numerous observations have shown that synthesis of a compound via different pathways induces different isotopomer distributions (18,19,(28)(29)(30)(31)(32). No exception to this rule has been observed, and it agrees with the theory of isotope effects.…”

Section: /D6supporting

confidence: 81%

Detecting long-term metabolic shifts using isotopomers: CO₂-driven suppression of photorespiration in C₃plants over the 20th century

Ehlers

Augusti

Betson

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

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Terrestrial vegetation currently absorbs approximately a third of anthropogenic CO 2 emissions, mitigating the rise of atmospheric CO 2 . However, terrestrial net primary production is highly sensitive to atmospheric CO 2 levels and associated climatic changes. In C 3 plants, which dominate terrestrial vegetation, net photosynthesis depends on the ratio between photorespiration and gross photosynthesis. This metabolic flux ratio depends strongly on CO 2 levels, but changes in this ratio over the past CO 2 rise have not been analyzed experimentally. Combining CO 2 manipulation experiments and deuterium NMR, we first establish that the intramolecular deuterium distribution (deuterium isotopomers) of photosynthetic C 3 glucose contains a signal of the photorespiration/photosynthesis ratio. By tracing this isotopomer signal in herbarium samples of natural C 3 vascular plant species, crops, and a Sphagnum moss species, we detect a consistent reduction in the photorespiration/photosynthesis ratio in response to the ∼100-ppm CO 2 increase between ∼1900 and 2013. No difference was detected in the isotopomer trends between beet sugar samples covering the 20th century and CO 2 manipulation experiments, suggesting that photosynthetic metabolism in sugar beet has not acclimated to increasing CO 2 over >100 y. This provides observational evidence that the reduction of the photorespiration/photosynthesis ratio was ca. 25%. The Sphagnum results are consistent with the observed positive correlations between peat accumulation rates and photosynthetic rates over the Northern Hemisphere. Our results establish that isotopomers of plant archives contain metabolic information covering centuries. Our data provide direct quantitative information on the "CO 2 fertilization" effect over decades, thus addressing a major uncertainty in Earth system models.A tmospheric CO 2 levels have increased from ∼200 ppm during the last ice age to currently 400 ppm, and they may, according to pessimistic scenarios, exceed 1,000 ppm in the year 2100 (1). Understanding plant responses to increasing CO 2 is currently hampered by two fundamental limitations: First, it is unknown how well manipulation experiments represent responses to the gradual CO 2 increase over decades and centuries. In Free-Air CO 2 Enrichment (FACE) experiments, which most closely mimic natural conditions, increases in [CO 2 ] generally increase plant growth, but this "CO 2 fertilization" effect often declines after a few years of enrichment (2). Such transient responses may be related to the step increases in [CO 2 ] used in the experiments, their limited duration (2), or factors other than CO 2 becoming limiting (3). Second, in response to the [CO 2 ] increase since industrialization, genetic (4) and phenotypic plant responses (5-7) have been observed. Although century-scale changes have been detected in carbon isotopes (δ 13 C) and attributed to [CO 2 ], these responses are tied to differences in intercellular substrate concentrations that reflect several metabolic fluxes and dif...

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Section: /D6supporting

confidence: 81%

Detecting long-term metabolic shifts using isotopomers: CO₂-driven suppression of photorespiration in C₃plants over the 20th century

Ehlers

Augusti

Betson

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

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“…Glucose slightly bideuterated at 6R,6S (6,6 designates the average of these positions) was used to test that no ethanol was produced by glycolysis. Glucose from corn (Zea mays) was used as reference, the natural abundance ( 2 H/ 1 H) j having been previously determined for each hydrogen position j (19). Fermentation was also performed with slightly deuterated water to determine the extent to which this was a source of hydrogen in ethanol.…”

Section: Resultsmentioning

confidence: 99%

Non-equivalence of Hydrogen Transfer from Glucose to the pro-R and pro-S Methylene Positions of Ethanol during Fermentation by Leuconostoc mesenteroides Quantified by 2H NMR at Natural Abundance

