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Identification of Chemical Ingredients of Peanut Stems and Leaves Extracts

using UPLC-QTOF-MS Coupled With Novel Informatics UNIFI Platform:
Chemical Ingredients,Peanut Stems and L...

Article  in  Journal of Mass Spectrometry · September 2016

DOI: 10.1002/jms.3887

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 Journal of
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Research article SPECTROMETRY
Received: 1 September 2016 Revised: 16 September 2016 Accepted: 21 September 2016 Published online in Wiley Online Library

(wileyonlinelibrary.com) DOI 10.1002/jms.3887

Identification of chemical ingredients of peanut

stems and leaves extracts using UPLC-QTOF-MS
coupled with novel informatics UNIFI platform
Lei Deng,a† Ai-Min Shi,a† Hong-Zhi Liu,a Naren Meruva,b Li Liu,a Hui Hu,a
Ying Yang,a Chun Huang,b Peng Lib and Qiang Wanga*
Peanut stems and leaves have been used traditionally as both herbal medicines and special food in Asia. In this study, the main
functional compounds of peanut stems and leaves extracts were identified using UPLC separation coupled to high resolution mass
spectrometry (QTOF-MS), and a traditional medicine library. Three different extraction solvents (ethyl acetate, petroleum ether
and n-butanol) were evaluated to prepare the extracts of peanut stems and leaves. A total of 283 chemical compounds were iden-
tified in peanut stems and leaves extracts, of which 207 compounds are tentatively new identifications in Genus Arachis. The in-
tegration of data acquisition and processing with the traditional medicine library provides a simple, efficient process to
effectively facilitate the identification of chemical ingredients in complex natural product extracts. The integrated workflow for
separation, detection and identification of functional compounds in natural products using UPLC/QTOF-MS greatly improves pro-
ductivity for development of traditional herbal medicines. Copyright © 2016 John Wiley & Sons, Ltd.

Keywords: peanut stems and leaves; chemical ingredients; functional compounds; UPLC-QTOF-MS; UNIFI software and traditional
medicine library

Introduction
Peanut stems and leaves commonly referred to as the stems and
leaves of Genus Arachis have been used traditionally for health ben-
efits and for therapeutic effects in Asia. While peanuts are grown
worldwide, including Asia, Africa and America,[1,2] large amount of
peanut stems and leaves cannot be used for its medicinal proper-
ties because of the limited information on its efficacy as a traditional
Chinese medicine. One of the objectives of this study is to address
these challenges by identifying the key chemical ingredients of
peanut stems and leaves extracts that may be the source of the tra-
ditional medicines.
In China, peanut stems and leaves have been used as traditional
Chinese medicine for about 600 years from Ming Hong-wu period.
According to Yunnan Great Dictionary of Chinese Medicine and
other Traditional Chinese Medicine Classics, peanut stems and
leaves can be used for treating insomnia and inflammation.[3] How-
ever, like other herbal medicines, the utilization of peanut stems
and leaves is limited because of uncertainty of effective compo-
nents and the mechanism of efficacy.[4] Therefore, it is important
to gain understanding on all of the chemical ingredients and the
mechanism of its function. In addition, it is desirable to generate a
chemical fingerprint of a given herb or plant extract to maintain
quality standards, identification of potential impurities and to deter-
mine differences among similar plants, varieties or harvesting times.
Identification of functional compounds in herbal plant extracts
can be a challenging analytical task as these complex extracts con-
tain hundreds or even thousands of individual chemical ingredients
with a wide range of concentrations. The conventional approach
for identification of components in traditional medicinal products
propose possible molecular formula and structure based on the ex-
act mass of molecular ion and then search the results against online
libraries to obtain possible identifications. The MS/MS fragmenta-
tion pathways can be further deduced for chemical structure confir-
mation. This process is time consuming and inefficient as it requires
manual intervention by researchers in almost every single step
throughout the entire process, but also requires high level of exper-
tise in natural products chemistry.
In recent years, ultra performance liquid chromatography (UPLC)
has been applied for high-resolution chromatographic separation,
excellent sensitivity and faster analyses of chemical ingredients of
natural product extracts such as peanut stems and leaves
extracts.[5] While UV and fluorescence detectors coupled to UPLC
separation have been used for analysis of functional compounds
in plant extracts, mass spectrometry detection is preferred as it pro-
vides higher degree of selectivity and sensitivity for identification of
trace level chemical ingredients in complex natural product
extracts.[6] Compared to nominal mass MS system, high resolution
* Correspondence to: Qiang Wang, Institute of Food Science and Technology,
Chinese Academy of Agricultural Sciences/Key Laboratory of Agro-Products
Processing, Ministry of Agriculture, P.O. Box 5109, Beijing 100193, China. E-mail:
wangqiang06@caas.cn
†
These authors contributed equally to this work.
a Institute of Food Science and Technology, Chinese Academy of Agricultural
Sciences/Key Laboratory of Agro-Products Processing, Ministry of Agriculture,
P.O. Box 5109, Beijing 100193, China
1157

is to manually extract each individual chromatographic peak, b Waters Corporation, Milford, MA, USA

J. Mass Spectrom. 2016, 51, 1157–1167 Copyright © 2016 John Wiley & Sons, Ltd.
 Journal of
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SPECTROMETRY L. Deng et al.

