Identification of Flavonol and Xanthone Glycosides From Mango

Download as pdf or txt
Download as pdf or txt
You are on page 1of 6

5006 J. Agric. Food Chem.

2003, 51, 5006−5011

Identification of Flavonol and Xanthone Glycosides from Mango


(Mangifera indica L. Cv. “Tommy Atkins”) Peels by
High-Performance Liquid Chromatography-Electrospray
Ionization Mass Spectrometry
ANDREAS SCHIEBER,* NICOLAI BERARDINI, AND REINHOLD CARLE
Institute of Food Technology, Section Plant Foodstuff Technology, Hohenheim University,
Garbenstrasse 25, D-70599 Stuttgart, Germany

Flavonol O- and xanthone C-glycosides were extracted from mango (Mangifera indica L. cv. “Tommy
Atkins”) peels and characterized by high-performance liquid chromatography-electrospray ionization
mass spectrometry. Among the fourteen compounds analyzed, seven quercetin O-glycosides, one
kaempferol O-glycoside, and four xanthone C-glycosides were found. On the basis of their
fragmentation pattern, the latter were identified as mangiferin and isomangiferin and their respective
galloyl derivatives. A flavonol hexoside with m/z 477 was tentatively identified as a rhamnetin glycoside,
which to the best of our knowledge, has not yet been reported in mango peels. The results obtained
in the present study confirm that peels originating from mango fruit processing are a promising source
of phenolic compounds that might be recovered and used as natural antioxidants or functional food
ingredients.

KEYWORDS: Mango; Mangifera indica (L.); peels; flavonols; xanthones; HPLC-MS/MS

INTRODUCTION In a previous study, the presence of a broad pattern of


Mango (Mangifera indica L., Anacardiaceae) is one of the phenolic compounds, especially of flavonol glycosides, in
most important tropical fruits. Mango and mango products such mango puree concentrate was demonstrated for the first time
as puree, nectar, leather, chutneys, pickles, and canned slices (13). It was assumed that these phenolics may in part originate
experience worldwide popularity and have also gained increasing from the peel, because mango puree is prepared from both
importance in the European market (1). Major byproducts of peeled and unpeeled fruits, and especially because total poly-
mango processing are peels and seeds, amounting for 35 and phenolics are higher in the peel than in the pulp at all stages of
60% of the total fruit weight, respectively (2). Because these mango fruit development (14). However, because the sample
byproducts represent a serious disposal problem, various at- examined was a commercial puree concentrate, the origin of
tempts at utilizing seed kernels and peels have been made in the polyphenolics could not be conclusively elucidated.
the past decades. While a number of investigations have been In continuation of our investigations on the recovery of natural
conducted on the composition and possible utilization of mango food ingredients from byproducts of fruit processing (15, 16),
seed kernels (3-7), studies on peels are scarce. polyphenolics were extracted from mango peels and character-
Srirangarajan and Shrikhande (8) investigated the chemical ized by HPLC with diode array and mass spectrometric
and physical characteristics of mango peel pectin and suggested detection.
its commercial exploitation. Sudhakar and Maini (9) developed
a standardized method for the recovery of pectin from “Tota- MATERIALS AND METHODS
puri” mango peels. In more recent investigations, mango peels
were reported to be a good source of dietary fiber containing Standards. Standards used for identification purposes with HPLC
and MS were as follows: quercetin 3-O-xyloside, quercetin 3-O-
large amounts of total extractable polyphenolics (2). This high
arabinofuranoside (Plantech, Reading, UK); quercetin, quercetin 3-O-
content of polyphenolics was reflected by high antioxidative arabinopyranoside, quercetin 3-O-arabinoglucoside (Roth, Karlsruhe,
activity in in vitro studies (10, 11). Because total extractable Germany); mangiferin [2-C-β-D-glucopyranosyl-1,3,6,7-tetrahydroxy-
polyphenolics were determined by the Folin-Ciocalteu assay, xanthone], quercetin 3-O-galactoside, quercetin 3-O-glucoside, quercetin
no conclusions could be drawn as to their chemical structures. 3-O-rhamnoside, kaempferol 3-O-glucoside, isorhamnetin 3-O-gluco-
Furthermore, owing to their lack of selectivity, spectrophoto- side, rhamnetin (Extrasynthese, Lyon, France).
metric methods tend to overestimate the phenolic content (12). Sample Preparation. Mature Peruvian mango fruits of the cultivar
Tommy Atkins were obtained from the local market. The peels were
* Corresponding author. Tel.: ++49-(0) 711-459-3125. Fax: ++49- removed from the flesh with a stainless steel knife, immediately
(0) 711-459-4110. E-mail: [email protected]. lyophilized, and finely ground using an S1/2 ball mill (Retsch, Haan,

