Improving accuracy and accessibility in ¹H-¹H coupling measurements by using ¹³C satellites

Sinnaeve, Davy

Document type :

Communication dans un congrès avec actes

Permalink :

http://hdl.handle.net/20.500.12210/126788

Title :

Improving accuracy and accessibility in ¹H-¹H coupling measurements by using ¹³C satellites

Author(s) :

Sinnaeve, Davy [Orateur]

Facteurs de Risque et Déterminants Moléculaires des Maladies liées au Vieillissement - U 1167 [RID-AGE]
Biologie Structurale Intégrative [ERL 9002 - INSERM U1167 - BSI]

Conference title :

The 19th European Magnetic Resonance Congress (EUROMAR 2023)

Conference organizers(s) :

Groupement Ampere

City :

Glasgow

Country :

Royaume-Uni

Start date of the conference :

2023-07-09

Publication date :

2023-07-12

English keyword(s) :

NMR spectroscopy

HAL domain(s) :

Chimie/Chimie analytique

English abstract : [en]

In organic molecules, ¹H-¹H couplings are both abundant and valuable for constitutional, configurational and conformational structure elucidation studies. The downside of their abundance is that it results in complex and ...
Show more >In organic molecules, ¹H-¹H couplings are both abundant and valuable for constitutional, configurational and conformational structure elucidation studies. The downside of their abundance is that it results in complex and broad multiplets that may overlap, obstructing extraction of individual couplings. Pure shift experiments alleviate the overlap problem by delivering fully homodecoupled ¹H spectra, boosting spectral resolution by an order of magnitude. They can elegantly be combined with selective 2D J-resolved experiments, such as SERF, G-SERF or PSYCHEDELIC, allowing individual coupling measurement with a minimum of spectral overlap [1].However, all of these experiments fail when coupling partners have very close chemical shifts. First, the multiplets of these coupling partners may overlap, preventing selective inversion of one coupling partner. Second, the strong coupling condition between these protons affects the accuracy of coupling measurements with third protons. Here, a new selective 2DJ experiment based on the BIRD element [2,3] is presented that avoids this issue by exploiting the property that, at natural ¹³C abundance, one-bond ¹H-¹³C couplings resolve the chemical shift degeneracy. The new experiment, coined SERFBIRD, thus allows measurement of ¹H-¹H couplings that were inaccessible using established methods, or with an improved accuracy. Although applicable to any compound, it is a particularly powerful tool for carbohydrate analysis [4].An important limitation of BIRD is that it cannot deal with protons coupled to a geminal proton, which has hindered homodecoupling of ¹H-¹³C experiments of methylene protons in general. Strategies that overcome this issue will be presented, making individual ¹H-¹H coupling measurement also possible on the ¹³C satellites of methylene protons.[1] D. Sinnaeve, eMagRes 2021, 9, 267. [2] J.R. Garbow et al., Chem. Phys. Lett. 1982, 93, 504. [3] J. Aguilar et al., Angew. Chem. Int. Ed. 2011, 50, 9716. [4] F.X. Cantrelle and D. Sinnaeve, in prep.Show less >

Language :

Anglais

Peer reviewed article :

Oui

Audience :

Internationale

Popular science :

Non

ANR Project :

RMN à haute résolution et anisotrope pour dévoiler des ensembles conformationnels de biopolymères flexibles : une stratégie générale

Collections :

Facteurs de risque et déterminants moléculaires des maladies liées au vieillissement (RID-AGE) - U1167

Source :

Harvested from HAL

Submission date :

2025-04-03T03:52:01Z

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