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NMR-Based Configurational Assignments of Natural Products: Gibbs Sampling and Bayesian Inference Using Floating Chirality Distance Geometry Calculations

Immel, Stefan ; Köck, Matthias ; Reggelin, Michael (2022):
NMR-Based Configurational Assignments of Natural Products: Gibbs Sampling and Bayesian Inference Using Floating Chirality Distance Geometry Calculations. (Publisher's Version)
In: Marine Drugs, 20 (1), MDPI, e-ISSN 1660-3397,
DOI: 10.26083/tuprints-00020283,
[Article]

Abstract

Floating chirality restrained distance geometry (fc-rDG) calculations are used to directly evolve structures from NMR data such as NOE-derived intramolecular distances or anisotropic residual dipolar couplings (RDCs). In contrast to evaluating pre-calculated structures against NMR restraints, multiple configurations (diastereomers) and conformations are generated automatically within the experimental limits. In this report, we show that the "unphysical" rDG pseudo energies defined from NMR violations bear statistical significance, which allows assigning probabilities to configurational assignments made that are fully compatible with the method of Bayesian inference. These "diastereomeric differentiabilities" then even become almost independent of the actual values of the force constants used to model the restraints originating from NOE or RDC data.

Item Type: Article
Erschienen: 2022
Creators: Immel, Stefan ; Köck, Matthias ; Reggelin, Michael
Origin: Secondary publication DeepGreen
Status: Publisher's Version
Title: NMR-Based Configurational Assignments of Natural Products: Gibbs Sampling and Bayesian Inference Using Floating Chirality Distance Geometry Calculations
Language: English
Abstract:

Floating chirality restrained distance geometry (fc-rDG) calculations are used to directly evolve structures from NMR data such as NOE-derived intramolecular distances or anisotropic residual dipolar couplings (RDCs). In contrast to evaluating pre-calculated structures against NMR restraints, multiple configurations (diastereomers) and conformations are generated automatically within the experimental limits. In this report, we show that the "unphysical" rDG pseudo energies defined from NMR violations bear statistical significance, which allows assigning probabilities to configurational assignments made that are fully compatible with the method of Bayesian inference. These "diastereomeric differentiabilities" then even become almost independent of the actual values of the force constants used to model the restraints originating from NOE or RDC data.

Journal or Publication Title: Marine Drugs
Journal Volume: 20
Issue Number: 1
Publisher: MDPI
Collation: 22 Seiten
Uncontrolled Keywords: distance geometry calculations, configurational analysis, chirality, NMR spectroscopy, residual dipolar couplings, assignment probabilities, statistical error analysis
Divisions: 07 Department of Chemistry
07 Department of Chemistry > Organ Chemistry
Date Deposited: 13 Apr 2022 11:29
DOI: 10.26083/tuprints-00020283
URL / URN: https://tuprints.ulb.tu-darmstadt.de/20283
URN: urn:nbn:de:tuda-tuprints-202834
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