10.1021/jf030218f CCC: $25.00 © 2003 American Chemical Society


Published on Web 07/18/2003
Flavonol and Xanthone Glycosides from Mango Peels J. Agric. Food Chem., Vol. 51, No. 17, 2003 5007

Germany). Aliquots of 2.5 g of the lyophilizate were weighed into an that are not sufficiently retained on conventional reverse phase
amber glass round-bottomed flask. After addition of 0.5 g of ascorbic systems. They have been demonstrated to be highly suitable
acid, the flask was flushed with nitrogen and the mixture extracted for the determination of phenolic compounds from apple and
with 50 mL of aqueous acetone (80%, v/v) for 3 h under stirring. The pear (17, 18) and strawberry (19). As can be seen from Figure
extract was centrifuged (10 min, 4000 rpm), and the residue extracted
1, about twenty major compounds were separated and detected
with 50 mL of aqueous acetone for 10 min. The organic solvent was
removed from the combined supernatants by evaporation in vacuo at
at 370 nm, fourteen of which could be characterized and
30 °C. The aqueous solution was transferred into a graduated flask identified.
and made up to 50 mL with deionized water. After microfiltration (5 Compound 1 was readily identified as mangiferin (Figure
µm), aliquots of 20 mL were used for further purification. Polyamide 2), a xanthone C-glycoside occurring in a variety of plants (20).
CC6 (2 g, 0.05-0.16 mm) (Macherey-Nagel, Dueren, Germany) was Compound 2 displayed identical UV and mass spectrometric
filled into an Econo-Pac column (BioRad, Munich, Germany) and data and was therefore assigned to isomangiferin (Figure 2).
successively conditioned with 25 mL methanol and 50 mL deionized Mass spectrometric analysis of both compounds showed a
water prior to application of the peel extract to the column. After
pseudomolecular ion of m/z 421 and a loss of 120 amu (atom
washing with water (50 mL), the polyphenolic fraction was recovered
by elution with methanol (100 mL). The eluate was evaporated to
mass units) in the MS2 event (Table 1), a fragmentation behavior
dryness, and the residue was dissolved in 0.5 mL of aqueous methanol. typical of C-glycosides. In contrast to flavonoid O-glycosides,
The solution was membrane-filtered (0.45 µm, Whatman Inc., Clifton, C-glycosides do not generate abundant aglycone ions (21).
NJ) and used for HPLC. While no evidence for the presence of homomangiferin was
HPLC Analysis. The separation of phenolic compounds was obtained, two compounds (3 and 4) also displaying xanthone
performed using an Agilent HPLC, series 1100 (Agilent, Waldbronn, UV spectra were detected. Mass spectrometric analysis revealed
Germany) equipped with ChemStation software, a model G1322A a pseudomolecular ion of m/z 573. In the MS2 event, a loss of
degasser, a model G1312A binary gradient pump, a model G1329/ 152 amu indicative of a galloyl moiety was observed. Because
1330A thermoautosampler, a model G1316A column oven, and a model further fragmentation (MS3, MS4) was almost identical to
G1315A diode array detector. The column used was a 150 × 3.0-mm
mangiferin and isomangiferin, it is concluded that these
i.d., 4-µm C18 Hydro-Synergi (Phenomenex, Torrance, CA), with a
4.0 × 2.0-mm i.d. C18 ODS guard column, operated at a temperature compounds represent galloylated xanthone C-glycosides. The
of 25 °C. The mobile phase consisted of 2% (v/v) acetic acid in water occurrence of mangiferin 6′-O-gallate has been described in
(eluent A) and of 0.5% acetic acid in water and acetonitrile (50:50, mango leaves, but no evidence was obtained for the presence
v/v; eluent B). The gradient program was as follows: 0-25% B (15 of its isomer (22). Because the nongalloylated xanthone gly-
min), 25-30% B (35 min), 30-80% B (10 min), 80-100% B (5 min), cosides elute in the order mangiferin-isomangiferin, it is
100-0% B (0.5 min). The injection volume for all samples was 4 µL. reasonable to assume that mangiferin 6′-O-gallate elutes prior
Simultaneous monitoring was performed at 320 nm (xanthones), and to the isomangiferin derivative. Mangiferin has been shown to
370 nm (flavonols) at a flow rate of 0.6 mL/min. Spectra were recorded be the predominant constituent of mango stem bark aqueous
from 200 to 600 nm (peak width 0.2 min, data rate 1.25/s). decoctions traditionally used as a nutritional supplement in Cuba
LC-MS Analyses. LC-MS analyses were performed with the same (23). Furthermore, there is ample evidence that mangiferin
