Analytical Methods

Authentication of lotus root powder adulterated with potato starch and/

or sweet potato starch using Fourier transform mid-infrared
spectroscopy
Jia Liu
a
, Yu Wen
a
, Nan Dong
a
, Chunli Lai
a
, Guohua Zhao
a,b,c,
a
College of Food Science, Southwest University, Chongqing 400715, PR China
b
Key Laboratory of Food Processing and Technology of Chongqing, Chongqing 400715, PR China
c
Chongqing Sweet Potato Engineering and Technology Centre, Chongqing 400715, PR China
a r t i c l e i n f o
Article history:
Received 12 July 2012
Received in revised form 11 December 2012
Accepted 2 May 2013
Available online 12 June 2013
Keywords:
Lotus root powder
Adulteration
Fourier transform mid-infrared
Partial least squares
a b s t r a c t
Fourier transform mid infrared (FT-MIR) spectroscopy combined with chemometrics techniques were
developed for classication and quantication of cheaper starches (potato and sweet potato starch) in
lotus root powder (LRP). By performing principal component analysis (PCA), it was possible to distinguish
between adulterated and non-adulterated LRP. The coefcient of determination (R
2
) and standard devi-
ation ratio (SDR) of calibration set were found to be 0.95870.9898 and 3.6310.2, depending on the pre-
treatment of spectra. The external validation set gave a coefcient of determination (R
2
) and standard
deviation ratio (SDR) of 0.9810 and 5.47, respectively. Moreover, the limit of detection (1%), the limit
of quantication (3%), reasonable recovery (92.3101.5%), satisfactory intra-assay (2.95.5%) and inter-
assay (11.013.5%) precision illustrated the good performance of the present method. The results
obtained in this study indicate that FT-MIR spectroscopy can be used as an easy, rapid and novel tool
to detect the LRP adulterated with cheaper starches.
2013 Elsevier Ltd. All rights reserved.
1. Introduction
With the rapid development of the Chinese economy, the qual-
ity of life and demand for healthy food have improved signicantly.
However, this has brought with an increase in unhealthy practises
in food processing. In recent years, authentication of foodstuff has
posed a major challenge for regulatory agencies. Labelling of prod-
ucts in which high-cost ingredients are substituted for cheaper
ones is a common practise in authentication of products (Rohman
& Che Man, 2011). Thus, to maintain the market order, regulatory
bodies and food processors urgently need rapid methods of con-
rming the authenticity of foods.
Infrared (IR) spectroscopy as an emergent analytical technique
has become a well-accepted method. It is environment-friendly
and does not demand complicated sample preparation procedure
(De Luca et al., 2011). The ngerprints of functional groups in many
compounds enable IR spectroscopy to be widely used in food
and pharmaceutical analysis (Bittnera et al., 2011). However,
broad and overlapping absorption peaks (high dimensions and
complexity) make it complicated to do quantitative analysis with
MIR spectra (Liu, Chen, Dong, Ming, & Zhao, 2012). The modern
multivariate statistical techniques offer greater possibilities to
analysis a very high number of data obtained using different ana-
lytical techniques (De Luca et al., 2011). Partial least-squares
(PLS) regression, for advantages of simplicity and ease of use, is
one of the most widely used calibration models, which has proved
effective in improving model performance in the presence of
linearity (Blanco, Coello, Iturriaga, Maspoch, & Pages, 2000; Wold,
Sjostrom, & Eriksson, 2001).
The combination of IR and chemometric methods in food
adulteration has attracted lots of interests in recent years. It is
widely used in numerous foodstuff adulteration such as adulter-
ating honey with corn syrup, high fructose corn syrup and in-
verted sugar (Gallardo-Velzquez, Osorio-Revilla, Zuiga-de Loa,
& Rivera-Espinoza, 2009); mango juice adulterated with sucrose
(Jha & Gunasekaran, 2010); lard adulteration in cake, chocolate
and chocolate products (Che Man, Syahariza, Mirghani, Jinap, &
Bakar, 2005; Syahariza, Che Man, Selamat, & Bakar, 2005); soya
bean meal adulterated with melamine (Haughey, Graham,
Cancout, & Elliott, 2012); virgin coconut oil adulterated with
corn and sunower oils (Rohman & Che Man, 2011); edible veg-
etable oil adulterated with used frying oil (Zhang et al., 2012);
extra virgin olive oil adulteration with edible and palm oils
(Maggio, Cerretani, Chiavaro, Kaufman, & Bendini, 2010; Rohman
and Che Man, 2010).
