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Journal of Pharmaceutical and Biomedical Analysis 111 (2015) 16

Contents lists available at ScienceDirect

Journal of Pharmaceutical and Biomedical Analysis


journal homepage: www.elsevier.com/locate/jpba

Chemometric analyses for the characterization of raw and processed


seeds of Descurainia sophia (L.) based on HPLC ngerprints
Xidan Zhou a , Liying Tang a , Hongwei Wu a , Guohong Zhou a , Ting Wang a , Zhenzhen Kou a ,
Shunxin Li b , Zhuju Wang a,
a
b

Institute of Chinese Materia Medica, China Academy of Chinese Medical Science, Beijing 100700, China
Department of Chinese Medicine, Nanyang Medical College, Nanyang, Henan 473000, China

a r t i c l e

i n f o

Article history:
Received 6 December 2014
Received in revised form 5 March 2015
Accepted 8 March 2015
Available online 17 March 2015
Keywords:
Descurainia sophia (L.)
High-performance liquid chromatography
with diode array detector ngerprints
Multivariate statistical analysis
Processing mechanism
Plantago depressa Willd

a b s t r a c t
The seeds of Descurainia sophia (L.) (short for DSS below), with a long history of medicinal utilization in
China, have attracted the attention of many Chinese medicine practitioners for the potent efcacy. In the
present study, the raw and processed DSS were differentiated by several chemometrics methods based
on HPLC ngerprints. Moreover, peaks which were mainly responsible for the differentiation between
raw and roasted DSS were found. Therefore, the method of the chromatographic ngerprints combined
with multivariate statistical analysis was effective and reasonable in orientating chemical constituents
which were mainly responsible for the differentiation between raw and roasted materials, thus shedding
light on illustrating the processing mechanism. Whats more, this method can also be applied in the
identication of authenticity.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Descurainia sophia (L.) Webb ex Prantl, an annual dicot belonging
to family Brassicaceae (Cruciferae), has been used in folk medicines
for the treatment of throat diseases, measles and smallpox in the
middle Asia [1,2]. In China, its seeds (DSS) have been extensively
exploited to relieve cough, prevent asthma, reduce edema and promote urination for thousands of years [3,4]. However, parallel to
most Chinese medicinal herbs, DSS have been encountering the
challenges of varietal complexity and counterfeit incorporation. In
view of the morphological specicity and high similarity of adulterants, it seems inaccessible that either morphological characteristics
or microscopic characteristics could be able to distinguish them
accurately and handily.
Currently, the chromatographic ngerprint technique plays an
important role in the quality control of Chinese medicinal herbs,

Abbreviations: DAD, diode array detector; DSS, the seeds of Descurainia sophia
(L.); HCA, hierarchical cluster analysis; PCA, principle components analysis; PLSDA, partial least squares discriminant analysis; PDS, the seeds of Plantago depressa
Willd.; RDSS, the roasted seeds of Descurainia sophia (L.); TCM, traditional Chinese
medicine.
Corresponding author at: Institute of Chinese Materia Medica, China Academy
of Chinese Medical Science, No. 16 Nanxiaojie, Dongzhimennei Ave., Beijing 100700,
China. Tel.: +86 10 64033301; fax: +86 10 64033301.
E-mail address: wangzhuju@sina.com (Z. Wang).
http://dx.doi.org/10.1016/j.jpba.2015.03.010
0731-7085/ 2015 Elsevier B.V. All rights reserved.

