From Relative to Absolute Stereochemistry of Secondary Metabolites: Applications in Plant Chemistry

Pereda‐Miranda, Rogelio; Bautista, Elihú; Martínez-Fructuoso, Lucero; Fragoso‐Serrano, Mabel

doi:10.1007/s43450-022-00333-y

Cited by 7 publications

(3 citation statements)

References 183 publications

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“…This oligosaccharide core is notably present in murucoidin XIV, previously identified in M. mammosa, I. operculata, I. batatas , and I. murucoides [ 1 ]. However, it is imperative to note that reference signals of the high-affinity glycolipid to the enzyme were not discernible in the NMR spectra [ 16 ]. These findings mirror those observed with α -glucosidase enzymes.…”

Section: Discussionmentioning

confidence: 99%

Identification of Hypoglycemic Glycolipids from Ipomoea murucoides by Affinity-Directed Fractionation, In Vitro, In Silico and Dynamic Light Scattering Analysis

Rosas-Ramírez,

Arreguín-Espinosa,

Escandón-Rivera

et al. 2024

Plants

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In the pursuit of identifying the novel resin glycoside modulators glucose-6-phosphatase and α-glucosidase enzymes, associated with blood sugar regulation, methanol-soluble extracts from the flowers of Ipomoea murucoides (cazahuate, Nahuatl), renowned for its abundance of glycolipids, were employed. The methanol-soluble extracts were fractionated by applying the affinity-directed method with glucose-6-phosphatase enzymes from a rat’s liver and α-glucosidase enzymes from its intestines. Mass spectrometry and nuclear magnetic resonance were employed to identify the high-affinity compound as a free ligand following the release from the enzymatic complex. Gel permeation through a spin size-exclusion column allowed the separated high-affinity molecules to bind to glucose-6-phosphatase and α-glucosidase enzymes in solution, which led to the identification of some previously reported resin glycosides in the flowers of cazahuate, where a glycolipid mainly structurally related to murucoidin XIV was observed. In vitro studies demonstrated the modulating properties of resin glycosides on the glucose-6-phosphatase enzyme. Dynamic light scattering revealed conformational variations induced by resin glycosides on α-glucosidase enzyme, causing them to become more compact, akin to observations with the positive control, acarbose. These findings suggest that resin glycosides may serve as a potential source for phytotherapeutic agents with antihyperglycemic properties.

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Section: Discussionmentioning

confidence: 99%

Identification of Hypoglycemic Glycolipids from Ipomoea murucoides by Affinity-Directed Fractionation, In Vitro, In Silico and Dynamic Light Scattering Analysis

Rosas-Ramírez,

Arreguín-Espinosa,

Escandón-Rivera

et al. 2024

Plants

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“…Future research should prioritize the assignment of chiral carbon configurations to fully elucidate their role in the Ascochyta–legume interaction. The absolute assignment of fungal secondary metabolite configurations through advanced spectroscopic methods, including NMR and optical techniques, is indispensable for comprehensively understanding their biological relevance [ 62 , 63 , 64 ]. Accurate molecular structure determination provides insights into the compound’s bioactivity and potential ecological roles.…”

Section: Discussionmentioning

confidence: 99%

Comparative Analysis of Secondary Metabolites Produced by Ascochyta fabae under In Vitro Conditions and Their Phytotoxicity on the Primary Host, Vicia faba, and Related Legume Crops

