Phytochemistry Letters 20 (2017) 186–190

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Phytochemistry Letters
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Short communication

Benzofuranylethanoid and phenylethanoid esters from Pteropyrum scoparium MARK

(Jaub. & Spach)
⁎
Zamzam Y.S. Al-I’shaqi, Majekodunmi O. Fatope , Maymoona S.M. Al-Badi, Ruwaya I. Al-Shueili,
Badria Al-Habsi, John Husband
Department of Chemistry, College of Science, Sultan Qaboos University, P.O. Box 36, 123, Al Khod, Muscat, Oman

A R T I C L E I N F O A B S T R A C T

Keywords: Pteropyrum scoparium Jaub. & Spach (Polygonaceae) is a naturally growing shrub used as food crop in Oman. The
Benzofuranylethanoid caproate chemical investigation of the ethyl acetate extracts of the leaf afforded phenylethanoid, benzofuranylethanoid
Phenylethanoid laurate and ethyl esters of caproic and lauric acids (1–3), proanthocyanidin trimer epicatechin-3-O-gallate-(4 → 8)-
Proanthocyanidin epicatechin-3-O-gallate-(4 → 8)-epicatechin-3-O-gallate (4) and epicatechin-3-O-gallate (5). Compounds 1 and 3
Pteropyrum scoparium
are new and isolated for the first time from P. scoparium. The structures of compounds were assigned based on 1D
and 2D NMR spectroscopy and ESI–MS analysis. Compounds 1 and 3 were tested for free radical scavenging anti-
oxidant properties and found to inhibit 2,2′-diphenyl-1-picrylhydrazyl radical (DPPH%) by 1.7% and 41.0%,
respectively compared to 71% and 78% for gallic acid and butylated hydroxyanisole used as control.

1. Introduction incorporating benzofuranylethanoid and phenylethanoid moieties were

Food or beverage crops belonging to families Fabaceae, Vitaceae,
Ericaceae, Rosaceae, Hamamelidaceae, Mimosaceae, Poaceae,
Pinaceae, Rubiaceae, Cannabinaceae, Ebenaceae, Polygonaceae and
Elueagnaceae are rich in oligomeric flavonoids (Monagas et al., 2010;
Nakatsubo et al., 2002; Lea, 1978). When present in fruits, vegetables,
wines and cereals, oligomeric flavonoids impact aroma, astringency,
bitterness (Kallithrata et al., 1997; Gacon et al., 1996), color stability
(Haslam, 1980) and texture to food quality (Aron and Kennedy, 2008;
Prior and Gu, 2005). They often confer therapeutic benefits (Prior and
Gu, 2005; Tourino et al., 2008; Kusano et al., 2011) on consumers and
have found commercial uses as adhesives and tanning agents (Cutting,
1997). We have investigated the leaves of Pteropyrum scoparium Jaub. &
Spach (Polygonaceae) known as “Sidaf” and found known proantho-
cyanidins (Monagas et al., 2010) and new benzofuranylethanoid and
phenylethanoid esters of lauric and caproic acids.
P. scoparium is a regionally endemic desert shrub in Oman
(Ghazanfar, 1991 Ghazanfar and Al-Sabahi, 1993). The fresh leaves
are chewed with dried sprat mixed with onion, lemon and salt or added
to meat in pit cooking. Other naturally growing plants traditionally
eaten in Oman include Aizoon canariense L. (Aizoaceae), Diplotaxis harra
(forssk) Boiss (Brassicaceae), Caralluma quadrangula (forssk) N. E. Br
(Apocynaceae) and Rumex vesicarius L. (Polygonaceae).
In this investigation, new laurate (1) and caproate (3) esters
isolated from edible leaves of the plant together with known ethyl
laurate (2), epicatechin-3-O-gallate-(4 → 8)-epicatechin-3-O-gallate-
(4 → 8)-epicatechin-3-O-gallate (4) and epicatechin-3-O-gallate (5).
Their structures were established from spectral data. Compound 3
showed 2,2′-diphenyl-1-picrylhydrazyl radical (DPPH%) scavenging
activities.
2. Results and discussion
Multiple chromatography of hexane and EtOAc extracts of the
leaves of P. scoparium yielded compounds 1–5 (Fig. 1).
Compound 1 whose molecular formula was established as
C20H32O3 from HR-ESIMS m/z 343.2273 [M+Na]+ (calcd. for
C20H32O3Na 343.2249) was obtained as whitish crystal. The IR
spectrum showed absorption bands at 3311 (broad), 1729, 1465 and
722 cm−1 characteristic of hydroxy, ester and phenyl group, respec-
tively. The 1H and 13C NMR data (Table 1) revealed the presence of one
primary methyl, twelve methylene groups, a di-substituted benzene
ring and one ester carbon. The methyl group resonated at δΗ 0.88 as a
triplet (J = 7.0 Hz). Eight of the methylene groups resonated as over-
lapped multiplets between δ Η 1.20–1.40 corresponding to H-4′–H-11′.
Three other methylene groups were observed as triplets at δ Η 2.28
(J = 7.1 Hz, H-2′), 2.85 (J = 6.7 Hz, H-2) and 4.22 (J = 6.7 Hz, H-1)
and were assigned to the acetoxymethylene, benzylic and oxymethy-

