Investigation of monomeric and oligomeric wine stilbenoids in red wines by ultra-high-performance liquid chromatography/electrospray ionization quadrupole time-of-flight mass spectrometry

Article abstract of DOI:10.1002/rcm.6636

RATIONALE Stilbenoids are secondary plant metabolites responsible for the protection of multiple plant species including grape vine from bacterial and fungal infection. Red wine has been shown to be a major source of these compounds in the human diet, where they display an array of health benefits. Providing a more complete profile of the stilbenoids present in red wine, this study detects 41 stilbenoid compounds, 23 of which have never before been detected in red wine. METHODS Red wine extracts were scanned using an ultra-high-performance liquid chromatograph coupled to a hybrid quadrupole time-of-flight mass analyzer. Multiple targeted MS/MS precursor ion scan experiments were performed using electrospray ionization operated in negative mode. Precursor ion masses were scanned for the monomeric and oligomeric stilbenoids, as well as modifications such as O-glycosylation, methoxylation and oxidation products of these compounds. Accurate mass precursor and characteristic product ions afforded partial structural elucidation and assignment of these compounds. RESULTS A total of 41 (both known and novel) stilbenoids were detected in extracted red wine. In addition to the well-known monomeric stilbenes, several resveratrol-resveratrol homodimers (m/z 453.1344), resveratrol-piceatannol heterodimers (m/z 469.1293) and piceatannol-piceatannol homodimers (m/z 485.1236) were detected. Modified dimers of resveratrol including O-glycosylated (m/z 615.1872), methoxylated (m/z 485.1606) and oxidized (m/z 471.1449) dimers were also detected. Multiple trimers of resveratrol (m/z 679.1978) were detected for the first time in red wine, as well as some known and some novel stilbenoid tetramers (m/z 905.2604). CONCLUSIONS In summary, 41 stilbenoids were detected in red wine, 23 for the first time. Both monomeric and oligomeric stilbenoids were partially identified and assigned by their accurate mass precursor ions and characteristic stilbenoid fragmentation patterns. Knowledge gained from these experiments contributes to a more complete understanding of the origin of the beneficial properties of red wine. Copyright

Full text of DOI:10.1002/rcm.6636

Research Article
Received: 27 March 2013
Revised: 16 May 2013
Accepted: 23 May 2013
Published online in Wiley Online Library
Rapid Commun. Mass Spectrom. 2013, 27, 1815–1827
wileyonlinelibrary.com) DOI: 10.1002/rcm.6636
(
Investigation of monomeric and oligomeric wine stilbenoids in red
wines by ultra-high-performance liquid chromatography/electrospray
ionization quadrupole time-of-flight mass spectrometry
Ryan Moss , Qinyong Mao , Dennis Taylor and Cédric Saucier1,2*
1
2
1,2
1
Department of Chemistry, The Irving K. Barber School of Arts & Sciences, The University of British Columbia, Okanagan
Campus FIP 357, 3333 University Way, Kelowna, BC, Canada, V1V 1 V7
2
The University of Adelaide, School of Agriculture, Food and Wine, Waite Campus, Private Mail Bag 1, Glen Osmond, South
Australia 5064, Australia
RATIONALE: Stilbenoids are secondary plant metabolites responsible for the protection of multiple plant species including
grape vine from bacterial and fungal infection. Red wine has been shown to be a major source of these compounds in the
human diet, where they display an array of health benefits. Providing a more complete profile of the stilbenoids present in
red wine, this study detects 41 stilbenoid compounds, 23 of which have never before been detected in red wine.
METHODS: Red wine extracts were scanned using an ultra-high-performance liquid chromatograph coupled to a
hybrid quadrupole time-of-flight mass analyzer. Multiple targeted MS/MS precursor ion scan experiments were
performed using electrospray ionization operated in negative mode. Precursor ion masses were scanned for the
monomeric and oligomeric stilbenoids, as well as modifications such as O-glycosylation, methoxylation and oxidation
products of these compounds. Accurate mass precursor and characteristic product ions afforded partial structural
elucidation and assignment of these compounds.
RESULTS: A total of 41 (both known and novel) stilbenoids were detected in extracted red wine. In addition to the well-known
monomeric stilbenes, several resveratrol-resveratrol homodimers (m/z 453.1344), resveratrol-piceatannol heterodimers
(
m/z 469.1293) and piceatannol-piceatannol homodimers (m/z 485.1236) were detected. Modified dimers of resveratrol
including O-glycosylated (m/z 615.1872), methoxylated (m/z 485.1606) and oxidized (m/z 471.1449) dimers were also detected.
Multiple trimers of resveratrol (m/z 679.1978) were detected for the first time in red wine, as well as some known and some
novel stilbenoid tetramers (m/z 905.2604).
CONCLUSIONS: In summary, 41 stilbenoids were detected in red wine, 23 for the first time. Both monomeric and
oligomeric stilbenoids were partially identified and assigned by their accurate mass precursor ions and characteristic
stilbenoid fragmentation patterns. Knowledge gained from these experiments contributes to a more complete
understanding of the origin of the beneficial properties of red wine. Copyright © 2013 John Wiley & Sons, Ltd.
Stilbenoids are a class of non-flavanoid polyphenolic
compounds abundant in several families of plants families
including Vitaceae. Within Vitis vinifera, stilbenoids are often
referred to as phytoalexins, compounds that can act as
antifungal agents to ward off infection. Because these
metabolites are present in multiple constituents of the
grapevine, including the stems, leaves and berries, they are
regularly transferred into wine during maceration and time
Many studies on wine have focused on the monomeric
stilbenoids, such as resveratrol, piceatannol, and their glycosides,
[4–6]
piceid and astringin.
