Dataset Information

Synthesis and shift-reagent-assisted full NMR assignment of bacterial (Z8,E2,?)-undecaprenol.

ABSTRACT: The repeating isoprene unit is a fundamental biosynthetic motif. The repetitive structure presents challenges both for synthesis and for structural characterization. In this synthesis of the (Z8,E2,?)-undecaprenol of prokaryotic glycobiology, we exemplify solutions to these challenges. Allylation of sulfone-derived carbanions controlled the stereochemistry, and its proof-of-structure was secured by Eu(hfc)3 complexation to disperse the overlaid resonances of its 1H NMR spectrum.

SUBMITTER: Lee M

PROVIDER: S-EPMC5749266 | biostudies-literature | 2017 Nov

REPOSITORIES: biostudies-literature

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Synthesis and shift-reagent-assisted full NMR assignment of bacterial (Z8,E2,ω)-undecaprenol.

Lee Mijoon M Hesek Dusan D Zajíček Jaroslav J Fisher Jed F JF Mobashery Shahriar S

Chemical communications (Cambridge, England) 20171101 95

The repeating isoprene unit is a fundamental biosynthetic motif. The repetitive structure presents challenges both for synthesis and for structural characterization. In this synthesis of the (Z8,E2,ω)-undecaprenol of prokaryotic glycobiology, we exemplify solutions to these challenges. Allylation of sulfone-derived carbanions controlled the stereochemistry, and its proof-of-structure was secured by Eu(hfc)3 complexation to disperse the overlaid resonances of its ...[more]

PMID: 29139490

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Project description:BackgroundExcessive lactate production, a hallmark of cancer, is largely formed by the reduction of pyruvate via lactate dehydrogenase (LDH) to L-lactate. Although D-lactate can also be produced from glucose via the methylglyoxal pathway in small amounts, less is known about the amount of D-lactate produced in cancer cells. Since the stereoisomers of lactate cannot be distinguished by conventional 1H NMR spectroscopy, a chiral NMR shift reagent was used to fully resolve the 1H NMR resonances of D- and L-lactate.MethodsThe production of L-lactate from glucose and D-lactate from methylglyoxal was first demonstrated in freshly isolated red blood cells using the chiral NMR shift reagent, YbDO3A-trisamide. Then, two different cell lines with high GLO1 expression (H1648 and H 1395) were selected from a panel of over 80 well-characterized human NSCLC cell lines, grown to confluence in standard tissue culture media, washed with phosphate-buffered saline, and exposed to glucose in a buffer for 4 h. After 4 h, a small volume of extracellular fluid was collected and mixed with YbDO3A-trisamide for analysis by 1H NMR spectroscopy.ResultsA suspension of freshly isolated red blood cells exposed to 5mM glucose produced L-lactate as expected but very little D-lactate. To evaluate the utility of the chiral NMR shift reagent, methylglyoxal was then added to red cells along with glucose to stimulate the production of D-lactate via the glyoxalate pathway. In this case, both D-lactate and L-lactate were produced and their NMR chemical shifts assigned. NSCLC cell lines with different expression levels of GLO1 produced both L- and D-lactate after incubation with glucose and glutamine alone. A GLO1-deleted parental cell line (3553T3) showed no production of D-lactate from glucose while re-expression of GLO1 resulted in higher production of D-lactate.ConclusionsThe shift-reagent-aided NMR technique demonstrates that D-lactate is produced from glucose in NSCLC cells via the methylglyoxal pathway. The biological role of D-lactate is uncertain but a convenient method for monitoring D-lactate production could provide new insights into the biological roles of D- versus L-lactate in cancer metabolism.

Dataset Information

Synthesis and shift-reagent-assisted full NMR assignment of bacterial (Z8,E2,?)-undecaprenol.

Publications

Synthesis and shift-reagent-assisted full NMR assignment of bacterial (Z<sub>8</sub>,E<sub>2</sub>,ω)-undecaprenol.

Similar Datasets

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