⁎
Corresponding author.
E-mail address: majek@squ.edu.om (M.O. Fatope).

http://dx.doi.org/10.1016/j.phytol.2017.04.030
Received 15 November 2016; Received in revised form 10 April 2017; Accepted 24 April 2017
1874-3900/ © 2017 Phytochemical Society of Europe. Published by Elsevier Ltd. All rights reserved.
Z.Y.S. Al-I’shaqi et al.
Fig. 1. Structures of compounds 1–5.
lene hydrogens. A phenolic hydroxyl group at C-6 was observed as a
broad singlet at δ Η 5.30 in the 1H NMR. The 4-substituted phenyl
group was discerned as an A2X2 coupling system with protons H-4 and
H-8 observed as overlapped signals at δH 6.75 (d, J = 8.7 Hz) and H-5
and H-7 at δH 7.06 (d, J = 8.7 Hz), respectively. Analysis of the HSQC
spectrum showed the oxymethylene, benzylic and acetoxymethylene
protons are bonded to carbons with resonance signals at δ 64.9, 34.4
and 34.3, respectively. The HMBC spectrum showed cross peaks of
signals at δH 4.22 (t, J = 6.7 Hz, H-1) with δC 173.9 (C-1′), 34.4 (C-2)
and 129.9 (C-3), and at δH 2.85 (t, J = 6.7 Hz, H-2) with δC 64.9 (C-1),
129.9 (C-3) and 130.0 (C-4 and C-8), corroborating an ester linkage of
the β-phenylethoxy group to the carbonyl carbon of a C12 fatty acid
(Fig. 2). From these and other spectroscopic data, compound 1 was
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Phytochemistry Letters 20 (2017) 186–190
identified as β-(p-hydroxyphenyl) ethyl laurate (1).
Compound 2 showed similarities in NMR spectral characteristics to
1 except for the replacement of β-(p-hydroxyphenyl)ethoxy signals in
compound 1 with O-CH2-CH3 (Table 2). It was obtained as white
crystals and its molecular formula was established to be C14H28O3. The
oxygenated methylene group signals at δH 4.14 (2H, q, J = 7.1 Hz, H-1)
(δC 60.8) and a primary methyl signal at δH 1.03 (overlapped signal) (δC
14.6) were easily discerned in the NMR spectra. Taken together,
compound 2 was identified as ethyl laurate.
Compound 3 was obtained as brownish powder and showed a
prominent peak at m/z 331.1544 [M+Na]+ (calc. for C17H24O5Na
331.1522) in the HR-ESIMS establishing a molecular formula of
C17H24O5. It showed absorption bands at 3400 (broad), 2916, 1733
Z.Y.S. Al-I’shaqi et al. Phytochemistry Letters 20 (2017) 186–190

Table 1 Table 2
1
H and 13C NMR data (Chloroform-d1 500 MHz for 1
H and 126 MHz for 13
C) for 1
H and 13C NMR data (Chloroform-d1 700 MHz for 1
H and 176 MHz for 13
C) for
Compound 1. Compound 2.

a 1
Position δC δH (multi., J in Hz) H–1H COSY HMBC Position δC
a
δH (multi., J in Hz) 1
H–1H COSY HMBC