While these compounds are the most
abundant stilbenes found in wine, they do not represent the full
range of stilbenoids that can be present in a wine. More recently,
oligomeric products of resveratrol such as ϵ-viniferin, δ-viniferin,
and pallidol have been reported using UV, fluorescence and
[7–10]
mass spectrometry detection methods.
However, some
[
1]
on solids. This makes wine a very interesting focus for
stilbenoid screening as it is known to be a substantial source
studies have shown that a much larger range of stilbenoids can
[11]
be found within the Vitis genus than just these compounds.
[2]
of these compounds in the human diet. Not only are
stilbenoids known for their role as protective phytochemicals,
but they have also been the popularized by the reported
health benefits of resveratrol, a stilbenoid, including cardio-
High-performance liquid chromatography coupled with
mass spectrometry (HPLC/MS) can allow for the separation,
detection, and partial identification of trace amounts of natural
products within complex samples. Multiple studies have used
HPLC/tandem mass spectrometry (MS/MS) to detect
[3]
protective, antioxidant, and anti-carcinogenic effects.
[12–14]
stilbenoids in plant and wine extractions.
Although full
identification of unknown compounds is only possible
through comparison with authentic standards, or isolation
and determination by nuclear magnetic resonance (NMR)
spectroscopy, it is possible to partially identify them through
accurate mass fragmentation patterns.
*
Correspondence to: C. Saucier, Department of Chemistry, The
Irving K. Barber School of Arts & Sciences. The University
of British Columbia, Okanagan Campus FIP 357, 3333
University Way, Kelowna, BC, Canada V1V 1 V7.
E-mail: cedric.saucier@ubc.ca
Rapid Commun. Mass Spectrom. 2013, 27, 1815–1827
Copyright © 2013 John Wiley & Sons, Ltd.

R. Moss et al.
In the present study, red wine was screened by selecting
the precursor ion masses of potential stilbenoids and their
derivatives to gain a profile of which oligomers were
present. The partial identification of compounds was
facilitated by electrospray ionization quadrupole-time-
of-flight (QTOF) tandem mass spectrometry, which can
provide MS/MS fragmentation along with precursor and
product ion masses with low parts-per-million accuracy.
Using characteristic stilbenoid fragmentations, 41 stilbenoid
oligomers were partially identified in red wine. This
included 23 stilbenoids not previously identified in wine.
For structures, see Fig. 1.
were Okanagan Valley (VQA, Okanagan Valley) 2010 pinot
noir, merlot and cabernet sauvignon, sampled in August
2011, and stored at –20 °C before extraction.
Synthesis of authentic standards of (± ±-trans-ϵ-viniferin,
(± ±-trans-δ-viniferin and (± ±-pallidol
The synthesis of trans-ϵ-viniferin (13), trans-δ-viniferin (16)
and pallidol (7) was achieved by employing a modified
[15]
procedure to that reported by Takaya et al.
As we wished
not to have to purify by preparative HPLC as described by
Takaya et al., coupled with the fact that we wished to
synthesize large quantities of these dimers, we devised a
simple purification procedure that relied upon acetylation
prior to purification. Thus, to a stirred solution of trans-
EXPERIMENTAL
resveratrol (1) (500 mg) and K
120 mL) at room temperature was slowly added an aqueous
solution (10 mL) of K Fe(CN) (575 mg) over 5 min and the
2 3
CO (245 mg) in MeOH
(
Reagents and samples
3
6
Deionized water was purified with a MilliQ water system
mixture was stirred for a further 30 min. The mixture was
then concentrated in vacuo and loaded directly onto a flash
chromatography column and the organics eluted with ethyl
acetate. The fraction containing the crude dimers was then
concentrated in vacuo and then dissolved in CH Cl (60 mL)
(
Millipore, Bedford, MA, USA). HPLC grade acetonitrile
and diethyl ether were purchased from Fisher Scientific
Waltham, MA, USA). Formic acid was purchased from
Sigma Aldrich (St. Louis, MO, USA). The red wines used
(
2
2
Figure 1. Tentative structures of the major compounds found in red wine extracts studied. 1, 2 trans- and cis-resveratrol, 3 trans-
piceatannol, 4, 5 trans- and cis-piceid, 6 trans-astringin, 7 pallidol, 8 parthenocissin A, 9 quadrangularin A, 10 ampelopsin D,
1
1, 13 cis- and trans-ϵ-viniferin, 12, 14 cis- and trans-ω-viniferin, 16, 17 trans- and cis-δ-viniferin, 19, 20 trans- and cis-scirpusin A,
1 restrisol A or B, 25 scirpusin B, 26, 27 parthenostilbenin A and B, 28 ϵ-viniferin glucoside, 30 ampelopsin C, 31, 32 E- and
2
Z-miyabenol C, 39 hopeaphenol, 41 isohopeaphenol.
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Study of wine stilbenoids in red wines by UPLC/ESI-QTOFMS
and DMSO (10 mL). Ac O (0.83 mL) and Et N (1.23 mL) were
2
3
UHPLC/ESI-MS/MS
then added and the reaction mixture kept at ambient
temperature for 24 h. The reaction was then quenched with
For separation, an Agilent 1290 series UHPLC system
(
Agilent Technologies, Santa Clara, CA, USA) equipped with
NaHCO (30 mL) and the organics extracted with EtOAc
3
binary pump, solvent degasser, thermostatted column
compartment and a diode-array detector (DAD) was used.