HPLC system as described above connected in series with a Bruker
displays a multitude of pharmacological effects such as hypo-
(Bremen, Germany) model Esquire 3000+ ion trap mass spectrometer
fitted with an ESI source. Negative ion mass spectra of the column lipidemic (24), antidiabetic (25), antioxidant (26,27), hepato-
eluate were recorded in the range m/z 50-1000. Nitrogen was used as protective (28), as well as immunomodulatory, antiviral, and
the dry gas at a flow rate of 10.0 L/min and at a pressure of 60.0 psi. antitumor (29-31) activities. Very recently, inhibitory effects
The nebulizer temperature was set at 365 °C. Collision-induced in bowel carcinogenesis of male F344 rats have also been
dissociation spectra were obtained with a fragmentation amplitude of described (32). Therefore, extracts from mango peels represent
1.2 V (MS/MS) and 1.5 V (MS>2) for flavonoids, 1.2 V (MS/MS) a valuable source of mangiferin and further xanthone glycosides.
and 1.7 V (MS>2) for xanthones, 1.2 V (MS/MS and MS3) and 1.7 V Compounds 5-11 were identified as quercetin O-glycosides
(MS4) for xanthone gallates, 1.5 V (MS/MS) for flavonoid aglycones.
(Figure 3) based on their UV and mass spectra and by
Helium was used as the collision gas (1.2 × 10-5 mbar). Quercetin
3-O-galactoside was used for the optimization of ionization parameters. comparison with standard substances (Table 1). Compound 14
represented the quercetin aglycone. It is interesting to note that
the profile of flavonol glycosides obtained in the present study
RESULTS AND DISCUSSION is almost identical to that found in mango puree concentrate in
Extraction and Purification of Phenolic Compounds. In previous investigations (13), with quercetin 3-O-galactoside and
our previous study, polyphenolics were extracted from a quercetin 3-O-glucoside being the predominant compounds.
commercial mango puree concentrate with organic solvents and However, at that time, only part of these flavonol glycosides
fractionated on Sephadex LH20. The eleven fractions obtained could be identified, owing to the lack of reference samples.
after elution with water-methanol mixtures were analyzed for Improved methods and the availability of a greater range of
their phenolic compounds, yielding phenolic acids, mangiferin, standard substances now allowed the unambiguous identification
flavonol glycosides, and a gallotannin (13). However, this of most of the flavonol glycosides extracted from mango peels.
procedure proved to be time consuming, tedious, and hardly Consistent with the results of a very recent study on the
applicable to routine analysis of a great number of samples. collision-induced dissociation of flavonoid glycosides (33),
Therefore, phenolic compounds from mango peels were purified homolytic and heterolytic cleavage was observed under the mass
by solid-phase extraction using polyamide. Hydrolyzable tannins spectrometric conditions applied. In most cases, quercetin
were not considered in the present study because their isolation glycosides produced a Y0- ion at m/z 301 as the predominant
and characterization is currently underway and will be reported fragment caused by heterolytic cleavage. The formation of the
in a separate communication. radical aglycone as the main fragment was observed only for
HPLC Analysis of Xanthone and Flavonol Glycosides. A compounds 5 and 9. The data given in Table 1 for the MS3
stationary phase with hydrophilic endcapping was used for the event include fragments recorded for both pathways.
analysis of phenolic compounds. Such types of phases have been Compound 5 showed a pseudomolecular ion of m/z 595
developed especially for the separation of very polar analytes identical to quercetin 3-O-arabinoglucoside (peltatoside), how-
5008 J. Agric. Food Chem., Vol. 51, No. 17, 2003 Schieber et al.

Figure 1. Separation of xanthone C- and flavonol O-glycosides by high-performance liquid chromatography (370 nm). Peak assignment: (1) Mangiferin,
(2) isomangiferin, (3) and (4) mangiferin gallate and isomangiferin gallate (tentatively identified), (5) quercetin 3-O-diglycoside, (6) quercetin 3-O-galactoside,
(7) quercetin 3-O-glucoside, (8) quercetin 3-O-xyloside, (9) quercetin 3-O-arabinopyranoside, (10) quercetin 3-O-arabinofuranoside, (11) quercetin 3-O-
rhamnoside, (12) kaempferol 3-O-glucoside, (13) rhamnetin 3-O-glycoside, (14) quercetin (aglycone).

