Saponins and flavonoid glycosides from the leaves of Ziziphus mauritiana Lam. native of a forest area of Ivory Coast

Article abstract of DOI:10.1016/j.phytol.2020.03.001

Ziziphus mauritiana Lam (Rhamnaceae) is traditionally used in the treatment of various ailments. The aim of the present study is to identify the major compounds of the methanol extract of the leaves of Ziziphus mauritiana growing in Ivory Coast. The methanol extract of this plant was purified by combining silica gel and RP18 HPLC to give an undescribed compounds, 6’’’-O-malonyl-ziziphus saponin I (1) along with nine known compounds from which two saponins, six flavonoids, and one chalcone derivate.The structures of these compounds were elucidated by analysis of 1D- and 2D-NMR spectroscopic data and mass spectrometry (HR-ESI-MS). A part from zizyphus saponin I (2), all the others compounds were isolated for the first time from the leaves of this species.

Full text of DOI:10.1016/j.phytol.2020.03.001

PhytochemistryLetters37(2020)5–9
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Phytochemistry Letters
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Saponins and flavonoid glycosides from the leaves of Ziziphus mauritiana
Lam. native of a forest area of Ivory Coast
Chardin Seri Seria,b,*, Timothée Aboua Okpekona, Philomene Akoua Yao-Kouassia,
Abdulmagid Alabdul Magidb, Charlotte Sayaghb, Laurence Voutquenne-Nazabadiokob
a Université Félix Houphouët-Boigny d’Abidjan-Cocody, Laboratoire de Chimie Organique et de Substances Naturelles, 22 BP 582 Abidjan 22, Cote d’Ivoire
b Université de Reims Champagne Ardenne, CNRS, ICMR UMR 7312, 51097, Reims, France
A R T I C L E I N F O
A B S T R A C T
Keywords:
Ziziphus mauritiana Lam (Rhamnaceae) is traditionally used in the treatment of various ailments. The aim of the
present study is to identify the major compounds of the methanol extract of the leaves of Ziziphus mauritiana
growing in Ivory Coast. The methanol extract of this plant was purified by combining silica gel and RP18 HPLC
to give an undescribed compounds, 6’’’-O-malonyl-ziziphus saponin I (1) along with nine known compounds
from which two saponins, six flavonoids, and one chalcone derivate.The structures of these compounds were
elucidated by analysis of 1D- and 2D-NMR spectroscopic data and mass spectrometry (HR-ESI-MS). A part from
zizyphus saponin I (2), all the others compounds were isolated for the first time from the leaves of this species.
Ziziphus mauritiana
Rhamnaceae
Saponin
Flavonoid
1. Introduction
and induce kidney tissue damages in rats (Attemene et al., 2017), but
no compounds were formerly identified. In addition, the saponin ex-
Ziziphus mauritiana Lam. (Rhamnaceae) is a thorny shrub and sar-
mentous, up to 1–2 m tall, distributed in the sub-Sahelian zone of
Africa, from Senegal to Somalia (CEE/ENDA, 1987; Fofie et al., 2018;
Sivasankari and Sankaravadivoo, 2017). It is found in the savannah,
central and north regions of Ivory Coast, where it is used in traditional
medicine against anemia, hypertonia, nephristis and nervous diseases
(Carol et al., 2012). This plant, introduced into the forest areas of Ivory
Coast, was used against diabetes, high blood pressure and various forms
of inflammation (Adama et al., 2016; Ba, 2005; Bhatia and Mishra,
2010; Cisse et al., 2000; Marwat et al., 2009; Memon et al., 2012;
Traore et al., 2008; Yansambou, 2002).The leaves are used in the
treatment of diarrhea, abscesses and gonorrhea, high blood pressure,
liver disorders and diabetes (Diallo et al., 2004; Gupta et al., 2012; Koffi
et al., 2008; Traore et al., 2008; Yansambou, 2002). Phytochemical
investigations carried out to date on Ziziphus mauritiana leaves showed
that the species consisted of cyclopeptide alkaloids, sterols, triterpene
saponins and flavonoids (Akino et al., 1996; Ashraf et al., 2015;
Ghasham et al., 2017; Sharma and Kumar, 1982). Recent studies
showed that leaf extract of this plant possess antimicrobial and anti-
oxidant activities (Ashraf et al., 2015; Ghasham et al., 2017;
Sivasankari and Sankaravadivoo, 2015), anti-inflammatory activity
(Abdallah et al., 2016; Kumar et al., 2017) and cause thrombocytosis
tract of leaves of Z. mauritiana possess antidiabetic and antioxidant
potential (Dubey et al., 2019). Similarly, less attention has been de-
voted to Z. mauritiana leaves growing in Ivory Coast (Attemene et al.,
2017; Fofie et al., 2018). Thus, in the context of this study, we purified
the methanol leaf extract of this species in order to identify its chemical
components. In this paper, we present the isolation and structural
characterization of an undescribed saponin (Fig. 1), together with nine
known compounds.