which can systematically characterize the constituents of samples


and focus on the identication and assessment of the components
[5]. Due to the complexity and world-wide applicability of Chinese
herbs, chromatographic ngerprinting has been accepted internationally as a strategy to assess the quality of such substances [6].
In this paper, HPLC-DAD was applied to construct the chromatographic ngerprints.
Processing is a characteristic pharmaceutical skill which signicantly discriminates western medicine from Chinese medicine.
Proper processing may remove or reduce the toxicity, drastic properties and side effects, promote therapeutic effects and modify the
nature and action. Hence, in order to guarantee the safety and effectiveness, it is signicant and necessary to control and regulate the
quality of processed products. As for DSS, due to the drastic effects
and potential side-effects in the case of raw DSS, processed DSS
have been dominating in clinical application [7]. As described in
the textbook, the raw DSS are usually indicated for ascites and
hyposarca while the roasted DSS are mainly used for cough and
dyspnea because roasting can moderate the extremely cold nature
and protect lung from drastic damage [8]. Thus, it is necessary to
discriminate raw and roasted DSS in clinical practice. Recently,
chemometrics have been increasingly applied to the botanical
and geographical characterization and authentication of food and
medicine [918]. In this study, HPLC ngerprints of the raw and
roasted DSS were compared, and the ngerprint data sets were
submitted for classication to several chemometrics methods, such

X. Zhou et al. / Journal of Pharmaceutical and Biomedical Analysis 111 (2015) 16

as principle components analysis (PCA), hierarchical cluster analysis (HCA) and partial least squares discriminant analysis (PLS-DA).
According to the statistical results combined with the chromatographic ngerprints, peaks responsible for discrimination between
raw and processed DSS were found and how they change in the
course of processing was also analyzed.
As mentioned above, there are plenty of adulterants of DSS in
medicinal markets. Meanwhile, DSS are mixed with the seeds of
other medicinal herbs as a result of the huge price difference [19].
In this study, HPLC ngerprints from the seeds of Plantago depressa
Willd. (PDS) were also obtained to compare with that of DSS, and
HCA was also conducted to differentiate them. Moreover, in order
to explore the inuence on the quality of PDS caused by varying
adulterating degree, chromatographic ngerprints of mixtures of
different proportions of DSS and PDS were performed.
2. Materials and methods
2.1. Materials and reagents
21 batches of raw DSS were purchased from different Chinese
medicinal herbs suppliers in the Chinese herbal medicine market
located in Bozhou, Anhui Province (Samples 19) and Anguo, Hebei
Province (Samples 1021), and authenticated by professor Suiqing
Chen, Department of Pharmacognosy of Henan University of TCM.
Then, RDSS (Samples 2235) were produced by roasting raw DSS
(chosen randomly from 21 batches of raw samples) according to the
processing method described in Chinese Pharmacopeia. In addition, 10 batches of PDS (Samples 3645) were obtained from the
Chinese herbal medicine market in Anguo where these seeds have
been found occasionally mixed with DSS. After the careful identication and authentication of these 10 batches of samples based
on their difference in morphological and microscopic characteristics, it turned out that only samples 38, 44, 45 were unadulterated
while the remaining were more or less mingled with DSS. All the
samples were stored in a dry ambience at constant temperature to
minimize any changes through degradation, and all the raw and
roasted voucher specimens were deposited in institute of Chinese
Materia Medica, China Academy of Chinese Medical Science.
Phosphoric acid (guaranteed reagent) was purchased from
Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China). Acetonitrile and methanol for HPLC analysis were supplied by
ThermoFisher Scientic Inc. (Shanghai, China). The water used
was ltered with the solvent lter (Tianjin Jinteng Experiment
Equipment Co., Ltd., Tianjing, China).
2.2. Sample preparation
The tested samples were crushed into powder with a pulverizer
for 1 min, and passed through a 65 m-mesh sieve. Each sample powder (1.0 g) was weighed accurately and reuxed in 20 mL
80% methanol solution for 30 min. The residue was sifted from the
extract, then this solution was ltered with a 0.45 m microporous
membrane, and a 5 L aliquot of the ltrate was injected for HPLC
analysis. The extract solutions of all the samples were summited
for HPLC analysis within 24 h after preparation to maintain the
samples stability.
2.3. Chromatographic conditions
All HPLC analyses were performed with a Dionex U-3000
series (Shanghai, China) equipped with a SR-3000 Solvent Rack,
a LPG-3400SDN Quaternary Pump, a WPS-3000SL Auto sampler,
an injector with a 100 L loop, a TCC-3000RS Column compartment, a DAD-3000RS detector and Chromeleon 7 chromatography
workstation. A Thermo Scientic Acclaim TM 120-C18 column