Comparison of retention time, UV spectra, and mass spectro-


metric data of the reference substance revealed the presence of
quercetin 3-O-rhamnoside (quercitrin).
Compound 12 was the only kaempferol glycoside detected
in the mango peel extract. It showed a pseudomolecular ion of
m/z 447 and prominent ions of the kaempferol aglycone of m/z
285 (Y0-) and m/z 284 (Y0-H)-. Because it coeluted with
the reference, it was identified as kaempferol 3-O-glucoside
(astragalin) (Figure 3).
Compound 13 showed a pseudomolecular ion of m/z 477 and
a prominent aglycone fragment of m/z 315. From these data
Figure 2. Structures of the xanthone C-glycosides mangiferin (1) and and the UV spectrum it could be deduced that 13 represented
isomangiferin (2). either isorhamnetin or rhamnetin attached to a hexose. Both
compounds are methoxylated flavonoids that only differ in the
ever, it did not coelute with the reference substance. It is position of the methyl group. Whereas rhamnetin is methoxy-
therefore concluded that 5 or the reference represents an isomer lated in position 7 of the A-ring (Figure 3), the methoxyl group
of peltatoside differing in conformation or linkage of the of isorhamnetin is localized in position 3′ of the flavonoid
saccharide moiety. A similar problem has been encountered in B-ring. Recently, Justesen (34) reported that methoxylated
a recent study of quercetin glycosides in apple pomace (18). flavonoid aglycones can be easily distinguished by means of
Compounds 6, 7, and 8 were identified as quercetin 3-O- mass spectrometry because of their different fragmentation
galactoside (hyperoside), 3-O-glucoside (isoquercitrin) and 3-O- profiles. Later, this strategy was used for the identification of
xyloside (reynoutrin), respectively. Mass spectrometric char- isorhamnetin glycosides in apples (35). In the present study,
acterization of compounds 9 and 10 provided evidence for the fragmentation of compound 13 was compared with that of
presence of further two quercetin pentosides with m/z 433 as isorhamnetin 3-O-glucoside and of the rhamnetin aglycone. The
the pseudomolecular ion. Spiking with reference substances latter compound was not available in glycosidic form. From
allowed their identification as quercetin 3-O-arabinopyranoside Table 1 it can be seen that isorhamnetin 3-O-glucoside
(guajaverin) and quercetin 3-O-arabinofuranoside (avicularin). generated a prominent ion of m/z 300 in the MS3 event, whereas
Both quercetin glycosides have also been found in apples (18), in the case of compound 13, the most abundant ion was m/z
however, to our knowledge, this is the first report on their 165, which exactly matched the fragmentation profile of the
simultaneous occurrence in mango. rhamnetin aglycone in the MS2 event. According to Justesen
Compound 11 provided a pseudomolecular ion of m/z 447 (34), the formation of an A-ring fragment of m/z 165 as the
and an aglycone fragment of m/z 301 and could therefore be most prominent fragment is a peculiarity of rhamnetin. There-
readily identified as quercetin attached to a desoxy hexose. fore, ample evidence for the first proof of a rhamnetin glycoside
Flavonol and Xanthone Glycosides from Mango Peels J. Agric. Food Chem., Vol. 51, No. 17, 2003 5009

Table 1. UV Spectra and Characteristic Ions of Xanthone and Flavonol Glycosides Extracted from Peels of Mangifera indica L. cv. “Tommy Atkins”a

