A trisaccharide chain in a saponin from the seeds of Barringtonia asiatica has been identified and sequenced as {[b-D-galactopyranosyl(1®3)- b-D-glucopyranosyl(1®2)]-b-D-glucuronopyranosyloxy} using a combination of homonuclear and heteronuclear correlation NMR spectroscopy. The 1H and 13C NMR signals of the sugar residues can be determined and distinguished from one other by use of the HMQC-TOCSY technique. Anomeric configurations were unambiguously assigned from the vicinal coupling constants 3JH-1,H-2 of the anomeric protons. Inter-glycosidic linkage assignments were elucidated using HMBC. Keyword: Barringtonia asiatica, carbohydrate, saponin, NMR
(1) Background: Extra-virgin olive oil (EVOO) is a precious and universally studied food matrix. Recently, the quantitative chemical composition was investigated by an innovative processing method for the nuclear magnetic resonance (NMR) experiments called Multi-Assignment Recovered Analysis (MARA)-NMR. (2) Methods: Any EVOO 13-carbon NMR (13C-NMR) profile displayed inconsistent signals. This mismatch was resolved by comparing NMR data to the official gas-chromatographic flame ionization detection (GC-FID) experiments: the analyses concerned many EVOOs but also the “exotic” Capparis spinosa oil (CSO). (3) Results: NMR and GC-FID evidenced the overwhelming presence of cis-vaccenic esters in the CSO and, more importantly, cis-vaccenic 13C-NMR resonances unequivocally matched the misunderstood 13C-NMR signals of EVOOs. The updated assignment revealed the unexpected relevant presence of cis-vaccenic ester (around 3%) in EVOOs; it was neglected, so far, because routine and official GC-FID profiles did not resolve oleic and cis-vaccenic signals leading to the total quantification of both monounsaturated fatty esters. (4) Conclusions: The rebuilt MARA-NMR and GC-FID interpretations consistently show a meaningful presence of cis-vaccenic esters in EVOOs, whose content could be a discrimination factor featuring specific cultivar or geographical origin. The study paves the way toward new quantification panels and scientific research concerning vegetable oils.
AbstractCare should be taken on recording the sometimes elusive 13C NMR signals for boron-bonded carbon atoms, since it is easy to extract information about coupling constants 1J(13C,11B) by measuring the respective line widths of 13C(B-C) and 11B NMR signals. This information can be confirmed by quantum-chemical calculations [B3LYP (6-311+G(d,p) level of theory] of nJ(13C,11B) in organoboranes and tetraorganoborates. For the latter, the signs for n = 2, 3, 4 were experimentally determined.
ABSTRACT
Various pulse techniques of NMR spectroscopy were applied to CR to assign some small signals in 13C and 1H NMR spectra for the rubber. First, the rubber was subjected to distortionless enhancement by polarization transfer and attached proton test. The small signals in the 13C NMR spectrum were assigned to secondary, tertiary, and quaternary carbons. Second, correlations between 13C and 1H were investigated by heteronuclear multiple quantum correlation, heteronuclear two bond correlation, and heteronuclear multiple bond correlation measurements to assign the small signals in the 13C NMR spectrum in detail. By using the resulting correlations between 13C and 1H, the small unassigned signals in 1H NMR spectrum were assigned to methylene and methine protons of the rubber.
IDENTIFICATION AND SEQUENCING BY NMR SPECTROSCOPY OF THE CARBOHYDRATE MOIETY IN A SAPONIN FROM Barringtonia asiatica