Robins

Petavy

Nemmaoui

et al. 2008

Journal of Biological Chemistry

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The anaerobic fermentation of glucose by Leuconostoc mesenteroides via the reductive pentose phosphate pathway leads to the accumulation of lactic acid and ethanol. The isotope redistribution coefficients (a ij ) that characterize the specific derivation of each hydrogen atom in ethanol in relation to the non-exchangeable hydrogen atoms in glucose and the medium water have been determined using quantitative 2 H NMR. First, it is confirmed that the hydrogens of the methylene group are related only to the 1 and 3 positions of glucose via the NAD(P)H pool and not to the 4 position, in contrast to ethanol produced by Saccharomyces cerevisiae. Second, it is found that the conversion factors (C f ) for the transfer of hydrogen to the pro-S and pro-R positions of the methylene group are not equivalent: the C f -1-R:C f -1-S ratio is 2.1, whereas the C f -3-R:C f -3-S ratio is 0.8. It is shown that this non-equivalence is not determined by the stereochemistry of the terminal NADH-and NADPH-dependent alcohol dehydrogenases, but is dependent on the cofactor selectivities of the reductive and oxidative steps of the reduced nucleotide cycle.

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“…2 and 3). Glucose from corn (Zea mays) was used as reference, and the natural abundance (D/H) i was determined for each hydrogen position (16) Thus, the affiliation was measured at natural abundance and at a 3-5-fold site-specific enrichment. In all fermentations conducted with either Lc.…”

Section: Resultsmentioning

confidence: 99%

Quantitative 2H NMR at Natural Abundance Can Distinguish the Pathway Used for Glucose Fermentation by Lactic Acid Bacteria

Roger

Lavigne

Mahmoud

et al. 2004

Journal of Biological Chemistry

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For any given metabolic pathway, isotope redistribution coefficients (a ij ) that characterize the specific derivation of each hydrogen atom can be defined. By using quantitative deuterium NMR, the redistribution of deuterium at natural abundance in lactic acid produced by the bacterial fermentation of glucose has been determined for each non-labile hydrogen atom of glucose or water and the hydrogen atoms of lactic acid. Distinct differences are observed in the lactic acid isolated from Lactococcus lactis and Leuconostoc mesenteroides that can be interpreted in terms of the different fermentative pathways used. Specifically, the affiliations observed between the H1, H3, and H4 positions of glucose with methyl and hydroxymethylene of lactic acid can give quantitative information on whether the glycolytic or the reductive pentose-phosphate pathway was involved in glucose catabolism.

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Hydrogen Isotopic Profile in the Characterization of Sugars. Influence of the Metabolic Pathway

Cited by 48 publications

References 20 publications

Detecting long-term metabolic shifts using isotopomers: CO₂-driven suppression of photorespiration in C₃plants over the 20th century

Detecting long-term metabolic shifts using isotopomers: CO₂-driven suppression of photorespiration in C₃plants over the 20th century

Non-equivalence of Hydrogen Transfer from Glucose to the pro-R and pro-S Methylene Positions of Ethanol during Fermentation by Leuconostoc mesenteroides Quantified by 2H NMR at Natural Abundance

Quantitative 2H NMR at Natural Abundance Can Distinguish the Pathway Used for Glucose Fermentation by Lactic Acid Bacteria

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Hydrogen Isotopic Profile in the Characterization of Sugars. Influence of the Metabolic Pathway

Cited by 48 publications

References 20 publications

Detecting long-term metabolic shifts using isotopomers: CO2-driven suppression of photorespiration in C3plants over the 20th century

Detecting long-term metabolic shifts using isotopomers: CO2-driven suppression of photorespiration in C3plants over the 20th century

Non-equivalence of Hydrogen Transfer from Glucose to the pro-R and pro-S Methylene Positions of Ethanol during Fermentation by Leuconostoc mesenteroides Quantified by 2H NMR at Natural Abundance

Quantitative 2H NMR at Natural Abundance Can Distinguish the Pathway Used for Glucose Fermentation by Lactic Acid Bacteria

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Detecting long-term metabolic shifts using isotopomers: CO₂-driven suppression of photorespiration in C₃plants over the 20th century

Detecting long-term metabolic shifts using isotopomers: CO₂-driven suppression of photorespiration in C₃plants over the 20th century