2. Results and discussion
The MeOH extract of dried and powdered leaves of Z. mauritiana
was subjected to silica gel column chromatography and prep-HPLC to
obtain three triterpene saponins (1-3) from which the compound 1
(Fig. 1), was previously undescribed, and seven phenolic compounds
(4-10).Their structures were elucidated on the basis of spectroscopic
evidence. Saponins 2 and 3 were identified as zizyphus saponin I
(Okamura et al., 1981; Yoshikawa et al., 1992) and lotoside III
(Bozicevic et al., 2017) which had been previously reported from leaves
of Z. mauritiana (Sharma and Kumar, 1982) and Z.spina-christi, respec-
tively. Phenolic compounds (4-10) were identified as quercetin 3-O-
[6’’-(3-hydroxy-3-methylglutaroyl)]-β-D-glucopyranoside (4) (Iwashina
⁎ Corresponding author at: Université Félix Houphouët-Boigny d’Abidjan-Cocody, Laboratoire de Chimie Organique et de Substances Naturelles, 22 BP 582 Abidjan
22, Côte d’Ivoire.
E-mail address: seriserichardin@yahoo.fr (C.S. Seri).
https://doi.org/10.1016/j.phytol.2020.03.001
Received 1 November 2019; Received in revised form 27 February 2020; Accepted 2 March 2020
1874-3900/©2020PhytochemicalSocietyofEurope.PublishedbyElsevierLtd.Allrightsreserved.

C.S. Seri, et al.
PhytochemistryLetters37(2020)5–9
Fig. 1. Structure of compound 1.
et al., 2004), quercetin-3-O-rubinobioside (5) (Rastrelli et al., 1995),
quercetin-3-O-rutinoside (6) (Rastrelli et al., 1995), quercetin-3-O-β-D-
xylopyranosyl-(1→2)-α-L-rhamnopyranoside (7) (Karla et al., 1994),
quercetin-3-O-β-D-xylopyranosyl-(1→2)-α-L-rhamnopyranoside-4’-O-α-
L-rhamnopyranoside (8) (Nawwar et al., 1984), kaempferol-3-O-ruti-
noside (9) (Kazuma et al., 2003) and 3’,5’-di-C-β-glucosylphloretin (10)
(Ogawa et al., 2001).
absolute configurations of these sugars were determined as D for glucose
and L for arabinose and 6-deoxytalose after acid hydrolysis. In the
HMBC spectrum, the anomeric proton signals at δH 4.37 (ara-1), 5.47
(6-deoxy-tal-1), and 4.48 (glc-1) showed cross peaks with the carbon
signals at δC 89.3 (aglycone-C-3), 73.9 (ara-C-2’), and 84.0 (ara-C-3’),
respectively (Fig. 2). These signals provided some evidences to de-
termine the linkages between the sugars and the aglycones. These lin-
kages were also confirmed by correlations, in the NOESY spectrum,
between aglycone-H-3/ara-H-1’, ara-H-2’/H-1’’ and ara-H-3’/glc-H-1’’’.
Additional signals were detected in the 13C NMR spectrum of compound
1: a methylene group (δH 3.77, δC 61.5), and signals attributable to
carboxylic groups in the DEPT spectrum (δC 168.4 and 170.2) (Table 1).