(4.6 mm 250 mm, 5 m) (Shanghai, China) was used. The mobile


phase consisted of 1% phosphoric acid (A) and acetonitrile (B).
The gradient program was developed as follows: 1014% B for
012 min, keep 14% B for 1218 min, 1419% B for 1830 min, stay
19% B for 3035 min, 1925% B for 3540 min, maintain 25% B for
4050 min, 2540% B for 5051 min, and nally hold 40% B for
5155 min. The ow rate was kept at 1.0 mL/min and the column
temperature was maintained at 30 C. The injection volume was
5 L and the detective wavelength was selected at 330 nm.
2.4. Methodology validation
All tests below were carried out on the raw DSS extract solutions
prepared as described in Section 2.2. The precision was determined
by replicating HPLC injections of the same sample solution 6 times
per day. Six independent samples were extracted and analyzed
in parallel for the evaluation of repeatability. The stability was
assessed by measuring a single sample solution stored at room
temperature for 0 h, 2 h, 4 h, 8 h, 16 h, and 24 h.
2.5. Data analysis
HPLC chromatographic data of the 45 tested samples were integrated automatically and exported as *.AIA format les for further
processing. First, the *.AIA les were imported into the similarity
evaluation system for chromatographic ngerprint of TCM (Version
2004 A) (Committee for the Pharmacopeia of PR China.). A reference
sample was selected stochastically from the most representational
ones among the middle of analysis sequence to generate a template. Then, all of the samples were overlaid based on the template,
and common peaks were rstly aligned to the ones in the template.
The relative retention time (RRT) and relative peak area (RPA) were
calculated simultaneously and can be exported as an excel le for
further statistical analysis. HCA and PCA were obtained by SPSS
16.0, and PLS-DA was conducted by the SIMCA-p 13.0 software
program.
3. Results and discussion
3.1. Optimization of extraction conditions
In order to obtain satisfactory extraction efciency, the
extraction methods (reuxing, ultrasonic and cold-macerating
extraction), extraction solvents (20% methanol, 40% methanol, 60%
methanol, 80% methanol and 100% methanol) and extraction time
(0.5 h, 1 h, 1.5 h, 2 h, and 2.5 h) were optimized by using univariate
test. The result indicated that reuxing extraction was more effective than ultrasonic extraction and cold-macerating extraction. It
was also found that 80% methanol was the most efcient extraction solvent among the tested different concentrations of methanol.
In addition, it was demonstrated that most components could be
extracted completely within 0.5 h. Finally, the sample solutions
were prepared by reuxing extraction with 20 mL 80% methanol
for 0.5 h.
3.2. Optimization of chromatographic conditions
Mobile phases, such as methanolwater, acetonitrilewater,
methanolacid aqueous solution, and acetonitrileacid aqueous
solution, were examined and compared to obtain good chromatographic behavior. As a result, acetonitrileacid aqueous solution
was better than others. Moreover, different kinds of acid aqueous
solutions (formic acid, acetic acid and phosphoric acid) were also
compared, it was demonstrated that phosphoric acid was more
helpful to improve the peak shape and resolution of many peaks.
Last, different concentrations of phosphoric acid (0.2%, 0.5%, 0.8%,

X. Zhou et al. / Journal of Pharmaceutical and Biomedical Analysis 111 (2015) 16

Fig. 1. The chromatographic ngerprints of DSS and PDS samples: (A) DSS; (B) RDSS; (C) PDS sample 43 and (D) PDS sample 45.

and 1%) were compared, and the data indicated that the optimal
condition was acetonitrile1% phosphoric acid aqueous solution.
3.3. Methodology validation
RRT and RPA of ten characteristic peaks were calculated for
the estimation of precision, repeatability and stability, and the
results were as follows: precisionthe relative standard deviations (RSD) of RRT and RPA were found not to exceed 0.41% and
2.69% respectively; repeatabilitybelow 0.19% and 2.77% respectively; and stabilityless than 0.27% and 4.04% respectively. Thus,
all results indicated that the quality of the studied samples and the
HPLC-DAD measurements were stable and under control.