0308-8146/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.foodchem.2013.05.155

Corresponding author. Address: College of Food Science, Southwest University,

#1 Tiansheng Road, Chongqing 400715, PR China. Tel.: +86 23 68 25 19 02; fax: +86
68 25 19 47.
E-mail address: zhaogh@swu.edu.cn (G. Zhao).
Food Chemistry 141 (2013) 31033109
Contents lists available at SciVerse ScienceDirect
Food Chemistry
j our nal homepage: www. el sevi er . com/ l ocat e/ f oodchem
Lotus root powder (LRP) is produced from lotus roots. It is
known for helping to improve human health (Niu, Zhao, Jia, & Li,
2012). Besides its main component of starch, LRP is rich in protein,
amino acids, reducing sugars, dietary bre, minerals, beta-caro-
tene, and vitamins. Nowadays, LRP is commercially available in
China and mainly consumed as breakfast and incorporated into
fast food and traditional confectionery as a functional ingredient
(Man et al., 2012). Costs of LRP are high, making it prone to be
adulterated with cheaper starches, such as potato starch and sweet
potato starch in order to increase prots. The traditional methods
to authenticate LRP are impractical due to their dependence on
sensory and microscope and cannot quantify the adulterants.
Meanwhile, there is no information available on the use of IR com-
bined with chemometrics for detection and quantication of adul-
terants in LRP. Therefore, the aim of the present study was to
investigate the feasibility of using Fourier transform mid-infrared
(MIR) spectroscopy as an alternative for quantitative analysis of
LRP adulterated with potato starch and sweet potato starch.
2. Materials and methods
2.1. Materials and regents
Lotus root powder (Youlian Food Co., Ltd. and Chunxiangyuan
Food Co., Ltd.), sweet potato starch (JiaXian Food Co., Ltd. and
Shuangxin Food Co., Ltd.), and potato starch (JingTian Agriculture
Development Co., Ltd. and JiaXian Food Co., Ltd.) were purchased
from a local supermarket. KBr (IR spectroscopy grade) was pur-
chased from Tianjin Guangfu Fine Chemical Research Institute
(Tianjin, China).
2.2. Instrumental analysis and spectral acquisition
2.2.1. Pellet preparation
All samples including lotus root powder, potato starch and
sweet potato starch were dried in an oven (DHG-9140, Qixing,
Shanghai, China) at 45 C overnight. After drying, the samples were
blended with dried KBr powder and pressed into tablets before
measurement. The apparatus used to get the KBr pellet was a tablet
producer (YP-2, ShanYue Scientic Instrument Ltd., Shanghai, Chi-
na) attached to a disc notch model. All tablets were prepared by
mixing dried KBr and sample in a 50/1 (w/w) proportion. 0.2 g of
the prepared mixture was used for each tablet, which was then
put into the sample holder of the FT-IR instrument for spectral
acquisition. Weight measurements were performed on an analyti-
cal balance (BS-223S, Sartorius Instrument System Co., Ltd., Beijing,
China) with a precision of 0.001 g.
2.2.2. Instrumental analysis
The MIR spectra of samples were recorded in transmittance
mode at 4 cm
1
interval over the spectral range from 500 to
4000 cm
1
, using a Perkin Elmer Spectrum 2000 FT-IR Spectrome-
ter with a deuterated triglycine sulphate (DTGS) detector. Spectral
readings were taken in triplicate for each sample and the mean of
these replicates was used in subsequent data analysis. In order to
reduce the noise of the instruments, the collected spectra were ra-
tioned against air as background.
2.3. Chemometric software for data processing and statistical
techniques used
Unscrambler (Version 9.5; Camo Inc., Trondheim, Norway) was
used for data processing. The chemometric procedures include the
following steps.