mass spectrometers (QTOF-MS) provides accurate mass informa- chromatographic grade, purchased from Sigma–Aldrich (Madrid,
tion with low mDa precision (e.g. <5 mDa) that can be used for Spain). Ethyl acetate, petroleum ether and N-butanol were pur-
predicting the elemental composition of the chemical entities and chased from Chinese Medicine Group Chemical Reagent Co., Ltd.,
fragment ion data that can be used for structural confirmation in and water was HPLC grade, made by Milli-Q Advantage A10
the absence of pure standards.[7] High throughput natural product (Massachusetts, United States). Rotary evaporator was purchased
screening solutions also require automated data processing and from Shanghai Ya Rong biochemical instrument factory. Glass
scientific libraries to enable identification of known and unknown microfiber filters (0.22-μm pore size) were purchased from Pall
chemical ingredients in natural product extracts.[8] Corporation (Michigan, United States).
In this study, a combination of UPLC separation, QTOF-MS detec-
tion and automated data processing software with scientific library
Instrument and informatics platform
was used for identification of functional components in three differ-
ent extracts (ethyl acetate, petroleum ether and n-butanol) of pea- UPLC-QTOF-MS
nut stems and leaves. The enhanced UPLC separation using 1.7-μm
The equipment used was an ACQUITY UPLC I-Class System coupled
column and MSE data acquisition that simultaneously collects accu-
rate mass precursor ion (full scan) and accurate mass fragment ions to a Xevo G2–XS QTOF mass spectrometer detector. All the chroma-
(MS/MS data) provides increased analyte information including iso- tography and MS equipments were purchased from Waters Corpo-
tope pattern matching and adducts. The streamlined workflow of ration (Massachusetts, United States). The capillary column used
UPLC/QTOF-MS with the informatics solution (automated data pro- was an ACQUITY UPLC® BEH C18, 1.7 μm (2.1 × 100 mm Column)
cessing and scientific library) makes analysis of functional com- from Waters Corporation (Massachusetts, United States).
pounds in natural products a routine task.
UNIFI software
The UNIFI informatics platform from Waters Corporation was used
Materials and methods to integrate data acquisition, data mining, library searching and re-
port generation. A natural product analytical workflow within UNIFI
Materials was used to analyze the chromatographic and mass spectral com-
ponents of the herbal medicine extract utilizing the various in-built
Peanut stems and leaves were harvested from Daming County,
tools such as a traditional medicine library, synthetic adulterant
Hebei Province, China. Formic acid and acetonitrile used were of
library and structure elucidation tool to effectively confirm the
ingredients in the herbal product.[8]
Table 1. The elution gradient of the samples The traditional medicine library within UNIFI contains more than
6000 compounds from 600 herbs and their associated compound
Time (min) %A %B Curve
details. UNIFI software also has a unique database function that al-
0 90 10 6 lows users to quickly add new compounds and create a customized
5 80 20 6 library of compounds that includes detailed metadata based on
10 65 35 6 their chemical structure. For structural elucidation of unknowns,
21 55 45 6 UNIFI software provides an elemental composition calculator that
23 45 55 6 can determine a number of possible formulas for an accurate mass
27.5 25 75 6 peak, based on isotope pattern matching and taking into account
30 10 90 6 fragment ion peaks. Elemental composition produces a list of pos-
sible formulas, each with an i-FIT score which signifies the relative
1158

Figure 1. shows the workflow of extracts identification process.

wileyonlinelibrary.com/journal/jms Copyright © 2016 John Wiley & Sons, Ltd. J. Mass Spectrom. 2016, 51, 1157–1167

Chemical ingredients, peanut stems and leaves
confidence for all suggested formulas. A formula with a confidence
score greater than 0.8 can be considered as a candidate for
identification.
Sample preparation and analysis
Sample preparation
The peanut stems and leaves were air-dried and ground into fine
powder and stored in a polyethylene bag at 20 °C until further
analysis. A 40-g sample of the peanut stems and leaves was ex-
tracted twice with 480 ml of hot water (at 98 °C) for duration of
3 h each time, followed by syringe filtration to remove solid
Figure 2. UPLC-QTOF-MSE BPI chromatogram of ethyl acetate phase (A); UPLC-QTOF-MSE BPI chromatogram of petroleum ether phase (B); UPLC-QTOF-MSE
BPI chromatogram of n-butanol phase (C).
J. Mass Spectrom. 2016, 51, 1157–1167 Copyright © 2016 John Wiley & Sons, Ltd.
Journal of
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SPECTROMETRY
residues.[9] The above extract was vacuum freeze dried and then
stored at 20 °C.
The analytical workflow for identification of functional compo-
nents in traditional medicinal plant extracts typically uses organic
solvents with different polarities to extract a wide range of
compounds[10] followed by analysis using chromatography, mass
spectrometry, NMR techniques and informatics software for data
analysis and compound identification.[11] For comprehensive
chemical characterization of Chinese traditional medicinal
plants,[12] multiple solvents have been applied including ethyl
acetate, petroleum ether and n-butanol to extract functional
components of peanut leaves.[13] In this study, the functional
components in aqueous freeze dried extract of peanut stems and
1159
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 Journal of
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SPECTROMETRY L. Deng et al.

leaves were extracted using three different organic solvents (petro-
leum ether, ethyl acetate and n-butanol) with differing polarities,
and the individual extracts were analyzed using UPLC/QTOF-MS.
The components acquired by the different solvents were named
as ‘ethyl acetate phase’, ‘petroleum ether phase’ and ‘n-butanol
phase’. Forty grams of the dried aqueous extract of peanut stems
and leaves was filled in a 20-cm-long filter paper tube, which was
placed in a 1000-ml capacity mini-sized soxhlet extraction unit with
a hot reflux device. Aqueous extracts were extracted 3 times, each
time for 2 h, at boiling temperature of different extraction
solvents.[14] All the phases were concentrated by a vacuum rotary
evaporator. After the concentration step, each individual phase
was reconstituted using HPLC grade acetonitrile, and the material
was concentrated to about 1 mg/l.[15] The prepared samples were
filled in PE centrifuge tube and stored in ultra low temperature
freezer at 80 °C temperature until analysis.
Sample analysis
Different solvent extracts were analyzed by UPLC-QTOF-MS with
UNIFI data acquisition and data processing software. The tempera-
ture of the UPLC column and sample were set at 45 °C and 5 °C. Wa-
ter and 0.1% formic acid were used as mobile phase A and
acetonitrile and 0.1% formic acid as mobile phase B. The flow rate
was 0.6 ml/min, and a 10-μl injection volume was used. A mixture
of 90/10 water/acetonitrile was used as the weak wash, and the vol-
ume of purge wash and wash solvent was set to 600 μl.[16,17] The
elution gradient used is listed in Table 1.