The column used for separation was a reversed-phase Zorbax
SB AQ (2.1 × 150 mm + 2.1 × 100 mm in series, 1.8 μm; Agilent
Technologies, Santa Clara, CA, USA). The mobile phase
consisted of A: water (0.1% formic acid) and B: acetonitrile
(
(
3 × 30 mL). The combined organics were washed with water
20 mL), dried (MgSO ) and the volatiles were removed
4
in vacuo. The acetates were then separated by simple column
chromatography (increasing polarity from 20% to 50% ethyl
acetate in petroleum spirit) to afford trans-ϵ-viniferin
pentaacetate and trans-δ-viniferin pentaacetate (120 mg, 1:2)
and pallidol hexaacetate (150 mg). The two viniferin acetates
were further separated by simple recrystallization (MeOH) at
ambient temperature to furnish pure trans-δ-viniferin
pentaacetate (50 mg). The mother liquors were then placed
at –20 °C resulting in the precipitation of a mixture of
trans-δ- and trans-ϵ-viniferin pentaacetates (45 mg). The mother
liquors were then evaporated to afford pure trans-ϵ-viniferin
pentaacetate (20 mg). Both the pallidol hexaacetate and the
trans-ϵ-viniferin pentaacetate had spectral data identical to
(
0.1% formic acid). The 50 min elution method was 10–18%
B over 5 min. A linear gradient was used from 18–40%B over
the next 40 min, followed by an increase from 40–100%B in
1
min. A plateau at 100%B for 2 min followed by a decrease
from 100–10%B over 1 min was used to clean the column. A
-min post-run isocratic step at 10%B was used to re-
3
equilibrate the column for the next analysis. The flow rate
was held constant at 0.35 mL/min at 40 °C.
[16,17]
those previously reported.
MS/MS
Deacetylation of the dimers was achieved by dissolving
each dimer (20 mg) in MeOH (10 mL) and water
MS/MS experiments were performed using the Agilent
UHPLC system described above coupled to an Agilent 6530
Series accurate mass QTOF tandem mass spectrometer
(
20 mL), followed by the addition of K
reaction mixture was kept at ambient temperature for
4 h, after which time it was neutralized with diluted
2 3
CO (30 mg). The
(
(
Agilent Technologies) operated in high mass resolution
4 GHz) mode. An electrospray ionization source in
2
HCl. The product was extracted with EtOAc (3 × 20 mL)
and the combined extracts washed with water (20 mL),
dried (MgSO ) and the volatiles were removed in vacuo.
4
negative ion mode equipped with Agilent Jet Stream
technology was used for ionization. Agilent MassHunter
5
.0 software was used for both data acquisition and analysis.
The crude product was then subjected to chromatography
employing ethyl acetate in petroleum spirit (7:1) as eluent
to furnish the target dimers in yields >90%. The proton
and carbon NMR spectra of the three dimers were in
accordance with those reported in the literature,
Nitrogen was used both as the drying and collision gas. The
nebulizer had a pressure of 25 psig with a drying gas flow
–
1
and temperature of 10 L.min and 325 °C, respectively. The
nitrogen sheath gas had a temperature of 400 °C and a flow
–
1
[
16]
[17–19]
[20–22]
rate of 12 L.min .
pallidol,
trans-ϵ-viniferin,
trans-δ-viniferin.
To optimize the fragmentor and capillary voltages for the
best possible ionization of these compounds, a preliminary
acquisition in simple MS mode was used. The fragmentor
and capillary voltages were fixed at 200 V and 2.25 kV,
respectively. A targeted MS/MS acquisition was used
Synthesis of authentic standards of (± ±-cis-ϵ-viniferin and
± ±-cis-δ-viniferin
(
(m/z 50–1200) with a fixed isolation peak width (1.3 m/z units)
and collision energy (CE) across all compounds initially. The
CE was then varied between 10 and 50 eV and optimal CE
values were chosen for each class of compounds to obtain
the most characteristic fragments (Table 1).
The synthesis of cis-ϵ-viniferin (11) and cis-δ-viniferin (17)
was achieved by employing a modified procedure to that
[
18]
reported by Yao et al.
Thus, the trans-viniferin (13 or 16,
5
–10 mg) was dissolved in d -MeOH (2 mL) and the solution
4
subjected to UV irradiation (365 nm) for 1 h. After this time a
steady state of the trans/cis dimers had been reached and
1
established by HNMR to be (1:1, trans/cis ϵ-viniferin) and
(
RESULTS AND DISCUSSION
1:3, trans/cis-δ-viniferin). The proton and carbon NMR
spectra of the cis isomers were in accordance with those
Three red wine extracts were analyzed to obtain their
stilbenoid profiles. In the initial targeted product ion scan
experiment, 41 potential compounds (shown in Table 1)
exhibiting characteristic neutral losses were isolated. To our
knowledge, 26 of these possible oligomeric stilbenes have
not yet been identified in wine.
[
18]
[21]
reported in the literature, cis-ϵ-viniferin,
cis-δ-viniferin.
It was further noted that the cis isomers isomerize back to
the trans isomers at ambient temperature over time and as
such the samples should be stored in solution at low
temperature in the dark.
The dimeric forms of resveratrol that have been previously
reported in wine include cis-ϵ-viniferin, trans-ϵ-viniferin,
cis-δ-viniferin, trans-δ-viniferin, pallidol, parthenocissen A,
Sample preparation
[
7,23,33]
Each red wine (100 mL) was extracted with diethyl ether
and quadrangularin A.