3.4. HPLC ngerprints of DSS, RDSS and PDS


45 batches of samples included 21 DSS, 14 RDSS and 10 PDS, and
their corresponding chromatographic ngerprints were recorded
at 330 nm, which were showed in Fig. 1. For the chromatographic
ngerprints of DSS and RDSS, it can be intuitively seen that many
chromatographic peaks changed to varying degrees. For example,
several peaks (25, 21) areas declined obviously, and even peaks 28,
41 disappeared after processing. On the contrary, many peaks, such
as 4, 22, 24, 26, 32 and 33, were present in the RDSS.
When it comes to the chromatographic ngerprints of 10 PDS, it
was apparent that the chromatographic ngerprints of samples 38,
44, 45 were different from that of the remaining samples because

Fig. 2. (A) HCA of DSS and RDSS samples and (B) HCA of DSS and PDS samples.

X. Zhou et al. / Journal of Pharmaceutical and Biomedical Analysis 111 (2015) 16

of the great variance of the existing conditions of ve main peaks


(13, 16, 18, 20, 25) located in 717 min, which were precisely the
characteristic and common peaks of DSS. In accordance with the
identication result above, chromatographic ngerprints also provided more accurate and intuitive evidence.
3.5. HCA for identication of DSS and RDSS, DSS and PDS
HCA is a means of structuring a complex set of observations
into unique, mutually exclusive groups (clusters) of subjects similar to each other with respect to certain characteristics [20,21].
HCA results of DSS and RDSS were showed in Fig. 2A. In a whole, it
was evident that DSS and RDSS samples were clearly clustered into
two groups, which means that the processing procedures caused
changes in the composition and/or content of components in DSS.
As for DSS and PDS, the HCA result (Fig. 2B) also conrmed the
obvious difference obtained by the chromatographic ngerprints
directly, which perspicuously classied 10 PDS samples into two
groups: 38, 44, 45 and the remaining samples.
3.6. PCA for identication of DSS and RDSS
Specically, PCA takes a data matrix of n objects by p variables,
which may be correlated, and summarizes it by uncorrelated axes
(principal components) that are linear combinations of the original
p variables [22,23]. To achieve a balance between clarity of representation and oversimplication, 52 peaks (variables), which were
present in at least 10 samples, were selected to conduct statistical
analysis. The PC1 versus PC2 biplot (Fig. 3) accounted for 57.38%
data variance (PC1 = 45.80%, PC2 = 11.58%), and two clusters of DSS
and RDSS were identied. The RDSS objects with relatively high

Fig. 3. PCA biplots PC1-PC2 (57.38% data variance explained) of DSS and RDSS samples (the red circles represent 52 variables; the blue circles stand for 35 samples).
(For interpretation of the references to color in this gure legend, the reader is
referred to the web version of this article.)

positive scores on PC1, grouped together fairly tightly, while most


DSS objects bunched together with negative PC1 scores. On PC2, the
two groups both had positive and negative scores. Thus, DSS were
discriminated from RDSS on PC1. According to the contributions to
PC1 of all variables, it can be easily seen that many variables were
responsible for the composition of PC1, among them peaks 4, 26,
24, 22 and 25 featured strongly in identifying DSS and RDSS.

Fig. 4. (A) PLS-DA score scatter plot of DSS and RDSS samples; (B) PLS-DA loading scatter plot of DSS and RDSS samples; (C) VIP (variable importance for the project) plot of
PLS-DA of DSS and RDSS samples.