[M −H ]- HPLC-ESI(−)-MSn experiment
peak identity HPLC-DAD λmax [nm] m/z m/z (% base peak)
1 mangiferin 241, 258, 275sh, 318, 366 421 −MS2 [421]: 403 (22), 331 (99), 301 (100)
−MS3 [421 f 301]: 273 (88), 258 (100)
2 isomangiferin 241sh, 256, 275sh, 317, 365 421 −MS2 [421]: 403 (10), 331 (90), 301 (100)
−MS3 [421 f 301]: 273 (73), 258 (100)
3 mangiferin gallateb 241, 258, 275sh, 318, 366 573 −MS2 [573]: 421 (100), 403 (10), 331 (11), 301 (14)
−MS3 [573 f 421]: 331 (40), 301 (100)
−MS4 [573 f 421 f 301]: 273 (100), 258 (30)
4 isomangiferin gallateb 241sh, 256, 275sh, 317, 366 573 −MS2 [573]: 421 (100), 403 (38), 331 (19), 301 (22),
283 (76), 259 (23)
−MS3 [573 f 421]: 331 (32), 301 (100)
−MS4 [573 f 421 f 301]: 273 (75), 258 (100)
5 quercetin 3-O-diglycoside 232, 256, 266sh, 296sh, 355 595 −MS2 [595]: 301 (51), 300 (100), 271 (19)
−MS3 [595 f 300]: 271 (100), 255 (51)
−MS3 [595 f 301]: 272 (53), 256 (51), 179 (80), 151 (100)
6 quercetin 3-O-galactoside 232, 256, 266sh, 296sh, 353 463 −MS2 [463]: 301 (100), 300 (34)
−MS3 [463 f 300]: 271 (100), 255 (64)
−MS3 [463 f 301]: 179 (79), 151 (100)
7 quercetin 3-O-glucoside 232, 256, 266sh, 296sh, 353 463 −MS2 [463]: 301 (100), 300 (22)
−MS3 [463 f 300]: 271 (100), 255 (65)
−MS3 [463 f 301]: 179 (94), 151 (100)
8 quercetin 3-O-xyloside 232, 256, 266sh, 296sh, 354 433 −MS2 [433]: 301 (100), 300 (18)
−MS3 [433 f 300]: 271 (100), 255 (47)
−MS3 [433 f 301]: 179 (97), 151 (100)
9 quercetin 3-O-arabinopyranoside 231, 256, 266sh, 296sh, 354 433 −MS2 [433]: 301 (77), 300 (100)
−MS3 [463 f 300]: 271 (100), 255 (49)
−MS3 [433 f 301]: 179 (100), 151 (81)
10 quercetin 3-O-arabinofuranoside 230, 257, 266sh, 296sh, 352 433 −MS2 [433]: 301 (100), 300 (11)
−MS3 [463 f 300]: 300 (21), 271 (100), 255 (69)
−MS3 [433 f 301]: 179 (98), 151 (100)
11 quercetin 3-O-rhamnoside 231, 256, 266sh, 296sh, 350 447 −MS2 [447]: 301 (100), 300 (32)
−MS3 [463 f 300]: 271 (100), 255 (54)
−MS3 [447 f 301]: 179 (100), 151 (90)
12 kaempferol 3-O-glucoside 232, 265, 294sh, 347 447 −MS2 [447]: 447 (22), 285 (94), 284 (100), 255 (31)
−MS3 [447 f 284]: 255 (100)
−MS3 [447 f 285]: 267 (34), 257 (100), 256 (64),
241 (31), 229 (51), 213 (30), 163 (28)
13 rhamnetin-hexoside 231, 257, 355 477 −MS2 [477]: 315 (100), 314 (29)
−MS3 [477 f 314]: 299 (100)
−MS3 [477 f 315]: 300 (23), 193 (25), 165 (100)
14 quercetin 230, 255, 266sh, 302sh, 371 301 −MS2 [301]: 179 (89), 151 (100)
Std mangiferin 240, 258, 275sh, 318, 366 421 −MS2 [421]: 403 (16), 331 (100), 301 (98)
−MS3 [421 f 301]: 273 (67), 272 (18), 258 (100)
Std quercetin 3-O-arabino-glucoside 231, 256, 266sh, 296sh, 355 595 −MS2 [595]: 301 (100), 300 (28), 271 (10)
−MS3 [595 f 300]: 271 (100), 255 (63)
−MS3 [595 f 301]: 179 (96), 151 (100)
Std quercetin 3-O-galactoside 232, 256, 266sh, 296sh, 353 463 −MS2 [463]: 301 (100), 300 (31)
−MS3 [463 f 300]: 271 (100), 255 (50)
−MS3 [463 f 301]: 179 (92), 151 (100)
Std kaempferol 3-O-glucoside 232, 265, 294sh, 347 447 −MS2 [447]: 447 (35), 285 (84), 284 (100), 255 (33)
−MS3 [447 f 284]: 255 (100)
−MS3 [447 f 285]: 267 (32), 257 (100), 256 (69),
241 (21), 229 (44), 213 (30), 197 (19), 163 (23)
Std isorhamnetin 3-O-glucoside 255, 265sh, 297sh, 354 477 −MS2 [477]: 477 (76), 357 (18), 315 (37), 314 (100)
−MS3 [477 f 314]: 286 (27), 285 (100), 271 (93), 243 (23)
−MS3 [477 f 315]: 300 (100)
Std rhamnetin 230, 256, 370 315 −MS2 [315]: 300 (26), 193 (37), 165 (100)

a Data of selected reference compounds (std) are also included. b Tentatively identified.