Figure 3. Summary plot of the identified components in the ethyl acetate phase of peanut stems and leaves using UPLC-QTOF-MS and UNIFI data
processing (D); summary plot of the identified components in the petroleum ether phase of peanut stems and leaves using UPLC-QTOF-MS and UNIFI
1160

data processing (E); summary plot of the identified components in the n-butanol phase of peanut stems and leaves using UPLCQTOF-MS and UNIFI data
processing (F).

wileyonlinelibrary.com/journal/jms Copyright © 2016 John Wiley & Sons, Ltd. J. Mass Spectrom. 2016, 51, 1157–1167
 Table 2. Summary of compounds identified using three different extraction solvents (1-ethyl acetate; 2-petroleum ether; 3-n-butanol)
Category Number Chemicals RT Chemical i-FIT Extractant Number Chemicals RT (min) Chemical i-FIT Extractant
(min) formula score formula score

Alkaloids 1 1-Methyl-2-[(Z)-7-tridecenyl]- 2.28 C23H33NO 0.86 1,2,3 7 Dihydro-N-methylisopelletierine 11.06 C9H19NO 0.99 1,2
4(1H)-quinolone
2 Evocarpine 5.17 C23H33NO 0.95 1,3 8 N-Phenyl-2-naphthylamine 23.73 C16H13N 0.98 1,2,3
3 1-Methyl-2-[(Z)-7-tridecenyl]- 5.81 C23H33NO 0.96 1,2,3 9 Solanidine 28.92 C27H43NO 0.94 1,2,3
4(1H)-quinolone
4 Indolol 8.44 C13H18N2O4SOO)O4S 0.82 1,3 10 Isaindigotidione 29.22 C23H22N2O5 0.82 1,2,3
5 Indolol 8.57 C13H18N2O4S 0.86 1,2,3 11 Isaindigotidione 29.94 C23H22N2O5 0.82 1,2,3
6 Elymoclavine 8.57 C16H18N2O 0.83 1,2,3

J. Mass Spectrom. 2016, 51, 1157–1167

Steroidal and glycosides 1 Campesterol acetate 27.63 C30H50O2 0.87 1,3 8 Cerevisterol 29.42 C28H46O3 0.94 1,3
2 Siraitic acid C 28.24 C28H40O4 0.98 1,2,3 9 α-Sitosterol 29.44 C30H50O 0.82 1,3
3 Siraitic acid C 28.49 C28H40O4 0.86 1,2,3 10 Siraitic acid C 29.57 C28H40O4 0.86 1,2,3
4 (24Z)-7,24-Titucalla-3β,27-diol 28.49 C30H50O2 0.89 1,3 11 α-Sitosterol 29.77 C30H50O 0.95 1,2,3
Chemical ingredients, peanut stems and leaves

5 Siraitic acid C 28.92 C28H40O4 1.00 1,3 12 Siraitic acid C 29.82 C28H40O4 0.96 1,2,3
6 Siraitic acid C 29.15 C28H40O4 0.97 1,2,3 13 α-Sitosterol 29.93 C30H50O 0.82 1,2,3
7 Siraitic acid C 29.41 C28H40O4 0.94 1,2
Terpenes 1 Digiprolactone 4.40 C11H16O3 0.83 1,2,3 16 7β-Senecioyloxyoplopa-3(14)Z, 25.17 C20H28O3 0.95 2
8(10)-dien-2-one
2 Yadanzigan 8.57 C26H38O14 0.95 1,2 17 Trifoside A 25.33 C46H72O18 0.80 1,2
3 Pterodontriol C 8.94 C15H28O3 0.94 1,2,3 18 Deoxypaeonisuffrone 25.33 C10H14O3 0.89 2
4 Dendronobilin G 9.44 C15H26O3 1.00 1,2 19 7β-(3-Ethyl-cis-crotonoyloxy)-14- 26.04 C21H32O4 0.93 1,2
hydroxynotonipetranone
5 Dendronobilin G 9.55 C15H26O3 0.98 1,2 20 7β-(3-Ethyl-cis-crotonoyloxy)-14- 26.14 C21H32O4 0.99 2
hydroxynotonipetranone
6 Dihydroactinidiolide 10.01 C11H16O2 0.84 2,3 21 Betulin_1 27.63 C30H50O2 0.85 1,2
7 Fraxinellonone 10.48 C14H14O4 0.90 2,3 22 4,8,12-Trimethyl-tridecanoic acid 28.24 C16H32O2 0.90 1,2,3
8 Isohistiopterosin A 11.90 C14H16O4 0.92 1,2 23 Arnidiol 28.49 C30H50O2 0.85 2
9 Oxyphyllenodiol A 15.31 C14H22O3 0.80 2 24 Lupenone 28.50 C30H48O 0.83 1,2

Copyright © 2016 John Wiley & Sons, Ltd.

10 14-Deoxyandrographolide 15.83 C20H30O4 0.98 1,2 25 Isoanhydrobelachinal 29.15 C30H44O4 0.99 2
14-Deoxyandrographolide
11 7β-Senecioyloxyoplopa-3(14)Z, 22.60 C20H28O3 0.86 2 26 Ulmoprenol 29.44 C30H50O 0.88 1,2
8(10)-dien-2-one
12 4,8,12-Trimethyl-tridecanoic acid 24.22 C16H32O2 0.86 1,2 27 Iridobelamal A 29.62 C30H50O4 0.85 2
13 4,8,12-Trimethyl-tridecanoic acid 24.38 C16H32O2 0.83 2 28 Ulmoprenol 29.77 C30H50O 0.92 2
14 7β-Senecioyloxyoplopa-3(14)Z, 24.77 C20H28O3 0.83 1,2 29 Diepilycocryptol 29.90 C30H50O4 0.91 1,2
8(10)-dien-2-one
15 4,8,12-Trimethyl-tridecanoic acid 24.85 C16H32O2 0.94 1,2 30 Ulmoprenol 29.93 C30H50O 1.00 2
Quinones 1 2,5-Dimethyl-1,4-benzoquinone 0.60 C8H8O2 0.98 1,2,3 12 1,3,6-Trihydroxy-5-ethoxylmethyl- 9.55 C17H14O6 0.91 2
anthraquinone
2 1,4-Dihydroxy-2-methyl-anthraquinone 6.70 C15H10O4 0.98 2 13 Rubiadin-1-methyl ether 10.48 C16H12O4 0.89 2
3 Questin 6.79 C16H12O5 0.90 1,2 14 Anhydroalkannin 11.90 C16H14O4 0.80 1,2
4 Questin 7.00 0.97 1,2 15 2,5-Dimethyl-1,4-benzoquinone 11.91 0.80 2
Journal of