2.3.1. Calibration and prediction sets
The range of adulterated LRP was covered from 0% to 100%. For
the calibration set, the adulteration proportions were in 116 sam-
ples set as 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% and
100% (w/w). Each proportion in the calibration set from 10% to 95%
was divided into three groups, including (1) LRP adulterated with
potato starch; (2) LRP adulterated with sweet potato starch; (3)
LRP adulterated with equal amount of potato starch and sweet po-
tato starch. To prepare the samples for calibration, LRP from You-
lian Food Co., Ltd. was adulterated with potato starch form
JingTian Agriculture Development Co., Ltd. and sweet potato starch
from Shuangxin Food Co., Ltd. For the validation set, the adultera-
tion proportions in 93 samples were set as 12%, 24%, 32%, 62%, 68%,
72%, 76%, 78%, 84%, 88% and 93% (w/w). Each proportion was also
divided into three groups as described in the calibration set. To
perform an external validation, samples for validation were pre-
pared with LRP from Chunxiangyuan Food Co., Ltd. and adulterated
with potato starch form Shuangxin Food Co., Ltd. and sweet potato
starch from Jiaxian Food Co., Ltd. Additionally, the calibration set
and the external validation set were prepared by different mem-
bers of laboratory personnel.
2.3.2. Principal component analysis (PCA)
MIR spectra of the calibration set were exported from Spectrum
3.0 software in JCAMP DX format and imported into chemometric
software for analysis. PCA was carried out on the pre-treated data
to cluster LRP and adulterated LRP.
2.3.3. Calibration step: cross validation
In the present study, partial least squares (PLS) analysis was
carried out to form linear models of prediction between spectral
data and the amount of adulterated starch in LRP. With the advan-
tage that all of the data available can be used to determine the cal-
ibration model, the leave-one-out cross-validation method was
employed to evaluate the established models (Szydowska-Czer-
niak, 2007; Tavallaie, Talebpour, Azad, & Soudi, 2011). In the cali-
bration set, the spectrum of one sample was randomly removed
and the remaining spectra were used for building a PLS model.
The left-out samples were then predicted by the PLS model. This
procedure was repeated until all the samples had been left out
once.
Once the calculation of the model was over, the leverage was
computed. The leverage is a measure of how far from the centre
an object is compared to the majority value (Shen et al., 2010). It
was used to detect any outlying samples in the original data set.
If the leverage value of the sample was are noticeably different
from the values of the other samples, which implies that it is
noticeably different from other samples, it must be removed (Urb-
ano Cuadrado, Luque de Castro, Perez Juan, & Gomez-Nieto, 2005).
The quality of calibration models were described by the root mean
square error of calibration (RMSEC), the root mean square error of
cross-validation (RMSECV) and the coefcient of determination be-
tween the predicted and the measured parameters in calibration
(R
2
c
), and cross-validation (R
2
cv
). In addition, the standard deviation
ratio (SDR) was also used to measure the precision of the PLS mod-
el from the root mean square (Liu et al., 2012):
SDR r=RMSEP
where r is the standard deviation of the validation set. An SDR va-
lue of 1 means no predictive power (equal to chance); 1.5 means
ability to separate lower from higher values; 2 means an already
reasonable model and above 3 means an excellent model.
In order to improve the reliability, accuracy and stability of
calibration models, it is necessary to preprocess the raw spectra
before analysis. These pre-treatments were done as following
(Gurdeniz & Ozen, 2009; Woodcock, Downey, & ODonnell, 2009):
3104 J. Liu et al. / Food Chemistry 141 (2013) 31033109
(1) Automatic baseline correction.
(2) Automatic smooth processing (9 smoothing points).
(3) Normalisation.
(4) First derivative with different data point gaps (5 pts, 9 pts,
13 pts).
(5) Second derivative with different data point gaps (5 pts, 9 pts,
13 pts).
The optimised model should have lowest RMSECV, highest R
cv
2
value, and highest SDR (Mantanus et al., 2010; Sinija & Mishra,
2009). In the calibration, special consideration was made in choos-
ing the optimal number of PLS factors at the lowest RMSECV
(Camps & Christen, 2009; Felkel, Drr, Glatz, & Varmuza, 2010).
2.3.4. External validation step
For the independent validation of the prediction accuracy of the
MIR calibration model, the external validation set was introduced
in the optimal model by using the LRP adulterated with potato
starch and sweet potato starch from another manufacturer. The re-
sult was evaluated by the root mean square error of prediction
(RMSEP), the coefcient of determination (R
2
) in validation and
the standard deviation ratio (SDR).