In the present study,
(
3 × 100 mL). The solvent was evaporated under vacuum at
compounds 7, 11, 13, 16, and 17 have been unambiguously
identified as pallidol, cis-ϵ-viniferin, trans-ϵ-viniferin,
trans-δ-viniferin, and cis-δ-viniferin, respectively, by comparison
with authentic standard compounds. Parthenocissen A and
room temperature and re-suspended in 1 mL of MeOH to
afford a concentrated red wine extract. The sample was kept
at 4 °C until analysis by UHPLC/ESI-QTOFMS.
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R. Moss et al.
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Study of wine stilbenoids in red wines by UPLC/ESI-QTOFMS
Rapid Commun. Mass Spectrom. 2013, 27, 1815–1827
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R. Moss et al.
–
quadrangularin A have been tentatively identified by
comparison with accurate mass fragmentation patterns from
the literature.
for trans-piceatannol (3) with an [M–H] ion at m/z 243,
which yielded fragments at m/z 201 and 159 from the
2 2
subsequent losses of C H O (42 Da) as above. Piceatannol
In addition to the homodimers of resveratrol, several
derivatives have been identified in various plants. These include
O-glycosylated dimers, methoxylated dimers, piceatannol-
resveratrol heterodimers, piceatannol homodimers, and even
was also confirmed by retention time and fragmentation
pattern through comparison with a pure standard.
Glycosylated monomers
[11]
additional oxidation products of these dimers. Although some
Piceid and astringin are the O-glycosides of resveratrol and
piceatannol, respectively. The identities of compounds 4 and
of these compounds such as pallidol-3-O-glycoside (29) and
[24]
ϵ-viniferin-glycoside (28) have been isolated in white wine, we
5
were confirmed as trans- and cis-piceid by the detection of
report ten dimers that have not yet been reported in wine but have
–
[25]
an [M–H] ion at m/z 389. In the MS/MS spectra of 4 and 5,
only one strong product ion at m/z 227 corresponding to the
loss of glucose (162 Da) was observed. Compound 6
displayed a low intensity signal that corresponded with both
retention time and fragmentation of trans-astringin, the
glycoside of piceatannol. The loss of glucose (162 Da)
resulting in an ion at m/z 243 was the only fragment visible
been described in cell cultures of Vitis vinifera. Many of these
stilbenoid dimer derivatives have also been identified in other
[26]
plant species as well as in the leaves and stems of Vitis vinifera.
The stilbenoid trimers and tetramers are also well
represented in many different species of plants, including
[
11]
Vitis vinifera.
Although trimeric and tetrameric stilbenoids
have been detected in the leaves and stems of grapevine, only
À
[10]
in the MS/MS spectrum of compound 6 with a [MÀH] ion
the tetramer hopeaphenol (39) has been identified in wine.
at m/z 405. Reference standards for cis/trans-piceid and trans-
astringin corresponded to compounds 4, 5, and 6, respectively.
In this study, eight potential trimers (30–37) and four
potential tetramers (38–41) have been found, displaying
similar fragmentation patterns to stilbenoid oligomers in the
literature. All precursor and product ion masses are
supported by accurate mass measurements with mass error
below 10 ppm.
Dimers (R + R±
Two structurally separate groups of resveratrol dimers exist
in nature. The 'viniferins' possess a 2,3-dihydrobenzofuran
ring system where a major product ion of m/z 347 is
observed,. The second group are typified by an indane ring
system which produces a highly abundant ion at m/z 359, such
Monomers
Monomeric stilbenes are the most abundant stilbenoids
found in wine. These were characterized by both MS/MS
fragmentation patterns and retention times as compared with
authentic standards. Compounds 1 and 2 were a pair of
[11]
as pallidol. A product ion scan of m/z 453.1344 was acquired
in order to detect 11 homodimers of resveratrol numbered 7–17
(Fig. 4). The structural identifications of stilbenoid oligomers
were based on the presence of characteristic product ions that
–
cis/trans isomers with an [M–H] ion at m/z 227, which
corresponded to deprotonated resveratrol (Fig. 2). The
MS/MS spectra of these two compounds were identical,
producing two product ions at m/z 187 and 143, which
originate from the neutral losses of 42 Da (C
(C O), 106 Da (C O) and 110 (C ).
In the MS/MS spectrum of compound 7, the [M–H] ion of
2
H
2
O), 94 Da
H
6 6
H
7 6
6 6 2
H O
–
were derived from the loss of one and two C
moieties, respectively. The loss of C O from the resorcinol
ring is characteristic of resveratrol and most other stilbenoids
2
H
2
O (42 Da)
m/z 453 produces two main product ions. The most abundant
–
H
2 2
ion at m/z 359 of composition
C
22
H
15
O
5
(measured
m/z 359.0933, error 2.23 ppm) is generated from the loss of a
[
27]
(Fig. 3).
The presence of cis- and trans-resveratrol was
single phenol group (94 Da). The loss of a second phenol
–
4
confirmed by comparison of retention times of pure
group (94 Da) produces C16
H
9
O
with m/z 265 (measured
standards. A similar fragmentation pattern was observed
265.0515, error 3.40 ppm). The identity of compound 7 is
Figure 2. Combined base peak chromatogram of m/z 227.0714, 243.0663, 389.1242, and 405.1191
showing compounds 1–6.
