Measurement of deuterium kinetic isotope effects in organic and biochemical reactions by natural abundance deuterium NMR spectroscopy

Pascal, Robert A.; Baum, Mary W.; Wagner, Carol K.; Rodgers, Lauren R.; Huang, Ded Shih

doi:10.1021/ja00281a005

Cited by 43 publications

(18 citation statements)

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“…In the paper by Martin et al [2], it was pointed out specifically that the 2 H content at the position labelled with H A in the formula of ()-a-pinene (9) was markedly depleted (by a factor of 4) with respect to the value corresponding to H B in the same compound, and that a similar depletion was also evident in the 2 H-NMR spectrum of (À)-a-pinene. A critical examination of the data published by Pascal et al on (À)-a-pinene [3] has confirmed this anomalous 2 H distribution [5]. In addition, inspection of the naturalabundance 2 H-NMR of ()-limonene (4) has revealed once again a significant depletion (by a factor of 2.5) in the 2 H content of the H A -atom of 4 [5].…”

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confidence: 72%

On the Early Steps of Cineol Biosynthesis in Eucalyptus globulus

Rieder

Jaun

Arigoni

2000

HCA

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Dedicated, on the occasion of his 75th birthday, to Albert Eschenmoser, from whom I learned, among many other things, that one plus one gives much more than two, if the ones communicate.Samples of [4-2 H 1 ]-1-deoxyxylulose (17a) and [2-13 C, 4-2 H 1 ]-1-deoxyxylulose (17b), have been prepared by modification of known procedures and fed in aqueous solution to twiglets of Eucalyptus globulus. The probes of cineol (6) isolated from these experiments were analyzed by GC/MS, 2 H-and 13 C-NMR techniques. In the experiments with 17b, the formation of five isotopomers of 6 could be detected. Their structure and relative abundance demonstrate that the 13 C-label is incorporated to the same extent into the two C 5 -units of 6, and that the 2 H label is retained to an extent of 57% in the starter dimethylallyl-diphosphate unit (DMAPP; 12), but completely or almost completely lost in the unit derived from isopentenyl diphosphate (IPP; 11), in the elongation step which leads to geranyl diphosphate (GPP; 1). These results confirm that the recently discovered mevalonate-independent pathway to IPP and DMAPP is operative in the biosynthesis of cineol, and indicate, together with previous finding, that, within this pathway, formation of IPP and DMAPP occurs in independent rather than in sequential steps. In addition, the demonstration of different metabolic origins for the olefinic Hatoms of GPP (1), the aliphatic C 10 -precursor of 6, paves the way for a realistic interpretation of the strikingly consistent but hitherto unexplained anomalies detected in the natural-abundance 2 H-NMR spectra of ()-and (À)-a-pinene and of ()-limonene.

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confidence: 72%

On the Early Steps of Cineol Biosynthesis in Eucalyptus globulus

Rieder

Jaun

Arigoni

2000

HCA

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“…This method has also been extensively used in studying kinetic isotope effects [27–29]. Since the concentrations of multi-substrates and/or multi-products need to be monitored, a multiplexed analytical technique is required to measure all of the concentrations of each of these components for data analysis.…”

Section: Techniques For Multiplexed High Throughput Measurements mentioning

confidence: 99%

“…Another technique used for these internal competition assays, nuclear magnetic resonance spectrometry (NMR), is used to determine the kinetic isotope effects between stable isotope labeled substrates and unlabeled substrates [27–29]. As more innovative methodologies have been developed to utilize this advanced technology, a very high degree of precision and accuracy can be obtained for the measurement of low abundance, stably isotope-labeled substrates [44–47].…”

Section: Techniques For Multiplexed High Throughput Measurements mentioning

confidence: 99%

Measuring specificity in multi-substrate/product systems as a tool to investigate selectivity in vivo

Kuo

Henry

Andrews

2016

Biochimica et Biophysica Acta (BBA) - Proteins and Proteomics

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Multiple substrate enzymes present a particular challenge when it comes to understanding their activity in a complex system. Although a single target may be easy to model, it does not always present an accurate representation of what that enzyme will do in the presence of multiple substrates simultaneously. Therefore, there is a need to find better ways to both study these enzymes in complicated systems, as well as accurately describe the interactions through kinetic parameters. This review looks at different methods for studying multiple substrate enzymes, as well as explores options on how to most accurately describe an enzyme’s activity within these multi-substrate systems. Identifying and defining this enzymatic activity should clear the way ro use in vitro systems to accurately predict the behavior of multi-substrate enzymes in vivo.

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“…10- 13 The 2 H NMR spectra of some cyclic monot erpenes have previously been described in several works. The data on selective distribution of this isotope in mol ecules of (1R) camphor, 7 (1R) and (1S) α pinenes, 8,14 (1S) β pinene, 8, 15 (R) (+) limonene, 16 and linalool 17 showed that the deuterium content in different structural fragments of molecules of these natural compounds dif fered substantially from the statistical value and depended on the plant source from which they were isolated.…”

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confidence: 97%

“…The first studies by 2 H NMR at the natural abundance level of the isotope already demonstrated convincingly wide chal lenges of using this method for analysis of mechanisms of chemical reactions and biosynthetic pathways and to determine sources of origin of natural organic com pounds. [4][5][6][7][8][9] Monoterpenes play a significant role in living nature as signal substances that transmit information between individuals of the same and different species and between organs of the same organism and perform protective func tions. 10- 13 The 2 H NMR spectra of some cyclic monot erpenes have previously been described in several works.…”

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confidence: 99%

Quantitative 2H NMR spectroscopy 2. “H/D-Isotope portraits” of cyclic monoterpenes and discrimination of their biosynthetic pathways

et al. 2005

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Site specific deuterium distribution in molecules of the representative series of natural monoterpenes was studied by quantitative 2 H NMR spectroscopy. "H/D isotope portraits" of these compounds have general characteristic features reflecting biosynthetic pathways. The data obtained suggest that monoterpenes in plants are formed through 1 deoxy D xylulose 5 phosphate (DXP pathway) rather than by the classical mevalonate scheme.

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Measurement of deuterium kinetic isotope effects in organic and biochemical reactions by natural abundance deuterium NMR spectroscopy

Abstract: Table IV. Molar Enhancement Factors (X10"2)°f or Selected Raman Bands of the Aromatic Amino Acids* at the Indicated Excitation Wavelengths tryptophan tyrosine phenylalanine histidine

Cited by 43 publications

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On the Early Steps of Cineol Biosynthesis in Eucalyptus globulus

On the Early Steps of Cineol Biosynthesis in Eucalyptus globulus

Measuring specificity in multi-substrate/product systems as a tool to investigate selectivity in vivo

Quantitative 2H NMR spectroscopy 2. “H/D-Isotope portraits” of cyclic monoterpenes and discrimination of their biosynthetic pathways

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