Barilli,

Reveglia,

Agudo-Jurado

et al. 2023

Toxins

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Ascochyta blight, caused by Ascochyta fabae, poses a significant threat to faba bean and other legumes worldwide. Necrotic lesions on stems, leaves, and pods characterize the disease. Given the economic impact of this pathogen and the potential involvement of secondary metabolites in symptom development, a study was conducted to investigate the fungus’s ability to produce bioactive metabolites that might contribute to its pathogenicity. For this investigation, the fungus was cultured in three substrates (Czapek-Dox, PDB, and rice). The produced metabolites were analyzed by NMR and LC-HRMS methods, resulting in the dereplication of seven metabolites, which varied with the cultural substrates. Ascochlorin, ascofuranol, and (R)-mevalonolactone were isolated from the Czapek-Dox extract; ascosalipyrone, benzoic acid, and tyrosol from the PDB extract; and ascosalitoxin and ascosalipyrone from the rice extract. The phytotoxicity of the pure metabolites was assessed at different concentrations on their primary hosts and related legumes. The fungal exudates displayed varying degrees of phytotoxicity, with the Czapek-Dox medium’s exudate exhibiting the highest activity across almost all legumes tested. The species belonging to the genus Vicia spp. were the most susceptible, with faba bean being susceptible to all metabolites, at least at the highest concentration tested, as expected. In particular, ascosalitoxin and benzoic acid were the most phytotoxic in the tested condition and, as a consequence, expected to play an important role on necrosis’s appearance.

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“…The determination of absolute configuration of chiral organic compounds is a crucial task in chemistry and is still challenging. Although several methods for enantiomer differentiation or even measuring enantiomeric excess exist, such as X-ray diffraction for crystalline molecules, , electronic or vibrational circular dichroism (CD spectroscopy) for small molecules, , Coulomb explosion imaging or microwave three-wave mixing in the gas phase and NMR spectroscopy on chirally derivatized compounds, they all have severe limitations , and additional methods are in need. Chirally aligned NMR spectroscopy has a high potential to become such a method.…”

Section: Introductionmentioning

confidence: 99%

Enantiomer Differentiation by Interaction-Specific Prediction of Residual Dipolar Couplings in Spherical-like Molecules

Elsing,

Luy,

Kozlowska

2024

J. Chem. Theory Comput.

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Residual Dipolar Couplings (RDCs) are averaged dipolar couplings between nuclear spins of atoms in a molecule that can be measured by nuclear magnetic resonance (NMR) spectroscopy upon partial alignment by a chiral alignment medium. The estimation of differences in alignment of enantiomers may, in principle, enable the determination of absolute configuration. Here, we use molecular dynamics (MD) simulations to mimic the alignment of chiral molecules (i.e., isopinocampheol, quinuclidin-3-ol, borneol, and camphor) to the chiral poly-γ-benzyl-L-glutamate (PBLG) polymer to predict RDCs in silico and compare calculated and experimentally measured residual dipolar couplings for the four enantiomeric pairs. The aim is to validate the computational scheme for the prediction of RDCs in chiral molecules and understand the interaction leading to the alignment in more detail. We determine the indispensable importance of hydrogen bonds between a chiral molecule and the alignment medium on the overall quality of the simulated alignment and interaction poses toward high agreement with experiments. A good correlation with experimental data is found for camphor and isopinocampheol, while the correlation for quinuclidin-3-ol and borneol is lower. We attribute this observation to the high difficulty of the RDC prediction for rather almost spherical molecules. The study reveals that the prediction of alignment with small enantiomeric differences is possible with an MD-based approach; however, extended simulation times (e.g., 50−100 μs) are required to sufficiently reduce the statistical uncertainty. This may be further used for the determination of the relative, as well as absolute, configuration of chiral molecules.

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From Relative to Absolute Stereochemistry of Secondary Metabolites: Applications in Plant Chemistry

Cited by 7 publications

References 183 publications

Identification of Hypoglycemic Glycolipids from Ipomoea murucoides by Affinity-Directed Fractionation, In Vitro, In Silico and Dynamic Light Scattering Analysis

Identification of Hypoglycemic Glycolipids from Ipomoea murucoides by Affinity-Directed Fractionation, In Vitro, In Silico and Dynamic Light Scattering Analysis

Comparative Analysis of Secondary Metabolites Produced by Ascochyta fabae under In Vitro Conditions and Their Phytotoxicity on the Primary Host, Vicia faba, and Related Legume Crops

Enantiomer Differentiation by Interaction-Specific Prediction of Residual Dipolar Couplings in Spherical-like Molecules

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