Hence, saponin was esterified with a malonyl moiety. The signals cor-
responding to the CH2-6 of glucose moiety (δH 4.55 and 4.26/ δC 65.0)
appeared downfield compared to those in 2 (δH 3.70 and 3.85/ δC
62.1), and there by indicated an attachment of the acyl moiety at this
position. The saponin was thus identified as jujubogenin 3-β-O-(6’’’-O-
malonyl)-β-D-glucopyranosyl-(1→3)-[6-deoxy-α-L-talopyranosyl-(1→
2)]-α-L-arabinopyranoside (1), and was named 6’’’-O-malonyl-zizyphus
saponin I (Fig. 1).
Compound 1 was isolated as white amorphous powder. The ESI-
HRMS (positive-ion mode) experiment revealed a sodium adduct ion
peak [M + Na]+ at m/z 1021.4992, in agreement with the molecular
formula C50H78O20Na (calcd for C50H78O20Na, 1021.4984).The mole-
cular ion of 1was 86 mass units higher than that of 2 (m/z 935.4969 [M
+ Na]+). These mass differences suggested that 1 contained a malonyl
group. The fragment ion at m/z 935.4992 [M-malonyl + Na]+ was
characteristic of a malonic acid ester (Stein et Zinsmeister, 1990). 1H
and 13C NMR spectra showed the presence of five methyl singulets in
the high field region (δH 0.79, 0.85, 0.99, 1.13 and 1.15), a 2-methyl-
propenyl group (δH 1.68 and 1.72, H3-26 and 27;δH 5.18, H-24), two
oxygenated quaternary carbons (δC 11.1, C-16; and δC 69.2, C-20), an
oxygenated methylene carbon (δC 66.7, C-30), oxygenated methine
carbon (δC 69.4, C-23), and a quaternary carbon (δC 54.4, C-14)
(Table 1). These NMR data of 1 were in good agreement with those of
jujubogenin (Qiang et al., 2016). The ROESY correlations between H-
17, Me-21 and H-22b, and between H-22a and H-23 as well as the
magnitude of the coupling constant between H-13 and H-17 (J = 6.5
Hz) were in agreement with the configuration of D-F rings of jujubo-
genin (Wang et al., 2013; Yu et al., 2013). The downfield shifts of C-3 (δ
89.3) suggested that 1 was a monodesmosidic saponin (Qiang et al.,
2016).
From a chemotaxonomic viewpoint, similar malonyl glycoside with
jujubogenin as aglycone, such as 1, were obtained in Z. spina-christi
(Bozicevic et al., 2017) and Colubrina retusa (Li et al., 1999) belonging
to Rhamnaceae family. Zizyphus saponin I (2) was previously isolated
from the leaves of Z. mauritiana (Sharma and Kumar, 1982), Z jujuba
(Yoshikawa et al., 1992) and Z. incurva (Devkota et al., 2013). Lotoside
III (3) was isolated from the leaves of Z spina-christi (Bozicevic et al.,
2017). Acylglycoside-flavonoids such as 4 have been obtained from
species such as Vaccinium (Ericaceae) (Kaisu et al., 2013) or Astragalus
(Fabaceae) (Semmar et al., 2002), but were isolated here for the first
time in Rhamnaceae family. All flavonoids (5-9) and 3’,5’-di-C-β-glu-
cosylphloretin (10) were previously isolated from the fruits of Z. jujuba,
and Z. spina-christi (Pawlowska et al., 2009), 7-9 were also identified in
the aerial parts of Z. incurva (Devkota et al., 2019), and 3 and 7 were
identified by LC/MS in the leaves of Z jujuba(Bozicevic et al., 2017).
They are to our knowledge describe here for the first time in Z. maur-
itiana leaves. Therefore, they could be used to establish a relationship
between these species.