C16H12O5 C8H8O2
MASS

5 1,3,6-Trihydroxy-5-ethoxylmethyl- 7.15 C17H14O6 0.93 2,3 16 Arnebinone 14.12 C18H22O4 0.89 2,3
anthraquinone

(Continues)
SPECTROMETRY

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1161
 1162

Table 2. (Continued)
Journal of
MASS

Category Number Chemicals RT Chemical i-FIT Extractant Number Chemicals RT (min) Chemical i-FIT Extractant
(min) formula score formula score

6 Denbinobin 7.19 C16H12O5 0.98 2 17 Isobutyrylshikonin 15.31 C20H22O6 0.80 2,3

7 (3R)-Claussequinone 7.76 C16H14O5 0.85 2,3 18 Arnebinone 20.00 C18H22O4 0.97 2
SPECTROMETRY

8 1,3,6-Trihydroxy-5-ethoxylmethyl- 8.00 C17H14O6 0.90 2 19 Danshenxinkun D 22.37 C21H20O4 0.93 2

anthraquinone
9 Aurantioobtusin 8.76 C17H14O7 0.91 2 20 Biflorin 22.61 C20H20O3 0.88 1,2
10 Methyl tanshinonate 8.82 C20H18O5 0.81 2 21 Tanshinone IIA 25.33 C19H18O3 0.95 2
11 1,3-Dihydroxy-2-ethoxymethyl- 9.15 C17H14O5 0.90 2
anthraquinone

wileyonlinelibrary.com/journal/jms
Coumarins and lignans 1 Aschantin 7.94 C22H24O7 0.88 2 11 Lirioresinol B dimethyl ether 24.12 C24H30O8 0.85 2,3
2 ( )-Melilotocarpan D 7.96 C17H16O6 0.86 1,2 12 Lirioresinol B dimethyl ether 24.61 C24H30O8 0.96 1,2,3
3 3-Acetyl-3,4-dihydro5, 8.83 C13H14O5 0.90 2,3 13 cis-3′,4′-Diisovaleryl khellactone 25.33 C26H30O5 0.84 1,2
6-dimethoxy-2(1)H-benzopyrone
4 6-Methoxy-hydrangenol 9.50 C16H14O5 0.89 1,2,3 14 2′-Deoxymeranzin hydrate 25.33 C15H18O4 0.99 1,2
5 Dalbergin 10.48 C16H12O4 0.88 1,2 15 Fraxin 29.22 C16H18O10 0.92 2,3
6 (6αR, 11αR)-10-Hydroxy-3, 11.38 C17H16O5 0.92 2,3 16 5,6-Dimethoxy-7-hydroxycoumarin 29.22 C11H10O5 0.80 1,2,3
9-dimethoxy-pterocarpan
7 (±)-Medicarpin 11.90 C16H14O4 0.80 1,2 17 Glehlinoside A 29.50 C34H42O14 0.91 2,3
8 2′-Deoxymeranzin hydrate 18.65 C15H18O4 0.92 2,3 18 Fraxin 29.92 C16H18O10 0.98 2,3
9 Anomalin 23.15 C24H26O7 0.82 2,3 19 5,6-Dimethoxy-7-hydroxycoumarin 29.94 C11H10O5 0.88 2,3
10 Lirioresinol B dimethyl ether 24.03 C24H30O8 0.82 2
Flavone and 1 Maltol 0.93 C6H6O3 0.94 1,2 10 2′-O-Methylisoliquiritigenin 11.38 C16H14O4 0.84 1,2,3
flavonoid glycoside
2 Maltol 1.38 C6H6O3 0.96 1,2 11 Neobavaisoflavone 11.90 C20H18O4 0.98 2,3
3 Persicogenin 7.96 C17H16O6 0.80 2,3 12 Neobavaisoflavone 16.95 C20H18O4 0.96 2,3
4 Irisolidone 8.44 C17H14O6 0.95 1,2,3 13 Norkurainol 23.71 C25H28O7 0.92 1,2
5 Bavachromene 8.57 C20H18O4 0.82 2 14 Procyanidin A2 24.03 C30H24O12 0.93 1,2
6 Skullcapflavone I 8.57 C17H14O6 0.99 1,2 15 Kushenol L 24.28 C25H28O7 0.84 2,3

Copyright © 2016 John Wiley & Sons, Ltd.

7 Isosakuranetin 9.50 C16H14O5 0.87 1,2 16 Kushenol R 24.61 C26H30O5 0.88 2,3
8 Tectochrysin 10.48 C16H12O4 0.82 2 17 Maltol 25.33 C6H6O3 0.88 1,2
9 5-Hydroxy-4′,7-dimethoxyflavanone 11.38 C17H16O5 0.82 1,2,3 18 Naringenin-4′-glucoside-7-rutinoside 29.93 C33H42O19 0.84 1,2,3
Miscellaneous 1 5-Hydroxymethyl-2-furaldehyde 0.93 C6H6O3 0.92 1,2 17 (10E)1,10-Heptadeca-diene-4, 9.55 C17H24O3 0.85 1,2
6-diyne-3,8,9-triol
2 5-Hydroxymethyl-2-furaldehyde 1.38 C6H6O3 0.83 1,2 18 2-Benzyl octanal 9.55 C15H22O 0.90 1,2
3 2-Methoxy cinnamaldehyde 3.06 C10H10O2 1.00 1,2 19 (E,Z)-3,4-Dimethyl-2,4-hexadiene 9.55 C8H14 0.83 1,2,3
4 p-Methoxybenzylacetone 4.40 C11H14O2 0.87 2,3 20 p-Anisaldehyde 11.90 C8H8O2 0.91 1,2
5 1-Deoxyeucommiol 4.60 C9H16O3 0.84 1,2 21 (10E)1,10-Heptadeca-diene-4, 24.46 C17H24O3 0.91 1,2
6-diyne-3,8,9-triol
6 Atractylodin 5.56 C13H10O 0.87 1,2 22 3,3′,5,5′-Tetramethoxy-trans-stilbene 25.12 C18H20O4 0.82 1,2
7 Benzopyran 5.56 C9H8O 0.91 2,3 23 Heptadecylamine 25.15 C17H37N 0.94 2,3
8 Atractylodin 5.72 C13H10O 0.92 2,3 24 3,3′,5,5′-Tetramethoxy-trans-stilbene 25.33 C18H20O4 0.85 1,2
9 Phenethyl alcohol 6.52 C8H10O 0.87 1,2 25 3,3′,5,5′-Tetramethoxy-trans-stilbene 25.79 C18H20O4 0.95 1,2,3
10 3-t-Butyl-1,2-dimetho-xyl-benzene 7.44 C12H18O2 0.83 1,2 26 n-Hexadecanal 27.63 C16H32O 0.86 2,3
11 Linalool 7.52 C10H18O 0.94 2,3 27 N-Isobutyl-(2E,4E)-octadecadienamide 27.67 C22H41NO 0.97 2,3