1 64.9 CH2 4.22, (t, J = 6.7) H-2 C-3, C-2, C-1′ 1 60.8 CH2 4.14, (q, J = 7.1) H-2 C-2
2 34.4 CH2 2.85, (t, J = 6.7) H-1 C-8, C-4, C-3, C-1′ 2 14.6 CH3 1.03, (overlap) H-1 C-1′, C-1
3 129.9C 1′ 174.3C
4 130.0 CH 7.06, (d, J = 8.3) H-5 C-6, C-5, C-2 2′ 34.8 CH2 2.28, (t, J = 7.5) H-3′ C-3′, C-1′
5 115.3 CH 6.75, (d, J = 8.3) H-4 C-6, C-3 3′ 25.4 CH2 1.61, m H-2′, H-3′ C-2′, C-1′
6 154.3C 4′ 29.5 CH2 1.20–1.40, m
7 115.3 CH 6.75, (d, J = 8.3) H-8 C-6, C-3 5′ 29.7 CH2 1.20–1.40, m
8 130.0 CH 7.06, (d, J = 8.3) H-7 C-6, C-3 6′ 29.8 CH2 1.20–1.40, m
OH 5.30, br s 7′ 30.0 CH2 1.20–1.40, m
1′ 173.9C 8′ 30.0 CH2 1.20–1.40, m
2′ 34.3 CH2 2.28, (t, J = 7.1) H-3′ C-3′, C-1′, 9′ 29.6 CH2 1.20–1.40, m
3′ 24.9 CH2 1.52, m H-2′, H-4′ C-4′, C-2′, C-1′ 10′ 32.3 CH2 1.20–1.40, m
4′ 29.2 CH2 1.20–1.40, m 11′ 23.1 CH2 1.20–1.40, m H-12′, H-10′
5′ 29.3 CH2 1.20–1.40, m 12′ 14.5 CH3 0.88, (t, J = 7.0) H-11′ C-10′, C-11′
6′ 29.5 CH2 1.20–1.40, m
7′ 29.6 CH2 1.2–1.4, m a
Multiplicities inferred from DEPT and HSQC experiment.
8′ 29.7 CH2 1.2–1.40, m
9′ 29.4 CH2 1.20–1.40, m
Table 3
10′ 31.9 CH2 1.20–1.40, m 1
H and 13C NMR data (Chloroform-d1 700 MHz for 1
H and 176 MHz for 13
C) for
11′ 22.7 CH2 1.20–1.40, m H-12′, H-10′
Compound 3.
12′ 14.1 CH3 0.88, (t, J = 7.0) H-11′ C-10′, C-11′
a 1
a Position δC δH (multi., J in Hz) H–1H HMBC
Multiplicities inferred from DEPT and HSQC experiments.
COSY

1 64.5 CH2 4.22, (t, J = 6.7) H-2 C-3, C-2, C-1′

2 34.3 CH2 2.82, (t, J = 6.7) H-1 C-8, C-4, C-3, C-
1
3 131.8C
4 129.0 CH 6.91, (d, J = 1.2) H-8 C-3, C-5
5 146.9C
6 129.1C
7 121.3C
8 140.6 CH 6.92, (d, J = 1.2) H-4 C-2, C-7
9 43.4 CH2 2.74, (dd, J = 13.9, 6.8) H-10 C-11, C-10, C-8
10 90.8 CH 4.85, (br) H-9, H-11
11A 68.3 CH2 4.14, (ddd, J = 8.6, 3.0, H11B, H-10
2.8)
11B 4.27, (ddd, J = 9.3, 5.8, H-11A, H-
2.4) 10
OH 5.8, br s
1′ 174.1C
2′ 34.7 CH2 2.28, (t, J = 7.1) H-3′ C-4′, C-3′, C-1′
3′ 25.4 CH2 1.62, m H-2′, H-4′ C-4′, C-2′, C-1′
4′ 32.3 CH2 1.20-1.35, m
5′ 23.1 CH2 1.20-1.35, m H-4′, H-6′
6′ 14.5 CH3 0.87, (t, J = 7.0) H-5′ C-5′. C-4′

a
Multiplicities inferred from DEPT and HSQC experiments.