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Study of wine stilbenoids in red wines by UPLC/ESI-QTOFMS
Figure 3. Fragmentation pathway of the stilbene monomers (1, 2, and 3) and their
glycosylated analogues (4, 5, and 6).
pallidol, a well-known symmetrical resveratrol dimer. The
retention time and fragmentation pattern of a pure reference
standard matched that observed for compound 7 (Fig. 4).
The three compounds 8, 9 and 10 displayed identical
MS/MS spectra, which can be indicative of a set of structural
isomers. Two high-abundance product ions originated from
therefore proposed that two of these three compounds are the
cis/trans isomers, quadrangularin A and parthenocissin A, and
the other is the regioisomer, ampelopsin D, that was isolated
[26,33]
from grapevine leaves.
Compounds 11 and 13 are cis/trans isomers of cis/trans-ϵ-
viniferin confirmed by their indistinguishable MS/MS spectra.
–
À
the [M–H] ion at m/z 453. An ion formed from the loss of
A [MÀH] ion of m/z 453 formed multiple product ions at 435,
–
5
phenol (94 Da) at m/z of 359 (C22
H
15
O
, measured 359.0907,
411, 369, 359, 347, and 333. This was in contrast to the indane-type
dimers discussed above, which produced few highly abundant
error –4.19 ppm). Further sequential losses of CO (28 Da)
–
3
and C
measured 289.0867, error 1.04 ppm). Minor ions at m/z 247,
21, and 205 of abundances less than 1% were observed that
could correspond to the losses of C O (42 Da), C (68 Da),
and two C O (84 Da), respectively, from the ion m/z 289. These
2
H
2
O (42 Da) produced an ion at m/z 289 (C19
H
13
O
,
product ions. Losses of H
O (84 Da), phenol (94 Da), 4-methylenecyclohexa-2,
5-dienone (106 Da), and C O (120 Da) were supported by
2 2 2
O (18 Da), C H O (42 Da), two
2 2
C H
2
8 8
H
–
2
H
2
3 2
O
accurate mass product ions of
m/z 435.1237, error 0.23 ppm),
C
C
28
H
H
19
O
19
5
(measured
(measured
–
2
H
2
26
O
5
3
–
4
low-abundance ions have been isolated in the MS spectrum of
m/z 411.1257, error 4.62 ppm), C24
H
17
O
(measured m/z 369.1126,
–
the ion at m/z 289 in two compounds which are cis/trans isomers
error 1.63 ppm), C H O (measured m/z 359.0927, error
22
15 5
[28]
–
that have been isolated in Parthenocissus laetevirens.
It is
0.56 ppm), C H O (measured m/z 347.0936, error 3.17 ppm),
21 15 5
Figure 4. (A) BPC scan of m/z 453.1344 showing compounds 7–17. (B) MS/MS BPC showing the transition
m/z 453.1344 → 359.0925 displaying the indane-type resveratrol dimers 7–10. (C) MS/MS BPC of the
transition m/z 453.1344 → 411.1238 highlighting the 'viniferin'-type dimers 11–17.
Rapid Commun. Mass Spectrom. 2013, 27, 1815–1827
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R. Moss et al.
–
5
13
and C20H O
(measured m/z 333.0774, error 1.5 ppm),
Dimers (R + P)
respectively. The proposed fragmentation pattern for ϵ-viniferin
is displayed in Fig. 5. In addition to cis/trans-ϵ-viniferin, the
compounds 12, 14, and 15 also share this exact fragmentation
pattern. Two compounds, cis- and trans-ω-viniferin, isolated in
grapevine leaves infected with Plasmopara viticola have a near
identical structure to ϵ-viniferin differing only in the
The MS spectra of compound 18 had a molecular ion at m/z 469
which could correspond to a resveratrol-piceatannol heterodimer
(
Fig. 6). The ion at m/z 469 produced four characteristic fragments
in the MS/MS spectrum at m/z 451, 385, 375, and 359 which were
generated from the losses of H O (18 Da), two C O (84 Da),
2
2 2
H
[
26,33]
phenol (94 Da), and resorcinol (110 Da), respectively. The identities
of these fragments were again supported by accurate mass
stereochemistry of the H7a and H8a chiral centers (Fig. 1).
For this reason, the fragmentation pattern of these
compounds would be indistinguishable from ϵ-viniferin
and it is therefore proposed that the identity of two of 12,
–
measurements of C H O (measured m/z 451.1187, error
0
28
19
6
–
.67 ppm), C H O (measured m/z 385.1082, error 0.36 ppm),
24 17 5
–
C H O (measured m/z 375.0899, error 6.67 ppm), and
2
2
15
6
1
4, or 15 correspond to cis/trans-ω-viniferin.
Compounds 16 and 17 have an [M–H] ion at m/z 453 indicating
–
–
C
22
H
O
15
5
(measured 359.0918, error 1.95 ppm). Compounds 19
–
and 20 provide identical MS/MS spectra from the [M–H] ion of
m/z 469, including the ions at m/z 451, 385, 375, and 359.
Compounds 19 and 20 differ from 18 as they display an ion at
m/z 241 rather than m/z 265. This could indicate that these
compounds are structural isomers depending on which section
of the dimer originates from piceatannol or resveratrol as the ion
a resveratrol dimer. The MS/MS spectra for these compounds are
similar to that of ϵ-viniferin with losses of H O (18 Da), C
42 Da), C (68 Da), two C O (84 Da), and phenol (94 Da),
2
2 2
H O
(
3
O
2
2 2
H
which produce ions at m/z 435, 411, 385, 369, and 359, respectively.