The 1H NMR spectrum of 1 exhibited three anomeric proton re-
sonances at δ 5.47 (1H, brs), 4.48 (1H, d, J = 7.6 Hz) and 4.37 (1H, d, J
= 7.1 Hz), which were linked to corresponding carbon at δ 101.3,
104.3 and 105.3 in the HSQC spectrum, respectively. By 1H-1H-COSY
and HSQC experiments, the three sugar spin systems were assigned to
β-glucopyranose, 6-deoxy-α-talopyranose and α-arabinopyranose, re-
spectively (Table 1), as in zizyphus saponin I (2). The β-glucopyranose
was identified by the J values from H-1’’’ to H-5’’’ up to 7 Hz that
showed all-trans diaxial interactions. The 6-deoxy-α-talopyranose was
identified by the small J values (brs) of H-1’’, H-2’’, H-3’’ and H-4’’and
the presence of the signal of methyl doublet at δ 1.21 (d, JH-5/H-6 = 6.6
Hz) while the 13C-NMR shifts of C-3’’ (δ 66.6) and C-5’’(δ 67.5) con-
firmed the α-configuration of the anomeric carbon (Kim et al., 2006;
Okamura et al., 1981). Finally, the α-arabinopyranose unit was iden-
tified by the small J values of H-3’/H-4’ (d, JH3’/H-4’ = 3.2 Hz), while
the 13C-NMR shifts of C-3’ (δ 84.0) and C-5’ (δ 65.7) confirmed the α-
configuration of the anomeric carbons (Okamura et al., 1981). The
3. Experimental
3.1. General experimental procedures
Optical rotations were measured on a Perkin Elmer model 341 po-
larimeter (589 nm, 20 °C). IR spectra were obtained on a Nicolet Avatar
320 FT-IR spectrometer with KBr disks. NMR data were performed in
6

C.S. Seri, et al.
PhytochemistryLetters37(2020)5–9
Table 1
1H and 13C NMR spectral data for compound 1 (in CD3OD).
Position
δH, m (J in Hz)
δC
HMBC
Position
δH, m (J in Hz)
δC
HMBC
1
0.96, m; 1.68 m
39.7
27.1
89.3
40.2
57.2
18.8
36.6
38.2
53.9
38.0
22.3
28.9
37.7
54.4
36.9
111.1
54.0
19.1
16.8
69.2
C3, C5, C9, C19
α-L-arabinose
2
1.66, m; 1.85 m
C4, C10
1’
2’
3’
4’
5’
4.37, d (7.1)
105.3
73.9
84.0
69.2
65.7
C3’, C5’, C3
C4’, C1’’
C1’, C5’, C1’’’
C2’
3
3.13, dd (7.3, 2.7)
C1, C5, C1’
3.91, dd (8.2, 7.1)
3.81, dd (8.2, 3.2)
4.02, m
4
–
–
5
0.75, d (9.5)
C1, C3, C28, C29
6
1.55, m
C4, C8, C10
3.51, m; 3.91, m
C1’, C3’
7
1.50, m
C5, C9, C14, C18
6-desoxy-α-L-talose
8
–
–
1’’
5.47, brs
101.3
70.8
66.6
73.3
67.5
16.6
C2’, C3’’, C5’’
C4’’
9
0.87, m
C1, C5, C7, C12, C14, C18, C19
2’’
3.86, brs
10
11
12
13
14
15
16
17
18
19
20
–
–
3’’
3.89, brs
C1’’, C5’’
C2’’, C6’’
C1’’, C3’’
C4’’
1.48, m; 1.64 m
C8, C10, C13
4’’
3.62, brs
1.69, m; 1.86 m
C9, C14, C17
5’’
4.29, q (6.6)
1.21, d (6.6)
2.48, m
C8, C15, C16
6’’
–
–
β-D-glucose
1.21, m; 2.08, d (8.9)
C8, C13, C17, C30
1’’’
2’’’
3’’’
4’’’
5’’’
6’’’
4.48, d (7.6)
3.3,3 dd (9.0, 7.6)
3.39, t (9.0)
104.3
74.4
77.6
71.2
75.1
65.0
C3’’’, C5’’’, C3’
C4’’’
–
–
1.03, d (6.5)
1.13, s
0.85, s
–
C12, C14, C15, C21, C22
C1’’’, C5’’’
C2’’’, C6’’’
C1’’’, C3’’’
C4’’’, C1’’’’
C9, C7, C14
C1, C5, C9
–
3.33, m
3.53, m
4.26 dd(11.2, 5.3)
4.55 dd (11.2, 1.8)
21
22
23
24
26
27
28
29
30
1.15, s
29.5
45.1
69.4
125.9
25.8
18.4
28.2
16.9
66.7
C17, C22
malonic acid ester
1.40, m; 1.48, d (12.6)
4.69, brt (9.7)
5.18, d (9.3)
1.72, s
C17, C21,C24
C16, C20, C25
C22, C26, C27
C24, C27
1’’’’
2’’’’
3’’’’
–
168.4
61.5
3.77 m
–
C1’’’’, C3’’’’
170.2
1.68, s
C24, C26
0.99, s
C3, C5, C29
C3, C5, C28
C8, C13, C15, C16
0.79, s
3.94, d (7.4); 4.02 m
MeOD on Bruker Avance 500 or 600 spectrometer. ESI-HRMS data were
gained using a Micromass Q-TOF high-resolution mass spectrometer.