might contribute to the antioxidant activity that has been shown


for mango peel dietary fiber (10, 11). The results are also
interesting from a technological point of view. Mango puree
concentrate, which represents an important intermediate for the
production of mango beverages and mango leather, is prepared
from both peeled and unpeeled fruits, depending on the cultivar
Figure 3. General structure and substitution pattern of flavonol glycosides used. Analysis of the phenolic profile of mango puree would
detected in mango peels. allow a clear statement whether fruits were peeled prior to
processing. This is particularly important because the peels
in mango peels is provided. Currently, methods for the prepara-
might contain allergenic alkylresorcinols which act as fungitoxic
tive isolation and structure elucidation of compound 13 are being
developed. compounds and may originate from the latex (36) but have also
The results obtained in the present study demonstrate that been detected in peels of unripe mango fruits (37).
the profile of xanthone and flavonol glycosides in mango peels We have recently established a new process for the combined
is even more complex than known so far. These compounds recovery of pectin and polyphenolics from apple pomace. The
5010 J. Agric. Food Chem., Vol. 51, No. 17, 2003 Schieber et al.

process comprises extraction of the dried pomace with diluted (12) Escarpa, A.; González, M. C. Approach to the content of total
mineral acids and adsorption of phenolic compounds to a extractable phenolic compounds from different food samples by
styrene-divinylbenzene copolymerizate that has been approved comparison of chromatographic and spectrophotometric methods.
for food use by the FDA (38). Because mango peels are not Anal. Chim. Acta 2001, 427, 119-127.
only rich in polyphenolics but also contain a high quality pectin (13) Schieber, A.; Ullrich, W.; Carle, R. Characterization of polyphe-
with a high degree of esterification (about 75%), this process nols in mango puree concentrate by HPLC with diode array and
mass spectrometric detection. Inn. Food Sci. Emerg. Technol.
may also be adopted to the recovery of phenolic compounds,
2000, 1, 161-166.
thus adding value to mango fruit processing. Currently, there
(14) Lakshminarayana, S.; Subhadra, N. V.; Subramanyam, H. Some
is an increasing tendency to maximize juice yields by the use
aspects of developmental physiology of mango fruit. J. Horticult.
of pectolytic and cellulolytic enzymes (39). However, apple Sci. 1979, 45, 133-142.
pomace resulting from mash liquefaction cannot be exploited (15) Schieber, A.; Stintzing, F. C.; Carle, R. Byproducts of plant food
for the recovery of pectin because the polysaccharides are partly processing as a source of functional compounds-recent develop-
depolymerized. On a long-term basis, enzymatic liquefaction ments. Trends Food Sci. Technol. 2001, 12, 401-413.
of fruits might lead to scarcity of apple pomace as a raw (16) Schieber, A.; Hilt, P.; Streker, P.; Endress, H.-U.; Rentschler,
material, and alternative sources of pectins are urgently needed. C.; Carle, R. A new process for the combined recovery of pectin
Because mango peels are available in large amounts and have and phenolic compounds from apple pomace. Inn. Food Sci.
been shown to contain high-quality pectin with a high degree Emerg. Technol. 2003, 4, 99-105.
of esterification (9) as well as dietary fiber (2), they are (17) Schieber, A.; Keller, P.; Carle, R. Determination of phenolic acids
promising sources of valuable compounds and should be and flavonoids of apple and pear by high-performance liquid
strongly considered for exploitation. To evaluate their potential chromatography. J. Chromatogr. A 2001, 910, 265-273.
as well as possible risks, economically relevant mango cultivars (18) Schieber, A.; Hilt, P.; Conrad, J.; Beifuss, U.; Carle, R. Elution
are currently being screened for their pectin contents and quality order of quercetin glycosides from apple pomace extracts on a
and for their phenolic profile and contents, including hydrolyz- new HPLC stationary phase with hydrophilic endcapping. J. Sep.
able tannins and alkylresorcinols. Sci. 2002, 25, 361-364.
(19) Hilt, P.; Schieber, A.; Yildirim, C.; Arnold, G.; Conrad, J.;