–
Accurate mass measurements support the identity of C H O
28
19
5
–
(
measured m/z 435.1220, error 4.14 ppm), C H O (measured
–
4
26
19 5
at m/z 241 (C H O , measured m/z 241.0514, error 3.32 ppm)
14
9
–
4
m/z 411.1222, error 3.89 ppm), C24
error 1.08 ppm), C22
H
17
O
(measured m/z 369.1136,
(measured m/z 359.0905, error
.57 ppm), and C H O (measured m/z 333.0741, error
could correspond to a loss of resveratrol (228 Da), while m/z 265
–
–
H
15
O
5
(
C H O , measured m/z 265.0492, error 5.28 ppm) is related to
16 9 4
–
5
20 13 5
consecutive losses of phenol and catechol or resorcinol
94 + 110 Da). Upon comparison with the literature, compounds
19 and 20 are tentatively identified as cis- and trans-scirpusin
8.41 ppm). Although these ions are similar to that of ϵ-viniferin,
(
the ions at m/z 411 and 369 have a much higher relative abundance
than in the MS/MS spectrum of ϵ-viniferin. Through comparison
with authentic reference standards, 16 and 17 were identified as
trans- and cis-δ-viniferin, respectively.
[29]
[13]
A,
which have been identified in grapevine stems,
while
compound 16 may be an unreported structural isomer of scirpusin
A or perhaps ampelopsin A, which also shares this exact mass.
Figure 5. The proposed fragmentation pathways showing the characteristic ions observed for compound 7 (left)
and 11, 13 (right).
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Rapid Commun. Mass Spectrom. 2013, 27, 1815–1827

Study of wine stilbenoids in red wines by UPLC/ESI-QTOFMS
Figure 6. Combined BPC of the stilbenoid oligomers 18–41 found in pinot noir wine extract.
[
24]
Dimers (P + P)
works,
and has nearly identical fragmentation patterns,
compound 28 is tentatively identified as cis- or trans-ϵ-
viniferin-O-glycoside.
–
Compound 25 showed an [M–H] ion at m/z 485, which
indicated a piceatannol dimer (Fig. 6). In the MS/MS spectrum
of m/z 485, the losses of H O (18 Da), two C H O (42 Da),
2 2 2
resorcinol (110 Da), and 2-hydroxy-4-methylenecyclohexa-2,5-
dienone (122 Da) yielded product ions at m/z 467, 401, 375, and
Compound 29 has an MS/MS spectrum again containing
the ion corresponding to a glycosylated resveratrol dimer at
m/z 615. Similar to the fragmentation of compound 28, the
most abundant product ion is generated from the loss of
glucose (162 Da) resulting in an ion representative of a dimer
3
63. Supporting accurate mass measurements confirmed these
–
7
ions as C28
C
19
H O
(measured m/z 467.1153, error 4.92 ppm),
(measured m/z 401.1012, error 2.99 ppm), C22
measured m/z 375.0895, error 7.19 ppm), and C21
–
6
of resveratrol C H O (measured m/z 453.1366, error
–
6
–
28 21
24
H
17
O
H
H
15
O
17
6
4
.86 ppm). From here, ions at m/z 359 and 289 are formed,
–
(
(
O
6
produced from the loss of phenol (94 Da) and consecutive
loss of two phenols (94 + 94 Da) and CO (28 Da) from m/z
measured m/z 363.0878, error 2.75 ppm), respectively, while
the consecutive losses of resorcinol and H O (18 +110 Da),
O (42 + 110 Da), and another resorcinol (110 + 110 Da)
produced the ions at m/z 357, 333, and 241. The fragmentation
pattern here is very similar to that of ϵ-viniferin, except that
instead of losses of phenol and 4-methylenecyclohexa-2,
-dienone groups, compound 25 loses resorcinol and 2-
hydroxy-4-methylenecyclohexa-2,5-dienone. Because of this,
5 is tentatively identified as a cis- or trans-piceatannol
2
4
53, respectively. Without taking into account the loss of
2 2
C H
glucose, the fragmentation pattern of compound 29 is
comparable to that of compounds 8, 9 and 10 which are
indane-type dimers. Compound 29 could therefore be a
glycosylated derivative of either parthenocissin A,
quadrangularin A, or ampelopsin D.
5
2
homodimer similar to ϵ-viniferin and scirpusin A. The
identity of 25 is possibly scirpusin B, which has been
detected in various plants including passionfruit.
Methoxylated dimers
–
[
30]
The [M–H] ions of compounds 26 and 27 were observed at
m/z 485, representative of a pair of potential methoxylated
dimers. These compounds produced identical MS/MS
spectra, indicating a pair of isomers. The precursor ion
generated four main product ions at m/z 453, 391, 359, and
255. The ion C28
Glycosylated dimers
–
The MS/MS spectrum of compound 28 contained a [M–H]
–
6
ion at m/z 615 which represented a resveratrol dimer with
H
21
O
(measured m/z 453.1338, error
O-glycosylation. The loss of glucose (162 Da) formed the most
1.32 ppm), corresponding to a resveratrol dimer, had a mass
–
À
abundant ion C28
H
21
O
6
(measured m/z 453.1371, error
difference from the [MÀH] ion of 32 Da, which could be
5
.96 ppm), which confirmed the presence of a glycosylated
methanol, confirming the presence of a methoxylated dimer.