2.3.5. Analytical characteristics test
In order to assess the limit of detection (LOD) and limit of quan-
tication (LOQ) of this method, low adulteration proportions (from
9% to 0.5%, w/w) were added to the calibration set one after an-
other. LOD was determined as the lowest adulteration proportion
added to the calibration set, which could be distinguished from
LRP (100%) after PCA analysis. According to the method proposed
by Urbano Cuadrado, Luque de Castro, Perez Juan, and Gomez-Nie-
to (2005), the model shows excellent precision when R
2
P0.90;
good precision when R
2
values from 0.70 to 0.89; good separation
between low, medium, and high values when R
2
values from 0.50
to 0.69. It also shows correct separation between low and high val-
ues when R
2
values from 0.30 to 0.49 and better for no analysing
(analysis) when R
2
values from 0.05 to 0.29. LOQ was determined
as the lowest adulteration proportion added to the calibration
set, which possessed the R
2
c
of the model up to the requirement
for quantitative analysis (R
2
P0.90). The standard deviation ratio
(SDR) was also introduced to measure the precision of the PLS
model from the root mean square: SDR = r/RMSEP where r is
the standard deviation of the validation set. A SDR value of 1 means
no predictive power at all (equal to chance); 1.5 means ability to
separate lower from higher values; 2 means an already reasonable
model and above 3 means an excellent model. Recovery was calcu-
lated using the following equation: (proportion found in sample/
proportion spiked in sample) 100%. Intra-assay relative standard
deviation (RSD) was measured in each proportion in three repli-
cates. Inter-assay relative standard deviation (RSD) was evaluated
on each proportion prepared by 10 laboratory personnel.
3. Results and discussion
3.1. FT-IR spectra of samples
The FTIR spectra and its rst derivative of LRP and cheaper
starches (CS) are presented in Fig. 1(A and B). An extremely broad
band occurs between 3600 and 3000 cm
1.
This is due to the
hydrogen-bonded hydroxyl groups that contribute to the complex
vibrational stretches associated with hydroxyl groups. The band at
2923 cm
1
is characteristic of CH stretches associated with the
ring methene hydrogen atoms. The band at 1640 cm
1
was due
to adsorbed water and bands between 1450 and 1350 cm
1
to
the angular deformation of CH (Policegoudra & Aradhya, 2008).
In the ngerprint region of the spectra of samples, the peaks near
1154 cm
1
and 1081 cm
1
were mainly attributed to CO bond
stretching (Fang, Fowler, Tomkinson, & Hill, 2002). Bands around
900 cm
1
may be due to skeletal stretching vibrations of starch
molecules (Lawal, Lechner, & Kulicke, 2008).
3.2. PCA analysis
Fig. 2(A) shows the score plot of the rst two PCs of PCA which
was carried out by analysing 116 spectra together. PC1 and PC2
respectively account for 69% and 22% of the total variation between
the samples, roughly showed three groups (LRP, LRP adulterated
with CS and CS) in the two-dimensional space probably based on
the type of samples. The LRP was on the negative side of both PC
1 (x-axis) and PC 2 (y-axis), and the CS mostly along the positive
values of PC 1. The adulterated LRP distributed between the LRP
and the CS. LRP adulterated with different CS did not give an appar-
ent regional distribution and it was difcult to discriminate which
kind of CS was adulterated in LRP. However, LRP and adulterated
LRP had no overlaps.
The relationship between the original variables and the load-
ings is usually been checked in order to determine the physical sig-
nicance of the PCs (Gori, Cevoli, Fabbri, Caboni, & Losi, 2012).
Fig. 2(B) shows the PCA loading spectra of the rst two factors,
which account for 91% of the total variation and reveal the features
between the samples. As shown in Fig.3, the highest positive load-
Fig. 1. FTIR spectra of LRP and adulterated LRP (LRP, lotus root powder). (A) FTIR
raw spectra; (B) rst derivative (9 pts) of FTIR spectra.