DEPT spectra displayed 17 carbon resonances (Table 3) attributable to

Fig. 2. 1H–1H COSY and HMBC correlations of compounds 1 and 3.
5 quaternary carbons (including one ester carbon), 8 methylenes (two
of which are oxygenated), one oxymethine and one methyl group. The
HMBC spectrum showed cross peaks from meta-coupled aromatic
and 1571 in the IR attributed to hydroxyl, ester and aromatic groups.
protons at δH 6.92 and 6.91 to δC 131.8 (C-3), 146.9 (C-5), 121.3 (C-
The 1H NMR gave signals for one primary methyl group at δH 0.87 (t,
7) and 34.3 (C-2) which supported structural isomer 3 (Fig. 3).
J = 7.0 Hz, H-6′) and six methylene groups at δH 1.20–1.35 (m, H-4′
Additional prominent HBMC interactions from δH 2.78 (d, J = 7.1, H-
and H-5′), 1.62 (m, H-3′), 2.28 (t, J = 7.1 Hz, H-2′); 2.74 (dd, J = 13.9,
9) and 4.85 (overlapped, H-10) to δC 140.6 (C-8), 90.8 (C-10), 68.3 (C-
6.8 Hz, H-9) and 2.82 (t, J = 6.7 Hz, H-2). It showed oxymethylene
11) and from δH 4.22 (t, J = 6.7 Hz, H-1) to δC 174.1 (C-1′) and 34.3
protons at δH 4.14 (ddd, J = 8.6, 3.0, 2.8 Hz, H-11A), 4.27 (ddd,
(C-2) further corroborated structure 3.
J = 9.3, 5.8, 2.4 Hz, H-11B) and 4.22 (t, J = 6.7 Hz, H2-1). The 1H
The β-phenylethanoid substructure in compounds 1 and 3 is likely
NMR further displayed resonances for one oxymethine proton at δH
derived from tyrosine via the shikimate pathway. Hydroxylation of the
4.85 (br, H-10), two AB-type aromatic protons with meta coupling at δH
β-(p-hydroxyphenyl)ethanoid precursor of compound 1 can give 2,4-
6.92 and 6.91 (d, J = 1.2 Hz, H-4 and H-8) and one phenolic hydroxyl
dihydroxyphenylethanoid which may sequentially undergo prenyla-
at δH 5.8 (Table 3). The HSQC spectrum showed H2-9 in contrast to H2-
tion, cyclization and decarboxylation reactions to build up the 3, 4, 5
11 to be isochronous. The H2-11 protons resonated as a diastereotopic
tri-substituted β-phenylethanoid pattern observed in compound 3. Four
pair with different chemical shifts. Their splitting pattern showed that
structural isomers of benzofuranylethanoid substructure (Fig. 3) can
they are coupled to H-10 and the hydroxyl proton at C-11. The presence
have meta-coupled protons. Structural isomer 3 was adopted based on
of meta-coupled protons in the 1H NMR spectrum is consistent with the
HSQC and HMBC data, biosynthetic considerations (Petersen et al.,
assigned 3, 4, 5-tri-substituted phenyl group in compound 3. The 13C
2010) and theoretical calculations. For the theoretical calculations,