resveratrol dimer. The fragmentation pattern below m/z 453
appeared identical to that of ϵ-viniferin with characteristic
benzofuran-type dimer fragments at m/z 359 and 347 due to
loss of phenol (94 Da) and 4-methylenecyclohexa-2,5-dienone
The characteristic stilbenoid loss of a phenol moiety (94 Da)
along with the consecutive loss of methanol and phenol
–
(32 + 94 Da) produced the ions
m/z 391.1182, error 1.28 ppm) and C22
C
23
H
H
19
O
16
6
(measured
(measured
–
O
5
(
106 Da) from the aglycone ion at m/z 453. Additional
ions were found below 1% relative abundance at m/z
35, 411, and 333 from losses of H O (18 Da), C
42 Da), and C O (120 Da), respectively. Because ϵ-
m/z 359.0914, error 3.06 ppm), respectively. Loss of 4-
(methoxymethylene)cyclohexa-2,5-dienone and phenol
–
4
4
(
2
2
H
2
O
(136+ 94 Da) formed the most abundant ion C15
11
H O
8
H
8
(measured m/z 255.0655, error 3.14 ppm). This fragmentation
viniferin-O-glycoside has been reported in wine in previous
pattern indicated that these compounds were a pair of
Rapid Commun. Mass Spectrom. 2013, 27, 1815–1827
Copyright © 2013 John Wiley & Sons, Ltd.
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R. Moss et al.
–
methoxylated indane-type resveratrol dimers. In addition to
the main product ions, ions at m/z 237, 227, 213, 211, and 187
were found below 1% abundance. The fragmentation patterns
of compounds 26 and 27 are identical to a methoxylated dimer
found in Parthenocissus laetevirens that was tentatively
identified as parthenostilbenin A or B. Because of this, it is
possible that compounds 26 and 27 are the cis/trans
methoyxlated dimers known as parthenostilbenin A and B.
seven peaks (Fig. 7). The [M–H] ion at m/z 679 indicated a
resveratrol trimer. The MS/MS spectra of 31 generated many
product ions atm/z 661, 637, 585, 573, 555, and 479, which were a
resultoftheneutrallossesofH O(18Da),C H O(42Da),phenol
2
2
2
(94 Da), and consecutive loss of 4-methylenecyclohexan-2,5-
dienone(106Da)withH O(18+106Da)andphenol(106 + 94Da),
respectively. Supported by accurate mass data, these ions were
identified as C H O (measured m/z 661.1864, error
[28]
2
–
8
4
2
30
–
0
.60ppm),C H O (measuredm/z637.1926,error9.10ppm),
40 30 8
– –
C H O (measured m/z 585.1572, error 2.91 ppm), C H O
3
6
26
8
35 26
8
Oxidized dimers
–
(
measured m/z573.1561,error1.05ppm),C H O (measured
35 24 7
–
Five compounds numbered 21–24 were detected when a
m/z 555.1455, error 1.08 ppm), and C H O (measured
29 20 7
product ion scan of m/z 471.1449 was performed. Compound
m/z 479.1169, error 6.89 ppm), respectively. Further
fragmentation is produced when CO (28 Da), CO-phenol
(122 Da) and CO-4-methylenecyclohexan-2,5-dienone
(106+ 28 Da) are lost from the ion at m/z 479 to form
m/z 451, 357, and 345. The proposed fragmentation pathway
is depicted in Fig. 7. This fragmentation pattern is
characteristic of miyabenol C, which has been observed in
Parthenocissus laetevirens with an authentic reference standard
–
2
1 produced four main product ions other than the [M–H]
–
ion at m/z 471. The ion at m/z 377 (C H O , measured
2
2
18
6
m/z 377.1024, error 1.59 ppm) was related to the characteristic
loss of phenol (94 Da), and consecutive loss of phenol and
carbon monoxide (122 Da) formed the ion at m/z 349
–
5
(C
21
18
H O
, measured m/z 349.1089, error 2.29 ppm). Neutral
loss of two phenols (188 Da) and a carbon monoxide
[28]
(
(
28 Da) resulted in the most abundant ion at m/z 255
and fragmentation information available.
have identified multiple isomers in Vitis vinifera.
Other studies
–
[25]
C
15
12
H O
4
, measured m/z 255.0667, error 1.84 ppm). Further
(134 Da) from m/z 255 produced another
However,
loss of C
highly abundant ion at m/z 121 (C
m/z 121.0290, error 3.30 ppm). The detection of
oxidized resvertrol dimer with this fragmentation pattern
8
H
6
O
2
it was only very recently that a trimeric stilbene, ampelopsin
–
[33]
7
H
6
O
2
, measured
C, was identified in wine by LC/NMR.
a
Tetramers
[
14,31,32]
has been reported in a number of studies to date.
These previous findings have tentatively identified
compound 21 as one of the isomers, restrisol A or B.
The three compounds 22, 23, and 24 showed comparable
The two compounds 39 and 41 were determined to be resveratrol
tetramers by the [M–H] mass at m/z 905. Based on very similar
fragmentation patterns, it is proposed that these compounds
are isomers of each other. The MS/MS spectra of the ion at
m/z 905 produced six characteristic stilbenoid product ions of
–
–
fragmentation patterns with an [M–H] ion of m/z 471. The
difference between these three compounds and compound 19
–
is the absence of the [M–phenol] ion at m/z 377 and a greater
m/z 811, 717, 611, 451, 359, and 265, supported by accurate mass
–
abundance of the ion at m/z 349 resultant from the loss of a
phenol-CO (122 Da) group. As with compound 19, additional
loss of C H O (134 Da) produces a highly abundant ion at
ions at C50
H
36
O
11 (measured m/z 811.2193, error 0.99 ppm),
–
–
C H O10 (measured m/z 717.1720, error 6.41 ppm), C37H O
44 30 24 9
(measured m/z 611.1322, error 4.09 ppm), C H O (measured
–
8
8
2
28 20 6
–
m/z 121. Although compounds that fit this description have
m/z 451.1171, error 3.77 ppm), C H O (measured
22 16 5
–
[25]
been found in the literature, they have not been characterized.