Mass spectra were recorded in the positive-ion mode in the range m/z
100–2000, with a mass resolution of 20000 and an acceleration voltage
of 0.7 kV. Chromatography Column CC was carried out on HP-20 resin
Sigma Aldrich. Flash chromatography was conducted on a Grace
Reveleris system equipped with dual UV and ELSD detection using
Grace® cartridges Silica gel or RP-18. HPLC separations were performed
on a Dionex apparatus equipped with an ASI-100 autosampler, an
Ultimate 3000 pump, a STH 585 column oven, a diode array detector
UVD 340S and a Chromeleon software. A prepacked RP-18 column
Phenomenex 250 × 15 mm, Luna 12 μm was used for semi-preparative
HPLC. The eluting mobile phase consisted of H2O with TFA (0.0025 %)
and CH3CN with a flow rate of 5 mL/min and the chromatogram was
monitored at 205 and 210 nm. TLC were carried out using silica gel 60
F254 pre-coated aluminium plates (0.2 mm, Merck). Spots were
visualized through developing agent (CHCl3/MeOH/H2O, 14:6:1) and
chromogenic agent (50 % aq. H2SO4) subsequent heating.
3.2. Plant material
The leaves of Z. mauritiana were collected in April 2017 in Sinfra (6°
37′ N, 5° 16′ O), west of Ivory Coast, and identified by comparing with
those found in literature. Further proof on these leaves was made by
experts of the Centre National de Floristique of Félix HOUPHOUËT-
BOIGNY University, Abidjan-Cocody. A voucher specimen (SSC N°1)
was deposited at the Centre National de Floristique.
3.3. Extraction and isolation
Dried and powdered leaves (500 g) of Ziziphus mauritiana were ex-
tracted successively in a Soxhlet with solvents by increasing polarity
Fig. 2. Key COSY (-), key HMBC (- > ) and key ROESY (- > ) correlations of 1.
7

C.S. Seri, et al.
PhytochemistryLetters37(2020)5–9
(CHCl3, MeOH). The MeOH extract (5 g) was separated by a flash
chromatography over silica gel using CHCl3/MeOH/H2O (9:1:0 to
0:0:10, each 3 L) as eluant, to give five fractions (S1-S5). Fraction S3
(82.3 mg) was purified by flash chromatography over RP-18, eluted
with H2O/CH3CN (9:1 to 1:9, in 30 min) to afford three sub-fractions
(A1-A3). The purification by semi-preparative HPLC of sub-fraction A1
(38.6 mg) led to compound 9 (2.2 mg). Fraction S4 (1621.3 mg) was
purified by preparative HPLC over RP-18(12 μm), eluted by a gradient
system of 20–30 % CH3CN in H2O during 60 min, to afford compounds
2 (120.4 mg), 3 (17.2 mg), 5–6 (53.2 mg) and 7 (9.3 mg). Fraction S5
(1588.5 mg) was purified by preparative HPLC over RP-18 (12 μm),
eluted by a gradient system of 20–30 % CH3CN in H2O during 45 min,
to give five sub-fractions (B1-B5). Sub-fraction B4(308.2 mg) was
purified by flash chromatography over silica gel, eluted with CHCl3/
MeOH/H2O (8:2:0 to 14:6:1), to yield three sub-fractions (C1-C3). Sub-
fraction C2(161.2 mg) was purified by a semi-preparative HPLC using a
gradient from 27 to 45% CH3CN in H2O during 10 min, then isocratic
elution at 45 % CH3CN for 20 min to yield 1.2 mg of compound 1 (Rt
29.5 min). Sub-fraction B3(97.2 mg) was submitted to a flash chroma-
tography over silica gel, eluted with CHCl3/MeOH/H2O (7:3:0 to
14:6:1) in 35 min, to afford compound 10 (14.1 mg) and four sub-
fractions (D1-D4). Sub-fraction D3(18.5 mg) was purified by semi-pre-
parative HPLC using a gradient from 27 to 45% CH3CN in H2O during
10 min, then isocratic elution at 45 % CH3CN for 22 min to yield 2.0 mg
of compound 4 (Rt 15.5 min) and 3.7 mg of compound 8(Rt 26.2 min).
