RESUMO
Lactuca sativa L. var. augustana has a basmati rice-like odor with a green note in the background. This typical odor is due to the release of 2-acetyl-1-pyrroline (2-AP) after heating, which is confirmed by volatile analysis. Recent metabolomic and genomic studies of different rice varieties highlighted that the presence of 2-AP was linked to the accumulation of γ-aminobutyraldehyde; genome-wide association studies also indicated that acyltransferases were involved. These results prompted us to analyze nonvolatile compound precursors in L. sativa L. var. augustana (celtuce) to search for compound derivatives with a 4,5-dioxohexan alkyl amine-like structure. Hypothetical synthetic compounds were prepared from a reductive amination between 4,5-dioxohexanal and glycine, alanine, aspartic acid, and glutamic acid to give 2-(2-acetylpyrrolidin-1-yl) alkanoic acid. We proved that 2-(2-acetylpyrrolidin-1-yl) propionic acid is present in L. sativa, which, when thermally treated, released 2-AP. Other 2-AP precursors occurring in this plant are discussed.
Assuntos
Lactuca/química , Extratos Vegetais/química , Pirróis/química , Genoma de Planta , Lactuca/genética , Espectrometria de Massas , Odorantes/análiseRESUMO
Transverse and longitudinal relaxation times (T1ρ and T1) have been widely exploited in NMR to probe the binding of ligands and putative drugs to target proteins. We have shown recently that long-lived states (LLS) can be more sensitive to ligand binding. LLS can be excited if the ligand comprises at least two coupled spins. Herein we broaden the scope of ligand screening by LLS to arbitrary ligands by covalent attachment of a functional group, which comprises a pair of coupled protons that are isolated from neighboring magnetic nuclei. The resulting functionalized ligands have longitudinal relaxation times T1((1)H) that are sufficiently long to allow the powerful combination of LLS with dissolution dynamic nuclear polarization (D-DNP). Hyperpolarized weak "spy ligands" can be displaced by high-affinity competitors. Hyperpolarized LLS allow one to decrease both protein and ligand concentrations to micromolar levels and to significantly increase sample throughput.