m/z 359.0915, error 3.62), and C H O (measured m/z 265.0494,
16 10 4
Additional studies need to be performed about the oxidation
products of resveratrol and its dimers including NMR studies.
error 6.79 ppm), respectively. The first three ions originate from
the consecutive losses of one (94 Da) and two (94 + 94 Da) phenol
groups followed by the loss of 4-methylenecyclohexan-2,
5-dienone (106 Da). Alternatively, minor fragments at m/z 799
Trimers
and 705 indicate that the loss of one 4-methylenecyclohexan-2,5-
dienone (106 Da) by itself as well as with a phenol (94 Da) is also
occurring. The ion at m/z 451 and its minor counterpart at m/z 453
are the result of the loss of a dimer (454 Da) and dehydrodimer
(452 Da), respectively. This suggests a symmetrical tetramer
splitting into two dimers. Neutral loss from the divided tetramer
occurs as additional losses of one (94 Da) and two (94 + 94 Da)
phenols produce the observed fragmentation at m/z 359 and
265. Although information about tetrameric stilbenes is scarce,
the most well-known tetramer of resveratrol is hopeaphenol,
A total of eight peaks were obtained when m/z 679 was
selected, which corresponded to trimers of resveratrol.
Limited information is available in the literature about these
compounds, and even less about their fragmentation
behaviour is known. These potential trimers exhibit two
noticeably different fragmentation patterns. Compound 30
had a ion at m/z 679 which produced three main fragments
at m/z 585, 491, and 385. These ions were generated from
the characteristic stilbene losses of phenol (94 Da), two
phenols (94 + 94 Da), and consecutive loss of two phenol
[10]
which has been found in multiple plants and wine. A known
isomer of hopeaphenol, isohopeaphenol, has also been detected
(
(
94 + 94 Da) and one 4-methylenecyclohexan-2,5-dienone
106 Da), respectively. Minor ions at m/z 573 and
[26]
in many plants. It is therefore proposed that compounds 39
and 41 are isomers of hopeaphenol.
4
79 which originate from the initial loss of 4-
methylenecyclohexan-2,5-dienone (106 Da) follow by a
subsequent loss of phenol (94 Da).
Compounds 38 and 40 produced similar MS/MS spectra to
the other tetramers. An [M–H] ion at m/z 905 followed by the
–
Meanwhile, compounds 31–37 show very similar
fragmentation patterns that cannot be distinguished, indicative
of a collection of trimeric isomers. Compound 31 will serve as a
model to explain the fragmentation behaviour common to these
major product ions at m/z 811, 717, and 611 resulting from the
consecutive loss of one (94 Da) and two (94+ 94 Da) phenols
and 4-methylenephenol (106 Da). Minor ions at m/z 887,
2
799, 793, and 705 corresponded to the loss of H O
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Study of wine stilbenoids in red wines by UPLC/ESI-QTOFMS
Figure 7. MS/MS spectra of compound 31 with precursor ion m/z 679.1974 with the proposed fragmentation
pathway for the compounds 31–37.
(
18 Da), 4-methylenecyclohexan-2,5-dienone (106 Da), phenol
to identify both precursor and product ions that were
characteristic of stilbenoids known in the literature and some
potentially new compounds.
A total of 41 stilbenoid compounds were detected, 6 of
which were monomers, up to as many as 23 dimers including
their many derivatives (glycosylated, methyoxylated and
oxidized), as well as resveratrol and piceatannol homo- and
heterodimers, 8 trimers and 4 tetramers. Some of these
compounds have previously been identified in wine; however,
in this study 23 were detected for the first time in red wine.
and subsequent loss of (94 + 18 Da) and 4-
2
H O
methylenecyclohexan-2,5-dienone (94+ 106 Da). Although this
compound shares much of the same fragmentation behaviour
as the other three tetramers, no ions above 1% abundance were
observed below m/z 611. These compounds may be non-
symmetrical tetramers of resveratrol.
CONCLUSIONS
The present study used MS/MS analysis to detect and
partially identify multiple monomer and oligomer stilbenoids
in extracted red wine samples. This was facilitated by
accurate mass ESI-QTOF which provided sufficient resolution
SUPPORTING INFORMATION
Additional supporting information may be found in the
online version of this article.
Rapid Commun. Mass Spectrom. 2013, 27, 1815–1827
Copyright © 2013 John Wiley & Sons, Ltd.
wileyonlinelibrary.com/journal/rcm

R. Moss et al.
n
analogues from wine grapes by HPLC/MS and HPLC/
DAD-UV. Food Chem. 2011, 127, 727.
Acknowledgements
The authors would like to thank their sponsors for important
funding: UBC (Okanagan campus-Office of the Provost –
International grant), NSERC (Discovery Grant) , CFI (Leader
Opportunity Fund grant).This project was also supported in
part by the School of Agriculture, Food and Wine at The
University of Adelaide, and by Australia's grape growers
and winemakers through their investment body, the Grape
and Wine Research and Development Corporation, with
matching funds from the Australian Government. QM thanks
the Faculty of Science for a PhD scholarship.
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