1H-NMR Fingerprinting of Vaccinium vitis-idaea Flavonol Glycosides
Version of Record online: 23 MAY 2013
Copyright © 2013 John Wiley & Sons, Ltd.
Special Issue: PCA focus issue on ‘Analysis of polyphenols’ (ICP2012)
Volume 24, Issue 5, pages 476–483, September/October 2013
How to Cite
Riihinen, K. R., Mihaleva, V. V., Gödecke, T., Soininen, P., Laatikainen, R., Vervoort, J. M., Lankin, D. C. and Pauli, G. F. (2013), 1H-NMR Fingerprinting of Vaccinium vitis-idaea Flavonol Glycosides. Phytochem. Anal., 24: 476–483. doi: 10.1002/pca.2444
- Issue online: 27 AUG 2013
- Version of Record online: 23 MAY 2013
- Manuscript Accepted: 30 MAR 2013
- Manuscript Revised: 17 MAR 2013
- Manuscript Received: 26 JAN 2013
- NIH. Grant Number: P41 GM068944
- 1H-NMR fingerprint;
- 1H iterative full spin analysis;
- food and dietary supplement analysis;
- flavonol glycosides
The fruits of Vaccinium vitis-idaea L. are a valuable source of biologically active flavonoid derivatives. For studies focused on the purification of its quercetin glycosides (QGs) and related glycosides from plants and for the purpose of biological studies, the availability of numeric datasets from computer-assisted 1H iterative full spin analysis (HiFSA), that is, 1H-NMR fingerprinting, can replace and assist the repetitive and tedious two-dimensional NMR identification protocol required for both known and new compounds, respectively.
To fully interpret the complex 1H-NMR fingerprints of eight QGs obtained from the berries of V. vitis-idaea and provide complete and unambiguous signal assignments.
Vaccinium vitis-idaea QGs were purified in a single run by long-bed gel permeation chromatography and identified by comparison with commercially available compounds using LC–MS combining ion-trap and time-of-flight detection and one- or two-dimensional NMR. The HiFSA analysis yielded full sets of 1H chemical shifts and proton–proton coupling constants, allowing for field-independent spectral simulation.
Signal assignments were achieved for the reference standards and the QGs that dominated in purified fractions. However, even mixtures of two to three QGs could be fitted using the HiFSA approach. In the case of the overlapped sugar resonances, the initial fitting of the 1H spectra of reference compounds, together with values extracted from the two-dimensional NMR data and literature data, assisted in the process.
The HiFSA method revealed for the first time the presence of Q-3-O-β-glucopyranoside and Q-3-O-β-glucuronopyranoside in the berries of V. vitis-idaea, and unambiguously confirmed the structures of Q-3-O-[4″-(3-hydroxy-3-methylglutaroyl)]-α-rhamnopyranoside, Q-3-O-α-rhamnopyranoside, Q-3-O-β-galactopyranoside, Q-3-O-α-arabinofuranoside, Q-3-O-β-xylopyranoside and Q-3-O-α-arabinopyranoside. Copyright © 2013 John Wiley & Sons, Ltd.