188
Z.Y.S. Al-I’shaqi et al.
Fig. 3. Structural isomers of tri-substituted phenyl group.
DFT-predicted chemical shifts for compounds 3 and 3a–c were directly
compared with experimental data reported in Table 3. Correlation (Fig.
S10) between 13C experimental and predicted chemical shifts was best
(R2 = 0.9725) for compound 3.
Compound 4 was obtained as a white solid and tentatively
identified as proanthocyanidin trimer epicatechin-3-O-gallate-(4 → 8)-
epicatechin-3-O-gallate-(4 → 8)-epicatechin-3-O-gallate. HR-ESIMS
data showed molecular ion peak at m/z 1347.9045 [M+Na+2H]+
(calcd. for C66H52O30Na, 1347.2445) and established molecular for-
mula C66H52O30 for compound 4. The structure of 4 was corroborated
by equation 290 + 288c + 152 g + 23 (developed for structural elu-
cidation of proanthocyanidin oligomers) where 290 is the terminal
epicatechin unit, c is the degree of polymerization of the epicatechin
units, g is the number of galloyl esters, and 23 is the atomic mass of
sodium (Ricardo-Da Silva et al., 1992). Compound 5 was elucidated as
epicatechin-3-O-gallate by comparison of its NMR data with literature
value (Adrienne et al., 1996).
Compounds 1 and 3 were tested for antioxidant activity using DPPH
radical scavenging procedure (Chen et al., 1999). Compound 3
inhibited DPPH radical by 1.7% and 41.0%, respectively compared to
71% and 78% for gallic acid and butylated hydroxyanisole used as
control.
In conclusion, our investigation resulted in the isolation of new
benzofuranylethanoid and phenylethanoid esters from edible leaves of
P. scoparium. The structures of the compounds were assigned from
spectral analysis. This work reports for the first time phenylethanoid,
benzofuranylethanoid and ethyl esters of caproic and lauric acids from
this plant which might have astringency, flavor and antioxidant
potentials.
3. Experimental
3.1. General experimental procedures
IR spectra were obtained with a Nicolet FT-IR spectrometer. 1H and
13
C NMR spectra were recorded in chloroform-d1 with Bruker Advance
NMR spectrometer operating at 500 MHz for 1H and 126 for 13C or
700 MHz for 1H and 176 MHz for 13C) with TMS as internal standard.
ESIMS was recorded on Quattro Ultima Platinum Tandem quadrupole
mass spectrometer (Micromass UK). HR-ESIMS data was acquired on
Waters™ Xevo Q-time of flight instrument after pre-calibration with
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Phytochemistry Letters 20 (2017) 186–190
sodium iodide. For chromatography, EM Science Silica gel 60
(70–230 mesh ASTM) was used. Whatman precoated silica gel (60A
K6F) plates were used for TLC, with compounds visualized by UV lamp
and spraying with 10% (v/v) H2SO4 or vanilline-H2SO4 followed by
heating.
3.2. Plant material
Pteropyrum scoparium was collected from Siha Altaibat in Saham at
altitude 618 m in Oman in September 2014 and a voucher specimen is
kept in the Herbarium of the Department of Biological Sciences, Sultan
Qaboos University, Oman.
3.3. Extraction and isolation
The leaves of P. scoparium (2.0 kg) were extracted with hexane
(2 × 6 L) and EtOAc (2 × 6 L) by maceration at rt for one week each,
and concentrated under vacuum at 40 °C to give 5.30 g of hexane and
7.80 g of EtOAc extracts, respectively. The EtOAc extract was fractio-
nated between 10% aq. MeOH and hexane to give MeOH (2.33 g) and
hexane (2.41 g) soluble residues, respectively. Column chromatography
of a portion of the aqueous MeOH soluble fraction (1.83 g) on (140 g
silica gel), using gradient mixtures of hexane – CHCl3, CHCl3 – Me2CO
and CHCl3-EtOH as eluent, gave fractions from which compounds 1–5
were isolated. Fractions eluted with chloroform gave compound 1
(0.36 g, 80–82 °C) as white crystals and also some brownish white
powdery fractions which were combined (0.7111 g). The combined
fractions were further chromatographed on SiO2 (50 g, 2 × 33 cm),
eluting with gradients of hexane-CHCl3 mixtures, and collecting frac-
tions in 100 mL portions to afford compounds 2 (43.4 mg) white
crystals, mp 74–76 °C, and 3 (23.2 mg) brown powder, mp 76–78 °C.
The fractions eluted with CHCl3- Me2CO (7:3) gave compound 5
(24.9 mg) identified as epicatechin-3-O-gallate, and those eluted with
CHCl3-EtOH (8:2) gave compound 4 (2.9 mg) identified as epicatechin-
3-O-gallate-(4 → 8)-epicatechin-3-O-gallate-(4 → 8)-epicatechin-3-O-
gallate based on HR-ESIMS data.
3.3.1. Compound (1)
White solid; mp 80–82 °C; IR υ max 3311 (broad), 2919, 2851, 1729,
1465, 722 cm−1; 1H NMR and 13C NMR, see Table 1; ESI–MS m/z
343.2273 [M+Na]+ (calcd. for C20H32O3Na 343.2249).
3.3.2. Compound (2)
White solid; mp 74–76 °C; IR υ max 2913, 2845, 1735, 1457, 1368,
1200, 1025 cm−1; 1H NMR and 13C NMR, see Table 2.
3.3.3. Compound (3)
Brown solid 76–78 °C; IR υ max 3400, 2916, 2848, 1733, 1571, 1461,
1243, 1163, 971, 794, 718 cm−1; 1H NMR and 13C NMR see Table 3
ESI–MS m/z 331.1544 [M+Na]+ (calc. for C17H24O5Na 331.1522)
3.4. Theoretical calculation
Density functional theory (DFT) was used to predict NMR chemical
shifts for compounds 3 and its structural isomers 3a–c. Structures were
optimized using Gaussian (G03W) software (Frisch et al., 2004) at the
B3LYP/6-31G (d) (gas −phase) level of theory, and isotropic shielding
constants calculated at the B3LYP/6-31 + G (d,p) level using the GIAO
method. The CPCM implicit solvent model was used in the NMR
calculation. Shielding constants were converted to chemical shift values
using the empirical scaling factors recommended by Tantillo and
coworkers (Lodewyk et al., 2012).
Acknowledgment
This work was supported by SQU through financial assistance to
Z.Y.S. Al-I’shaqi et al.
MOF (Grant IG/SCI/CHEM/11/02).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.phytol.2017.04.030.
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