Flavonoid glycosides and limonoids from Citrus molasses

Abstract

Molasses of tangerine orange (Citrus unshiu Markovich) is obtained as a waste product in the course of tangerine orange juice production. This molasses is expected to be a useful source of organic compounds such as flavonoids and limonoids. To elucidate a use for this molasses waste, we isolated and identified its organic constituents. Two new flavanonol glycosides were isolated from tangerine orange molasses, along with several flavonoids such as hesperidine, narirutin, eriodictyol, 3',4',5,6,7,8-hexamethoxy-3-O-beta-D-glucopyranosyloxyflavone, and 3',4',5,6,7,8-hexamethoxy- 3-beta-D-[4-O-(3-hydroxy-3-methylglutaloyl)]-glucopyranosyloxyflavone, and limonoids such as limonin, nomilin, and cyclic peptide, citrusin III. The structures of the new flavanonol glycosides were determined as (2R,3R)-7-O-(6-O-alpha-L-rahmnopyranosyl-beta-D-glucopyranosyl)-aromadendrin and 7-O-(6-O-alpha-L-rahmnopyranosyl-beta-D-glucopyranosyl)-3,3',5,7-tetrahydroxy-4'-methoxyflavanone by means of spectral analyses using (1)H-NMR, (13)C-NMR, and 2D-NMR. Of these compounds, flavanone glycoside, hesperidin and narirutin were isolated as the main constituents. Thus, molasses is a promising source of flavonoid glycosides.

Comparative characterization of phenolic and other polar compounds in Spanish melon cultivars by using high-performance liquid chromatography coupled to electrospray ionization quadrupole-time of flight mass spectrometry

“…Hesperidin (Peak 70), the only flavonoid detected in all the three varieties of melon studied, presented the fragmentation pattern depicted in Fig. 2 (b) and it has been characterized in other fruits (Kuroyanagi et al, 2008). Peak 67 has been tentatively identified as diosmetin rutinoside, since this compound and its fragment at m/z 299 have been previously reported in Cucurbitaceae (Siciliano, De Tommasi, Morelli, & Braca, 2004).…”

Chemical Profiles and Simultaneous Quantification of Aurantii fructus by Use of HPLC-Q-TOF-MS Combined with GC-MS and HPLC Methods

“…In addition, two polypeptides were found in AF. Compound 12 displayed a protonated molecule at m / z 728.3966 [M + H] + with the molecular formula C 36 H 53 N 7 O 9 , and corresponded to citrusin III [ 25 , 26 , 27 ], isolated previously from citrus plants. Compound 13 showed a protonated molecule at m / z 704.3978 [M + H] + with the molecular formula C 34 H 53 N 7 O 9 , which is consistent with the literature, and presumed as citrusin I [ 26 , 27 ].…”

The Chemistry and Pharmacology of Citrus Limonoids

“…Their amounts were found to be higher than those found in other citrus fruits [168]. The isolation and identification of both limonoids aglycones and glucosides by routinary HPLC and spectrometric or spectroscopic analyses is reported in several recent papers [48,52,169].…”

“…Actually, only 1, obacunone (3), and deoxylimonin (10) were used in the last decade as starting materials to obtain few related derivatives. Improved large-scale extraction methodologies and the abundantly available waste citrus materials [23,168,169,195] should allow easier access to starting materials in the future. Then, ligand efficiency metrics (LEM) guided derivatization of the latter should furnish new CL analogues to prove the reliability of CLs as defenders and promoters of human health.…”