title: Orthogonal Analysis Underscores the Relevance of Primary and Secondary Metabolites in Licorice.
abstract: Licorice botanicals are produced from the roots of Glycyrrhiza species (Fabaceae), encompassing metabolites of both plant and rhizobial origin. The composition in both primary and secondary metabolites (1°/2°Ms) reflects the physiologic state of the plant at harvest. Interestingly, the relative abundance of 1°Ms vs 2°Ms in licorice extracts remains undetermined. A centrifugal partition chromatography (CPC) method was developed to purify liquiritin derivatives that represent major bioactive 2°Ms and to concentrate the polar 1°Ms from the crude extract of Glycyrrhiza uralensis. One objective was to determine the purity of the generated reference materials by orthogonal UHPLC-UV/LC-MS and qHNMR analyses. The other objectives were to evaluate the presence of 1°Ms in purified 2°Ms and define their mass balance in a crude botanical extract. Whereas most impurities could be assigned to well-known 1°Ms, p-hydroxybenzylmalonic acid, a new natural tyrosine analogue, was also identified. Additionally, in the most polar fraction, sucrose and proline represented 93% (w/w) of all qHNMR-quantified 1°Ms. Compared to the 2°Ms, accounting for 11.9% by UHPLC-UV, 1°Ms quantified by qHNMR defined an additional 74.8% of G. uralensis extract. The combined orthogonal methods enable the mass balance characterization of licorice extracts and highlight the relevance of 1°Ms, and accompanying metabolites, for botanical quality control.
authors: †UIC/NIH Center for Botanical Dietary Supplements Research, Department of Medicinal Chemistry and Pharmacognosy, College of Pharmacy, University of Illinois at Chicago, 833 South Wood Street, Chicago, Illinois 60612, United States.
authors: Charlotte
authors: C
authors: Simmler
authors: †UIC/NIH Center for Botanical Dietary Supplements Research, Department of Medicinal Chemistry and Pharmacognosy, College of Pharmacy, University of Illinois at Chicago, 833 South Wood Street, Chicago, Illinois 60612, United States.
authors: Dejan
authors: D
authors: Nikolić
authors: †UIC/NIH Center for Botanical Dietary Supplements Research, Department of Medicinal Chemistry and Pharmacognosy, College of Pharmacy, University of Illinois at Chicago, 833 South Wood Street, Chicago, Illinois 60612, United States.
authors: David C
authors: DC
authors: Lankin
authors: †UIC/NIH Center for Botanical Dietary Supplements Research, Department of Medicinal Chemistry and Pharmacognosy, College of Pharmacy, University of Illinois at Chicago, 833 South Wood Street, Chicago, Illinois 60612, United States.
authors: Yang
authors: Y
authors: Yu
authors: ‡Physical Sciences Department, Rosary College of Arts and Sciences, Dominican University, River Forest, Illinois 60305, United States.
authors: J Brent
authors: JB
authors: Friesen
authors: †UIC/NIH Center for Botanical Dietary Supplements Research, Department of Medicinal Chemistry and Pharmacognosy, College of Pharmacy, University of Illinois at Chicago, 833 South Wood Street, Chicago, Illinois 60612, United States.
authors: Richard B
authors: RB
authors: van Breemen
authors: §Armen Instrument, Z.I. de Kermelin, 16 Rue Ampère, F-56890 Saint Avé, France.
authors: Alicia
authors: A
authors: Lecomte
authors: §Armen Instrument, Z.I. de Kermelin, 16 Rue Ampère, F-56890 Saint Avé, France.
authors: Céline
authors: C
authors: Le Quémener
authors: §Armen Instrument, Z.I. de Kermelin, 16 Rue Ampère, F-56890 Saint Avé, France.
authors: Grégoire
authors: G
authors: Audo
authors: †UIC/NIH Center for Botanical Dietary Supplements Research, Department of Medicinal Chemistry and Pharmacognosy, College of Pharmacy, University of Illinois at Chicago, 833 South Wood Street, Chicago, Illinois 60612, United States.
authors: Guido F
authors: GF
authors: Pauli
mesh_terms: D000975:Antioxidants / Q000378:metabolism; D002853:Chromatography, Liquid / Q000379:methods; D044950:Flavanones / Q000737:chemistry; D005960:Glucosides / Q000737:chemistry; D006035:Glycyrrhiza / Q000737:chemistry*; D029882:Glycyrrhiza uralensis / Q000737:chemistry*; D015394:Molecular Structure; D019906:Nuclear Magnetic Resonance, Biomolecular; D018517:Plant Roots / Q000737:chemistry; D014443:Tyrosine / Q000031:analogs & derivatives / Q000737:chemistry / Q000302:isolation & purification
chemical_list: D000975:Antioxidants; D044950:Flavanones; D005960:Glucosides; D014443:Tyrosine; C512196:liquiritin