(Continues)

J. Mass Spectrom. 2016, 51, 1157–1167

L. Deng et al.
 Table 2. (Continued)

Category Number Chemicals RT Chemical i-FIT Extractant Number Chemicals RT (min) Chemical i-FIT Extractant
(min) formula score formula score

12 2-Undecenal 7.91 C11H20O 0.81 1,2 28 Z-9,17-Octadecadienal 29.10 C18H32O 0.97 1,2
13 Cinnamaldehyde 7.97 C9H8O 0.81 2,3 29 (3,3-Dimethyldecyl)-benzene 29.10 C18H30 0.84 2
14 Panaxytriol 8.94 C17H26O3 0.88 1,2 30 n-Hexadecanal 29.40 C16H32O 0.96 1,2
15 (10E)1,10-Heptadeca-diene-4, 9.44 C17H24O3 0.85 1,2 31 N-Isobutyl-(2E,4E)-octadecadienamide 29.41 C22H41NO 0.93 2,3
6-diyne-3,8,9-triol
16 2-Benzyl octanal 9.44 C15H22O 0.92 1,2,3 32 3-(Hexadecyloxy)propane-1,2-diol 29.72 C19H40O3 0.95 2
Others 1 Pyrogallic acid 0.93 C6H6O3 0.99 1,2,3 71 Pseudolaric acid B 23.16 C23H28O8 0.93 1,2

J. Mass Spectrom. 2016, 51, 1157–1167

2 Pyrogallic acid 1.38 C6H6O3 0.91 1,2,3 72 Neonootkatol 23.58 C20H26O3 0.83 2,3
3 2,4-Dihydroxyaceto-phenone 2.98 C8H8O3 0.96 2,3 73 γ-Linoleic acid 23.76 C18H30O2 0.83 1,2
4 Methyl cinnamate 3.06 C10H10O2 0.99 2,3 74 Ambrettolid 23.93 C16H28O2 0.91 1,2,3
5 p-Cresol 3.06 C7H8O 0.87 1,2 75 Oxyphyllacinol 23.93 C20H26O3 0.80 1,2,3
6 Dihydrocaffeic acid 3.32 C9H10O4 0.89 2,3 76 Trichosanic acid 23.98 C18H30O2 0.80 2,3
Chemical ingredients, peanut stems and leaves

7 Benzeneuropyl acetate 4.40 C11H14O2 0.88 1,2 77 Bletilol B 24.03 C27H26O7 0.86 2,3
8 Gingerone 4.60 C11H14O3 0.84 1,2,3 78 γ-Linoleic acid 24.22 C18H30O2 0.88 1,2
9 2-Methoxy cinnamic acid 4.67 C10H10O3 0.92 2,3 79 Coronaric acid 24.22 C18H32O3 0.94 1,2
10 4-Ethylphenol 6.52 C8H10O 0.88 1,2,3 80 Trichosanic acid 24.38 C18H30O2 0.92 2,3
11 Ornithine 7.71 C5H12N2O2 0.84 2,3 81 Shogaol 24.46 C17H24O3 0.93 1,2
12 Caesalpins J 7.96 C17H16O6 0.83 1,2 82 Bletilol B 24.61 C27H26O7 0.95 1,2,3
13 Tyrosol 7.97 C8H10O2 0.84 1,2 83 Stearidonic acid 24.77 C18H28O2 0.84 2,3
14 Asparagine_1 7.97 C4H8N2O3 0.90 1,2,3 84 Saurufuran A 24.77 C20H28O3 0.82 1,2
15 O-Methoxycinnamic acid 7.97 C10H10O3 0.90 1,2 85 Trichosanic acid 24.85 C18H30O2 0.93 1,2
16 Salvianolic acid F 8.57 C17H14O6 0.85 1,2,3 86 Stearidonic acid 24.99 C18H28O2 0.89 1,2
17 Doederleinic acid 8.57 C7H8O4 0.90 1,2 87 (E,E)-9-Oxooctadeca-10,12-dienoic acid 24.99 C18H30O3 0.89 2,3
18 2,6-Di-tert-butyl-4-hydroxy toluene 8.94 C15H24O 0.83 2,3 88 Saurufuran A 24.99 C20H28O3 0.83 1,2
19 Ornithine 9.44 C5H12N2O2 0.93 1,2,3 89 Butyl isobutyl phthalate 25.12 C16H22O4 0.87 2,3
20 9-Hydroxy-10,12-pentadecadienoic 9.44 C15H26O3 0.91 2,3 90 Saurufuran A 25.17 C20H28O3 0.89 1,2,3
acid

Copyright © 2016 John Wiley & Sons, Ltd.