Klaiber, I.; Beifuss, U.; Carle, R. Detection of phloridzin in
ACKNOWLEDGMENT strawberries (Fragaria x ananassa DUCH.) by HPLC-PDA-
MS/MS and NMR spectroscopy. J. Agric. Food Chem. 2003,
We thank Ms. Ramona Fezer for technical assistance. 51, 2896-2899.
(20) Hostettmann, K.; Wagner, H. Xanthone glycosides. Phytochem-
istry 1977, 16, 821-829.
LITERATURE CITED
(21) Waridel, P.; Wolfender, J.-L.; Ndjoko, K.; Hobby, K. R.; Major,
(1) Loeillet, D. The European mango market: A promising tropical H. J.; Hostettmann, K. Evaluation of quadrupole time-of-flight
fruit. Fruits 1994, 49, 332-334. tandem mass spectrometry and ion-trap multiple-stage mass
(2) Larrauri, J. A.; Rupérez, P.; Borroto, B.; Saura-Calixto, F. Mango spectrometry for the differentiation of C-glycosidic flavonoid
peels as a new tropical fibre: Preparation and characterization. isomers. J. Chromatogr. A 2001, 926, 29-41.
Lebensm.-Wiss. Technol. 1996, 29, 729-733. (22) Tanaka, T.; Sueyasu, T.; Nonaka, G.; Nishioka, I. Tannins and
(3) Arogba, S. S. Physical, chemical and functional properties of related compounds. XXI. Isolation and characterization of galloyl
Nigerian mango (Mangifera indica) kernel and its processed and p-hydroxybenzoyl esters of benzophenone and xanthone
flour. J. Sci. Food Agric. 1997, 73, 321-328. C-glucosides from Mangifera indica L. Chem. Pharm. Bull.
(4) Arogba, S. S. Mango (Mangifera indica) kernel: Chromato- 1984, 32, 2676-2686.
graphic analysis of the tannin and stability study of the associated (23) Núñez Sellés, A. J.; Vélez Castro, H. T.; Agüero-Agüero, J.;
polyphenol oxidase activity. J. Food Comp. Anal. 2000, 13, 149- González-González, J.; Naddeo, F.; De Simone, F.; Rastrelli, L.
156. Isolation and quantitative analysis of phenolic antioxidants, free
(5) Puravankara, D.; Boghra, V.; Sharma, R. S. Effect of antioxidant sugars, and polyols from mango (Mangifera indica L.) stem bark
principles isolated from mango (Mangifera indica L) seed kernels aqueous decoction used in Cuba as a nutritional supplement. J.
on oxidative stability of buffalo ghee (butter-fat) J. Sci. Food Agric. Food Chem. 2002, 50, 762-766.
Agric. 2000, 80, 522-526. (24) Miura, T.; Iwamoto, N.; Kato, M.; Ichiki, H.; Kubo, M.;
(6) Kabuki, T.; Nakajima, H.; Arai, M.; Ueda, S.; Kuwabara, Y.; Komatsu, Y.; Ishida, T.; Okada, M.; Tanigawa, K. The suppre-
Dosako, S. Characterization of novel antimicrobial compounds sive effect of mangiferin with exercise on blood lipids in type 2
from mango (Mangifera indica L.) kernel seeds. Food Chem.
diabetes. Biol. Pharm. Bull. 2001, 24, 1091-1092.
2000, 71, 61-66.
(25) Miura, T.; Iwamoto, N.; Kato, M.; Ichiki, H.; Kubo, M.;
(7) Parmar, S. S.; Sharma, R. S. Effect of mango (Mangifera indica
Komatsu, Y.; Sasaki, H.; Ishida, T.; Tanigawa, K. Effect of
L.) seed kernels pre-extract on the oxidative stability of ghee.
mangiferin on muscle GLUT4 protein content in TSOD (Tsumu-
Food Chem. 1990, 35, 99-107.
ra, Suzuki, obese, diabetes) mouse, a new type 2 diabetic mice.
(8) Srirangarajan, A. N.; Shrikhande, A. J. Characterization of mango
peel pectin. J. Food Sci. 1977, 42, 279-280. Biomed. Res. 2001, 22, 249-252.
(9) Sudhakar, D. V.; Maini, S. B. Isolation and characterization of (26) Sánchez, G. M.; Re, L.; Giuliani, A.; Nuñez-Sellés, A. J.;
mango peel pectins. J. Food Process. PreserV. 2000, 24, 209- Davison, G. P.; León-Fernández, O. S. Protective effects of
227. Mangifera indica L. extract, mangiferin and selected TPA-
(10) Larrauri, J. A.; Goni, I.; Martin-Carron, N.; Rupérez, P.; Saura- induced biomolecules oxidation and peritoneal macrophage
Calixto, F. Measurement of health-promoting properties in fruit activation in mice. Pharmacol. Res. 2000, 42, 565-573.
dietary fibres: Antioxidant capacity, fermentability and glucose (27) Salvi, A.; Bruhlmann, C.; Migliavacca, E.; Carrupt, P.-A.;
retardation index. J. Sci. Food Agric. 1996, 71, 515-519. Hostettmann, K.; Testa, B. Protein protection by antioxidants:
(11) Larrauri, J. A.; Rupérez, P.; Saura-Calixto, F. Mango peel fibres Development of a convenient assay and structure-activity
with antioxidant activity. Z. Lebensm.-Unters. -Forsch. 1997, relationships of natural polyphenols. HelV. Chim. Acta 2002, 85,
205, 39-42. 867-881.
Flavonol and Xanthone Glycosides from Mango Peels J. Agric. Food Chem., Vol. 51, No. 17, 2003 5011