X. Zhou et al. / Journal of Pharmaceutical and Biomedical Analysis 111 (2015) 16

Fig. 5. Chromatographic ngerprints of PDS mixed with different percentages of DSS (S1: 100% PDS; S2: 10% DSS + 90% PDS; S3: 20% DSS + 80% PDS; S4: 30% DSS + 70% PDS;
S5: 40% DSS + 60% PDS; S6: 50% DSS + 50% PDS; S7: 60% DSS + 40% PDS; S8: 70% DSS + 30% PDS; S9: 80% DSS + 20% PDS; S10: 10% DSS + 90% PDS; S11: 100% DSS).

3.7. PLS-DA for identication of DSS and RDSS


As a supervised recognition pattern, PLS-DA can maximize the
difference among the groups and aid in the screening of the markers
responsible for class separation rather than explaining the variations within a data set [24,25]. In order to nd the potential
components for the discrimination between DSS and RDSS, PLSDA was also performed. First, a reasonably good separation of DSS
and RDSS was obtained in the scatter plot (Fig. 4A), which displayed
how 35 observations were situated with respect to each other and
showed the possible presence of outliers, groups, similarities and
other patterns in the data.
Moreover, the loading scatter plot (Fig. 4B) was also conducted,
which displayed the relation between the X-variables (52) and
the dummy Y-variables (2). By default, X-variables situated in the
vicinity of the Y-variables have the highest discriminatory power
between the classes. As showed, variables 25, 4, 26, 24, stand close
to the Y variables and far from the origin, guring that such variables
were strongly responsible for discrimination.
In order to weigh the effect of importance of every variable on
discrimination, the VIP (variable importance for the project) plot
(Fig. 4C) was performed, which summarized the importance of the
variables both to explain X and to correlate to Y. According to the VIP
plot, many variables had VIP-values larger than 1, which meant that
these variables were primarily responsible for the discrimination.
Among them, 26, 24, 4, 25, 32, 22 had the largest VIP-values, keeping consistent with the analytical result above. With R2X = 0.528,
R2Y = 0.989, Q2 = 0.976, the PLS-DA model was demonstrated to t
the data and predict new data well.
3.8. The establishment of chromatographic ngerprints of
mixtures of different proportions of DSS and PDS
Although microscopic identication was efcient in discriminating DSS from PDS, the application of the technique has still
limited because of its failure to provide valid information on quantication. Thus, chromatographic ngerprints of PDS mixed with
different percentages of DSS were performed, ranging from 10% to
90%. As it is seen from Fig. 5, the chromatographic peaks of PDS were
clustered together after 30 min, while the peaks of DSS were mainly
distributed in 520 min range. When more than 30% DSS was

incorporated into PDS, the front peaks belonging to DSS have gradually become the main and strong peaks. Consequently, these
samples were likely to produce completely different medicinal
effects from those pure PDS when applied in clinic. As a result, it
is necessary to establish the chromatographic ngerprints of mixtures of different proportions of DSS and PDS. That will provide
varying adulterating degree for reference more intuitively and
accurately.

4. Conclusion
In summary, whether the unsupervised HCA and PCA or supervised PLS-DA, both proved to be satisfactory for matching and
discriminating the chromatographic ngerprints of DSS and RDSS.
The results of PCA and PLS-DA indicated that peaks 26, 24, 4, 25,
22, 32 played dominating roles. Obviously, many new components
emerged after roasting. The accurate orientation of these peaks
makes it possible to explain the dissimilarity of efcacy fundamentally, shining a spotlight for revealing processing mechanism.
Similarly, this method can also be applied in the identication of
authenticity, which can detect the divergence among every sample more effectively and precisely, making up for the subjectivity
of morphological identication and inconvenience of microscopic
identication. The developed method was demonstrated to be simple, sensitive and reproducible, and will be widely adapted to other
Chinese medicinal herbs.

Acknowledgments
The authors are grateful to professor Suiqing Chen for authentication of all the samples.

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