21 9-Hydroxy-10,12-pentadecadienoic 9.55 C15H26O3 0.82 1,2 91 Stearidonic acid 25.17 C18H28O2 0.93 2
acid
22 Ornithine 9.55 C5H12N2O2 1.00 1,2,3 92 Anisic acid 25.33 C8H8O3 0.80 2,3
23 Methyl 3,4,5-trimethoxycinnamate 10.24 C13H16O5 0.95 1,2 93 p-Hydroxybenzoic acid 25.33 C7H6O3 0.81 12
,2
24 Dihydrooxyresveratrol 10.48 C14H14O4 0.99 2,3 94 Phthalic anhydride 25.33 C8H4O3 0.86 2,3
25 Odoriflavene 11.38 C17H16O5 0.81 1,2,3 95 Butyl isobutyl phthalate 25.33 C16H22O4 0.88 2
26 Benzylcaffeate 11.90 C16H14O4 0.99 1,2 96 Vitamin B1 25.33 C12H17ClN4OS 0.85 1,2,3
27 4-Hydroxyacetophenone 11.90 C8H8O2 0.98 1,2 97 Saurufuran A 25.54 C20H28O3 0.86 2,3
28 13-Hydroxy-9,11-hexadecadienoic 12.63 C16H28O3 0.86 1,2,3 98 Stearidonic acid 25.54 C18H28O2 0.86 1,2
acid
29 9,16-Dioxyhydroxy-10,12,14-triene-18 14.76 C18H30O4 0.80 2,3 99 Octahydrocurcumin 25.54 C21H28O6 0.85 2,3
carbonic acid
Journal of

30 Ambrettolid 14.76 C16H28O2 0.99 1,2,3 100 Pseudoaspidin 25.79 C25H32O8 0.91 1,2,3
MASS

31 Ambrettolid 15.34 C16H28O2 0.82 2,3 101 (E,E)-9-Oxooctadeca-10,12-dienoic acid 26.04 C18H30O3 0.81 2,3
32 15.34 C18H30O4 0.86 1,2 102 Stearidonic acid 26.14 C18H28O2 0.99 1,2,3

(Continues)
SPECTROMETRY

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1163
 1164

Table 2. (Continued)
Journal of
MASS

Category Number Chemicals RT Chemical i-FIT Extractant Number Chemicals RT (min) Chemical i-FIT Extractant
(min) formula score formula score

9,16-Dioxyhydroxy-10,12,
14-triene-18 carbonic acid
SPECTROMETRY

33 (E,E)-9-Oxooctadeca-10,12-dienoic acid 15.83 C18H30O3 0.87 2,3 103 6,9-Octadecadiynoic acid, methyl ester 26.14 C19H30O2 0.86 2,3
34 Di (2-ethyl butyl) phthalate 15.83 C20H30O4 0.85 1,2,3 104 Coronaric acid 26.23 C18H32O3 0.98 1,2
35 Stearidonic acid 15.83 C18H28O2 0.89 2,3 105 2-Monopalmitin 26.33 C19H38O4 0.91 2,3
36 Ambrettolid 16.04 C16H28O2 0.99 1,2 106 Δ8,11-Octadecadienoic acid 26.33 C18H32O2 0.87 2,3
37 9,16-Dioxyhydroxy-10,12, 16.05 C18H30O4 0.84 1,2,3 107 (E)-Hexadecyl-ferulate 27.07 C26H42O4 0.96 1,2
14-triene-18 carbonic acid

wileyonlinelibrary.com/journal/jms
38 Salidroside 16.10 C14H20O7 0.89 1,2 108 (E)-Hexadecyl-ferulate 27.64 C26H42O4 0.87 1,2,3
39 9,16-Dioxyhydroxy-10,12, 16.62 C18H30O4 0.83 1,2 109 (E)-Hexadecyl-ferulate 27.74 C26H42O4 0.88 1,2
14-triene-18 carbonic acid
40 Ambrettolid 16.62 C16H28O2 0.96 2,3 110 (E)-Hexadecyl-ferulate 27.99 C26H42O4 0.99 1,2
41 N-Benzoylphenylalanyl-L- 16.77 C27H28N2O4 0.98 1,2 111 Bis(2-ethylhexyl)phthalate 28.24 C24H38O4 0.99 2,3
phenylalaninol acetate
42 Ilexin II 16.78 C23H30O10 0.86 2,3 112 (E)-Hexadecyl-ferulate 28.24 C26H42O4 0.98 1,2,3
43 Ambrettolid 17.18 C16H28O2 0.92 1,2 113 Trichosanic acid 28.24 C18H30O2 0.88 2,3
44 9,16-Dioxyhydroxy-10,12, 17.18 C18H30O4 0.87 2,3 114 α-Monolinolein 28.39 C21H38O4 0.87 2,3
14-triene-18 carbonic acid
45 Trichosanic acid 18.33 C18H30O2 0.82 1,2 115 (E)-Hexadecyl-ferulate 28.49 C26H42O4 0.83 1,2
46 p-Hydroxyphenylethanol coumarate 18.65 C17H16O4 1.00 2,3 116 Bis(2-ethylhexyl)phthalate 28.49 C24H38O4 0.97 2
47 Di (2-ethyl butyl) phthalate 18.74 C20H30O4 0.96 2,3 117 (E)-Hexadecyl-ferulate 28.65 C26H42O4 0.96 1,2
48 (E,E)-9-Oxooctadeca-10,12- 18.94 C18H30O3 0.96 2,3 118 (E)-Hexadecyl-ferulate 28.79 C26H42O4 0.91 1,2
dienoic acid
49 Di (2-ethyl butyl) phthalate 18.94 C20H30O4 0.99 2 119 (E)-Hexadecyl-ferulate 28.92 C26H42O4 0.85 1,2
50 (E,E)-9-Oxooctadeca-10,12- 19.65 C18H30O3 0.94 1,2 120 Bis(2-ethylhexyl)phthalate 28.92 C24H38O4 0.91 2,3
dienoic acid
51 Di (2-ethyl butyl) phthalate 19.65 C20H30O4 0.87 2,3 121 (E)-Hexadecyl-ferulate 29.15 C26H42O4 0.85 1,2

Copyright © 2016 John Wiley & Sons, Ltd.