(28) Yoshikawa, M.; Ninomiya, K.; Shimoda, H.; Nishida, N.; (35) Schieber, A.; Keller, P.; Streker, P.; Klaiber, I.; Carle, R.
Matsuda, H. Hepatoprotective and antioxidative properties of Detection of isorhamnetin glycosides in extracts of apples (Malus
Salacia reticulata: Preventive effects of phenolic constituents domestica cv. “Brettacher”) by HPLC-PDA and HPLC-APCI-
on CCl4-induced liver injury in mice. Biol. Pharm. Bull. 2002, MS/MS. Phytochem. Anal. 2002, 13, 87-94.
25, 72-76. (36) Bandyopadhyay, C.; Gholap, A. S.; Mamdapur, V. R. Charac-
(29) Guha, S.; Ghosal, S.; Chattopadhyay, U. Antitumor, immuno-
terization of alkylresorcinol in mango (Mangifera indica L.)
modulatory, and anti-HIV effect of mangiferin, a naturally
latex. J. Agric. Food Chem. 1985, 33, 377-379.
occurring glucosylxanthone. Chemotherapy 1996, 42, 443-451.
(30) Yoosook, C.; Bunyapraphatsara, N.; Boonyakiat, Y.; Kantasuk, (37) Cojocaru, M.; Droby, S.; Glotter, E.; Goldman, A.; Gottlieb, H.
C. Anti-herpes simplex virus activities of crude water extracts E.; Jacoby, B.; Prusky, D. 5-(12-Heptadecenyl)-resorcinol, the
of Thai medicinal plants. Phytomedicine 2000, 6, 411-419. major component of the antifungal activity in the peel of mango
(31) Makare, N.; Bodhankar, S.; Rangari, V. Immunomodulatory fruit. Phytochemistry 1986, 25, 1093-1095.
activity of alcoholic extract of Mangifera indica L. in mice. J. (38) FDA Food Additive Regulation 21CFR173.65, Divinylbenzene
Ethnopharmacol. 2001, 78, 133-137. Copolymer.
(32) Yoshimi, N.; Matsunaga, K.; Katayama, M.; Yamada, Y.; Kuno, (39) Will, F.; Bauckhage, K.; Dietrich, H. Apple pomace liquefaction
T.; Qiao, Z.; Hara, A.; Yamahara, J.; Mori H. The inhibitory with pectinases and cellulases: Analytical data of the corre-
effects of mangiferin, a naturally occurring glucosylxanthone, sponding juices. Eur. Food Res. Technol. 2000, 211, 291-297.
in bowel carcinogenesis of male F344 rats. Cancer Lett. 2001,
163, 163-170.
(33) Hvattum, E.; Ekeberg, D. Study of the collision-induced radical
Received for review March 25, 2003. Revised manuscript received June
cleavage of flavonoid glycosides using negative electrospray
4, 2003. Accepted June 6, 2003. Financial support provided by fruit -
ionization tandem quadrupole mass spectrometry. J. Mass
Spectrom. 2003, 38, 43-49. International Fruit Foundation, Heidelberg-Schlierbach, Germany.
(34) Justesen, U. Collision-induced fragmentation of deprotonated
methoxylated flavonoids, obtained by electrospray ionization
mass spectrometry. J. Mass Spectrom. 2001, 36, 169-178. JF030218F

You might also like