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.phytol.2020.03.001.
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An aliquot of ziziphus saponin I (2) (40 mg) containing the same
sugars as compound 1 was refluxed with 5 mL of 2 N TFA for 4 h. After
cooling, the reaction mixture was extracted with EtOAc (3 × 5 mL) to
remove aglycones, and the water-soluble layer was evaporated to dry-
ness (20 mg). Two sugars were identified as glucose, and arabinose by
comparison with authentic samples on TLC over silica gel
(CH3COOEt:CH3COOH:CH3OH:H2O, 65:25:15:15), with a third sugar
similar in Rf to rhamnose attributed to 6-deoxy-talose.The purification
of sugars was achieved by prep. TLC with the same solvent to afford 6-
deoxy-talose [6.4 mg, Rf = 0.73, [α]2d0 -16 (c 0.58, H2O)]; arabinose
[2.8 mg, Rf = 0.59, [α]2d0 +43 (c 0.25, H2O)] and glucose [4.6 mg, Rf
= 0.48, [α]2d0 +21 (c 0.42, H2O)].The absolute configurations of these
sugars were determined as Dfor glucose and L for arabinose and 6-
deoxytalose.
Diallo, D., Rokia, S., Hamsétou, Y., Aminata, T., Kassoum, C., Ababacar, M., 2004. Etude
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Funding
Kumar, R.M., Gayatri, N., Sivasudha, T., Ruckmani, K., 2017. Profiling of bioactive
components present in Ziziphus mauritiana Lam for in vitro antioxidant and in vivo
anti-inflammatory activities. Int. Res. J. Pharm. Pharmacol. 8 (9), 19–24.
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Chardin SERI thanks the Service Cultural Action and Cooperation of
France Ambassy in Côte d’Ivoire for the EGIDE scholarship. The authors
are grateful to the “Service Commun d’Analyses” and “Groupe Chimie
des Substances Naturelles”, to the “Institut de Chimie Moléculaire de
Reims” for spectroscopic and spectrometric analyses, and to the CNF
(Centre National de Floristique) of the Félix Houphouët-Boigny
University, Abidjan-Cocody, Côte d’Ivoire, for the plant identification.
Marwat, S.K., Khan, M.A., Rehman, F.U., Ahmad, M., Zafar, M., Sultana, S., 2009.
Salvadora persica, Tamarix aphylla and Ziziphus mauritiana-three woody plant species
mentioned in Holy Quran and Ahadith and their ethnobotanical uses in north western
part (D.I. Khan) of Pakistan. Pak J. Nutr. 8, 542–547.
Memon, A.A., Memon, N., Luthria, D.L., Pitafi, A.A., Bhanger, M.I., 2012. Phenolic
compounds and seed oil composition of Ziziphus mauritiana L. Fruit. Pol. J. Food Nutr.
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Declaration of Competing Interest
Nawwar, M.A.M., Ishak, M.S., Michael, H.N., Buddrus, J., 1984. Leaf flavonoids of
Ziziphus spina-christi. Phytochemistry 15, 593–597.
Ogawa, K., Kawasaki, A., Omura, M., Yoshida, T., Ikoma, Y., Yano, M., 2001. 3’,5’-di-C-β-
The authors declare no conflict of interest.
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