52 Di (2-ethyl butyl) phthalate 19.76 C20H30O4 0.87 2 122 Bis(2-ethylhexyl)phthalate 29.16 C24H38O4 0.85 2
53 Oxyphyllacinol 20.20 C20H26O3 0.88 1,2,3 123 Thymidine 29.21 C10H14N2O5 0.86 1,2,3
54 Ambrettolid 20.20 C16H28O2 0.90 2,3 124 Mulberrofuran K 29.22 C39H32O8 0.89 2
55 (10E,9S,12S,13S)-Trihydroxy-10- 21.64 C19H36O5 0.92 2,3 125 3-O-Acetyl-caffeic acid 29.22 C11H10O5 0.90 1,2
octadecenoate
56 Stearidonic acid 21.69 C18H28O2 0.86 2,3 126 (E)-Hexadecyl-ferulate 29.41 C26H42O4 0.99 2
57 (10E,9S,12S,13S)-Trihydroxy-10- 21.76 C19H36O5 0.86 1,2 127 Bis(2-ethylhexyl)phthalate 29.41 C24H38O4 0.87 1,2
octadecenoate
58 Saurufuran A 22.08 C20H28O3 0.82 1,2 128 (E)-Hexadecyl-ferulate 29.57 C26H42O4 0.80 2,3
59 Stearidonic acid 22.08 C18H28O2 0.94 1,2 129 Scroside E 29.62 C30H38O16 0.98 1,2
60 Saurufuran A 22.25 C20H28O3 0.83 1,2 130 14-Methyl-hexadecanoic acid 29.64 C18H36O2 0.88 2
methylester
61 Stearidonic acid 22.31 C18H28O2 0.89 2,3 131 Hydroginkgolinic acid 29.70 C21H34O3 0.99 1,2,3
62 Lignoceryl ferulate 22.31 C34H58O4 0.90 2,3 132 2,3-Dihydroxypropyl oleate 29.72 C21H40O4 0.90 2,3
63 Saurufuran A 22.60 C20H28O3 0.81 2,3 133 Bis(2-ethylhexyl)phthalate 29.81 C24H38O4 0.99 1,2
64 Sarmentosin 22.61 C13H24O6 0.81 1,2 134 (E)-Hexadecyl-ferulate 29.82 C26H42O4 0.82 1,2

(Continues)

J. Mass Spectrom. 2016, 51, 1157–1167

L. Deng et al.
 Journal of
MASS
Chemical ingredients, peanut stems and leaves SPECTROMETRY

API positive polarity and sensitivity analyzer mode were selected

Extractant

1,2
1,2
2,3
2
2
for QTOF-MS data acquisition. A wide mass range of m/z 50–1000
was selected for acquiring accurate mass precursor and fragment
ion data. The corona voltage was 2.1 kV, the sampling cone voltage

score

0.99
0.80
0.87
0.88
0.80
i-FIT
was 40 V and the source temperature was 120 °C.[18] MSE mode was
selected for the acquisition: collision ramp energy from 15 to 45 V
was used.[19] Analysis was carried out in full scan mode, and the

C10H14N2O5
Chemical
formula

C31H42O18
C21H34O3
scan time was set to 0.2 s.[20]
C26H42O4

C11H10O5
One of the major challenges for LC-MS screening has been the
lack of robust streamlined workflows that allow quick and easy pro-
cessing from sample to report. Here, we demonstrate the utility of
RT (min)

29.83

29.94

29.94
29.94
29.91

the Natural Products Application solution with UNIFI and traditional

medicine library for identification of functional compounds in natu-
ral product extracts. The UNIFI software integrates the various data
processing steps such as data acquisition, peak picking, library
searching, compound identification and report generation. Addi-
tionally, structure elucidation tools within the software allow further
Chemicals

investigation of unknown peaks that have no suitable library match.

3-O-Acetyl-caffeic acid
Hydroginkgolinic acid
(E)-Hexadecyl-ferulate

The UNIFI software also enables compound screening by setting re-

tention time tolerances, and the absolute retention time identifica-
Neonuezhenide

tion tolerance was set at 0.1 min[21] (Fig. 1).

Thymidine

Results and discussion

Number

Identification of functional components by UPLC-QTOF-MS

136
137
135

138
139

analysis
Each sample was analyzed in duplicates by UPLC/QTOF-MSE mode.
Extractant

1,2
2
2,3

1,2
2,3
2

In TOF-MSE experiment, the mass spectrometer performs data ac-

quisition by rapidly switching from a low-collision energy (CE) scan
to a high-CE scan during a single LC run. The low-CE experiments
score

0.90
0.80
0.83

0.87
0.86
0.85
i-FIT

provide information about the intact molecular ion, for example,

[M + H] +, while the high-CE scan generates fragment ion informa-
tion. Alignment of the low-CE and high-CE data is automatically
performed by the software. The MSE raw data was processed using
Chemical
formula

the streamlined workflow of UNIFI software to quickly identify the

C34H58O4
C18H28O2
C17H24O4
C23H28O8
C18H28O2
C20H26O3

chemical components that met the match criteria with the scientific
library. The components identified in the solvent blank were
subtracted from the sample peak table.
22.61
22.61
22.61

22.96
22.74

23.12

Figure 2 shows the UPLC/TOF-MSE BPI (base peak intensity) chro-

(min)
RT

matogram of ‘ethyl acetate’, ‘petroleum ether’ and ‘n-butanol’ ex-

tracts of peanut stems and leaves. The advantages of using UPLC
for the analysis of complex plant extracts are fully demonstrated
here. Enhanced separation efficiency (sharper chromatographic
peaks) and higher peak capacity can be observed from the analysis
Chemicals

of different solvent extracts analyzed in 30 min. MSE provides the

molecular weight information of the compounds and the respec-
Lignoceryl ferulate

Pseudolaric acid B
Stearidonic acid

Stearidonic acid

tive fragment ion information, which can be matched to the tradi-

6-Gingerdione

Neonootkatol

tional medicine library for an in-depth ingredient analysis and

structural identification.

