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

Gerdov, S. M.; Grishin, Yuri K.; Roznyatovsky, Vitaly A.; Ustynyuk, Yu. A.; Кучин, А. В.; Alekseev, I. N.; Фролова, Л. Л.

doi:10.1007/s11172-005-0391-4

Cited by 2 publications

(2 citation statements)

References 21 publications

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“…These alternating hydrogen and carbon isotope patterns of CH 2 -chains are incompatible with a thermodynamic order (Section 2.1.3). Another example is the pathway-dependent 2 H pattern and 13 C content of isoprenoids [33,[206][207][208], whereas thermodynamics would demand an absolute independence of isotopic patterns from the pathway of synthesis. These findings demonstrate the existence of a reproducible 'order' in metabolism, produced by reaction mechanisms and KIEs (Figure 3, after [189]).…”

Section: Isotopic Order By Reaction Mechanisms and Metabolic Pathwaysmentioning

confidence: 99%

Multi-factorialin vivostable isotope fractionation: causes, correlations, consequences and applications

Schmidt

Robins

Werner

2015

Isotopes in Environmental and Health Studies

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Many physical and chemical processes in living systems are accompanied by isotope fractionation on H, C, N, O and S. Although kinetic or thermodynamic isotope effects are always the basis, their in vivo manifestation is often modulated by secondary influences. These include metabolic branching events or metabolite channeling, metabolite pool sizes, reaction mechanisms, anatomical properties and compartmentation of plants and animals, and climatological or environmental conditions. In the present contribution, the fundamentals of isotope effects and their manifestation under in vivo conditions are outlined. The knowledge about and the understanding of these interferences provide a potent tool for the reconstruction of physiological events in plants and animals, their geographical origin, the history of bulk biomass and the biosynthesis of defined representatives. It allows the use of isotope characteristics of biomass for the elucidation of biochemical pathways and reaction mechanisms and for the reconstruction of climatic, physiological, ecological and environmental conditions during biosynthesis. Thus, it can be used for the origin and authenticity control of food, the study of ecosystems and animal physiology, the reconstruction of present and prehistoric nutrition chains and paleaoclimatological conditions. This is demonstrated by the outline of fundamental and application-orientated examples for all bio-elements. The aim of the review is to inform (advanced) students from various disciplines about the whole potential and the scope of stable isotope characteristics and fractionations and to provide them with a comprehensive introduction to the literature on fundamental aspects and applications.

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Section: Isotopic Order By Reaction Mechanisms and Metabolic Pathwaysmentioning

confidence: 99%

Multi-factorialin vivostable isotope fractionation: causes, correlations, consequences and applications

Schmidt

Robins

Werner

2015

Isotopes in Environmental and Health Studies

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“…The 2 H NMR spectrum of compound 1 has been investigated in our earlier study. 1 The relative intensities of the lines in the 2 H NMR spectrum of compound 2 were not determined with sufficient accuracy because of the strong over lap of the signals. Hence, ketone 2 was reduced according to Scheme 1 to endo 4 (1 hydroxyethyl) 2 carene (3), whose 2 H NMR spectrum is rather well resolved (Fig.…”

Section: Methodsmentioning

confidence: 99%

Quantitative 2H NMR spectroscopy

et al. 2008

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The selectivity of deuterium distribution between the nonequivalent positions in 3 carene (1), 4 α acetyl 2 carene (2), and 4 (1 hydroxyethyl) 2 carene (3) has been measured by 2 H { 1 H} NMR spectroscopy at the natural abundance of deuterium. These "H/D isotope portraits" were shown to be typical of terpenes and terpenoids produced in plants via the biosynthetic DXP pathway. The mechanism of acylation of 1 was studied by the density functional theory method (PBE functional, TZ2p basis set). The six membered ring in com pound 1 is planar. However, the endo attack of electrophiles on this ring is more favorable both kinetically and thermodynamically. It was shown both experimentally and theoretically that the elimination of a hydrogen atom in the second reaction step proceeds stereoselectively at the C(2) atom from the anti position with respect to the three membered ring and occurs with pronounced nucleophilic assistance from the carbonyl group.

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

Cited by 2 publications

References 21 publications

Multi-factorialin vivostable isotope fractionation: causes, correlations, consequences and applications

Multi-factorialin vivostable isotope fractionation: causes, correlations, consequences and applications

Quantitative 2H NMR spectroscopy

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