UNIFI data processing

Number

65
66
67
68
69
70

With the UNIFI data processing workflow, the component informa-

tion is automatically matched with the traditional medicine library
for potential identifications. The traditional medicine library follows
Table 2. (Continued)

the 2010 edition of Chinese Pharmacopoeia and lists all the herbs
including compound name (both in Mandarin and English), chem-
ical structure, molecular formula, average molecular mass and
Category

mono-isotopic molecular mass of each compound as well as the

plant origins. The traditional medicine library can be incorporated
1165

into the UNIFI analysis method to show components with good

J. Mass Spectrom. 2016, 51, 1157–1167 Copyright © 2016 John Wiley & Sons, Ltd. wileyonlinelibrary.com/journal/jms
 Journal of
MASS
SPECTROMETRY
Table 3. Numbers of eight categories of chemicals in different extraction phases
Alkaloids Steroidal Terpenes
and glycosides
Ethyl acetate phase 11 13 17
Petroleum ether phase 9 8 30
N-butanol phase 10 12 5 5
match. All components with response value greater than 5000
counts and exact mass error less than 5 mDa were short-listed.
Figure 3 shows the summary plot of the identified components
of ‘ethyl acetate’, ‘petroleum ether’ and ‘n-butanol’ extracts of pea-
nut stems and leaves. Each listed chemical component contains the
following information: compound name, molecular formula, exact
mass mono-isotopic molecular weight, response intensity, reten-
tion time, exact mass error in mDa, ionization mode, adduct ions
and identification status. Compounds with good match can be con-
firmed, and the identification results can be summarized directly as
component tables or component plot. All unidentified components
can be further investigated using the structural elucidation tools to
confirm elemental composition, match with the theoretical frag-
ments and other online databases such as ChemSpider.
Comparison of different extraction phases
A total of 163, 238 and 139 chemicals were identified in ethyl ace-
tate phase, petroleum ether phase and n-butanol phase, respec-
tively. Using petroleum ether as the extractant provided most
number of chemical compounds compared to the ‘ethyl acetate
phase’ and ‘n-butanol phase’. Compared with the results from pre-
vious studies,[22–26] 207 chemicals were first identified in the species
of Genus Arachis from this investigation.
Table 2 shows all the chemicals identified in aqueous extracts of
peanut stems and leaves and listed based on their natural chemical
class. We identified totally eight different categories of chemicals.
The chemicals in each category were sorted based on their reten-
tion time. Sometimes, the same name chemicals were found more
than once because of the heterogeneous occurrence of substance.
Identified chemical compounds can be classified into 11 alkaloids,
13 steroidal and glycosides, 30 terpenes, 21 quinones, 19 coumarins
and lignans, 18 flavone and flavonoid glycoside, 32 miscellaneous
and 139 other miscellaneous compounds.
Table 3 shows numbers of eight categories of chemicals in differ-
ent extraction phases.
Based on the comparison of the chemical composition of the
three solvent extracts, we found that the most alkaloids, steroidal
and glycosides compounds were present in the ethyl acetate ex-
tract. Six other classes of compounds including terpenes, quinones,
coumarins and lignans, flavone and flavonoid glycoside, miscella-
neous and other miscellaneous compounds were predominant in
the petroleum ether extract. When using n-butanol as the extrac-
tion solvent, no significant advantage was noticed in terms of addi-
tional chemical information.
Conclusions
Several key functional ingredients in peanut stems and leaves
extracts were identified by UPLC separation coupled to QTOF-MSE
detection and automated data processing utilizing traditional med-
1166
icine library. UPLC provides significant benefits over traditional
wileyonlinelibrary.com/journal/jms Copyright © 2016 John Wiley & Sons, Ltd.
L. Deng et al.
Quinones Coumarins Flavone Miscellaneous Others
and lignans and flavonoid
glycoside
5 8 11 21 77
21 19 18 32 101
12 9 12 74
HPLC separations, such as short separation time, higher chromato-
graphic resolution and higher peak capacity. QTOF-MSE provides
exact mass molecular ion and fragment ion information for natural
product component identification and quantification. The integra-
tion of data acquisition, automated data processing and traditional
medicine library automates identification of component structures
in complex natural product samples.
A total of 283 chemical compounds were identified in the ex-
tracts of peanut stems and leaves extracts of which 207 compounds
are being reported for the first time in Genus Arachis. Identified
chemical compounds can be classified into 11 alkaloids, 13 steroi-
dal and glycosides, 30 terpenes, 21 quinones, 19 coumarins and
lignans, 18 flavone and flavonoid glycoside, 32 miscellaneous and
139 other miscellaneous compounds. In the study, we have used
three extractants to handle samples for the overall analysis of the
components of peanut stems and leaves extracts. However, except
the most alkaloids, steroidal and glycosides compounds were pres-
ent in the ethyl acetate extract, six other classes of compounds
were predominant in the petroleum ether extract. N-butanol had
no significant advantage on extracting the chemicals in the extracts
as the extraction solvent. This result has guiding significance for the
further study and application of the peanut stems and leaves in the
biomedical field.
While the peanut stems and leaves extracts consist of hundreds
of chemical components, in this study, compounds with a response
intensity value exceeding 5000 and accurate mass error less than
5 mDa were considered for potential identifications.
Three high content chemical ingredients (5-hydroxy-4′, 7-
dimethoxyflavanone, 2′-O-methylisoliquiritigenin and ferula acid)
were identified in peanut stems and leaves extracts that explicitly
function as sedative and promote sleep. This research finding
strongly correlates with the traditional Chinese medicine viewpoint
that the extracts of peanut stems and leaves can make people calm
down and promote sleep.[13] Additionally, the research findings
provide further insights into the functional components of peanut
stems and leaves to help promote its efficient usage as a traditional
medicine for curing insomnia.
In conclusion, we have demonstrated a simple and efficient
process for the identification of chemical ingredients in complex
natural product samples. The integrated analytical workflow using
UPLC-QTOF-MSE with the UNIFI informatics platform provides
efficient and innovative solutions for separation, detection and
identification of functional compounds in natural products while
greatly improving productivity for research and development of
traditional herbal medicines.
Acknowledgements
The study was supported by the projects as followed: Science and
Technology Innovation Project of Chinese Academy of Agricultural
Sciences (CAAS-ASTIP-201X-IAPPST), China–Argentina Food Science
Technology Center of Chinese Ministry of Science (No. KY201401005),
and National Key R&D Program.
J. Mass Spectrom. 2016, 51, 1157–1167

Chemical ingredients, peanut stems and leaves
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