J. Liu et al. / Food Chemistry 141 (2013) 31033109 3105
ing in PC 1 was found around 900 cm
1
. While, negative loadings
on PC 2 were found between 1750 and 1250 cm
1
and around
900 cm
1
. Bands around 900 cm
1
may be due to skeletal stretch-
ing vibrations of starch which appear to be a major contributor of
PC 1 and PC 2.
3.3. Calibration and validation of the PLS procedure
3.3.1. Optimization of calibration model
Results from the PCA analysis indicate that the obtained spectra
could provide enough information to be used in developing models
Fig. 2. Two-D scores plots (A) and the loading plots (B) of PCA results for 116 samples by PC1 and PC2 (PC, principal component). (w) potato starch; () sweet potato starch;
(j) lotus root powder; (q) lotus root starch adulterated with potato starch; (}) lotus root powder adulterated with sweet potato starch; (4) lotus root powder adulterated
with potato starch and sweet potato starch.
3106 J. Liu et al. / Food Chemistry 141 (2013) 31033109
for authentication of adulterated LRP. In the present study, the full
spectral range of 5004000 cm
1
was applied to determine the
adulteration in LRP. Effects of spectral pre-treatment methods
and the number of PLS factors on the results are discussed in the
study. Before calibration, leverage values were calculated to detect
outliers. If there are samples with leverage values that are notice-
ably different from the values of the other samples, which could be
due to operational errors, they will be considered as abnormal.
They will be examined closely to determine whether they can be
used for developing models or if they must be removed. For each
pre-treatment, the PLS model can be recalculated after the removal
of the outlier. The results with various spectral pre-treatment for
the determination of adulteration in the LRP are summarized in Ta-
ble 1. As can be seen, the worst prediction ability was obtained by
directly using the raw spectra, with R
2
cv
of 0.6563, RMSECV of 21.35
and SDR of 1.67. Calibration differences among different spectral
treatments were very small and good correlations were found be-
tween MIR spectra prediction and adulteration proportion, with a
coefcient of determination in cross validation (R
2
cv
) P0.9587
and SDR P3.63. It was found that taking derivatives of FT-IR spec-
tra effectively improve the R
2
and reduce the RMSECV of the PLS
model. First derivative with 9 pts was chosen as the spectral pre-
treatment method, for providing the lowest RMSECV (3.56), the
highest R
2
cv
(0.9898) and SDR (10.02) for PLS model. The optimiza-
tion of the number of PLS factors was carried out by performing PLS
Fig. 3. RMSECV (root-mean-square error of cross-validation) and R
2
(coefcient of determination) plotted as a function of the number of factors used in the PLS (partial least
squares) model.
Table 1
Results of calibration and validation of the PLS models on the raw spectra and spectra with various pretreatments.
Mathematical pretreatment Outliner PLS factors Calibration Cross-validation SDR
e
R
2 [a]
RMSEC (%)
b
R
2 [c]
RMSECV (%)
d
Raw spectra 5 4 0.6681 20.60 0.6563 21.35 1.67
Spectra pre-treatment
f
3 4 0.9622 6.98 0.9597 7.46 4.78
First derivative (5pts)
f,g
5 4 0.9790 5.22 0.9606 7.03 5.07
First derivative (9 pts)
f,g
5 4 0.9924 3.11 0.9898 3.56 10.02
First derivative (13 pts)
f,g
4 4 0.9845 4.47 0.9681 6.56 5.44
Second derivative (5 pts)
f,g
6 4 0.9867 4.19 0.9789 5.40 6.60
Second derivative (9 pts)
f,g
5 4 0.9844 4.51 0.9723 6.27 5.69
Second derivative (13pts)
f,g
2 4 0.9838 4.59 0.9587 9.82 3.63
a
Coefcient of determination in calibration.
b
Root-mean-square error of calibration.
c
Coefcient of determination in cross-validation.
d
Root-mean-square error of cross-validation.
e
Standard deviation ratio of cross-validation.
f
Pre-treatments of spectra include automatic baseline correction, automatic smooth processing and normalisation.
g
Pts, different data point gaps.
Fig. 4. MIR predicted values vs. adulteration proportion (%) in the calibration set
(s) and external validation set (N).
J. Liu et al. / Food Chemistry 141 (2013) 31033109 3107
models in which 15 PLS factors had been introduced. Many studies
had optimised this number in order to create a reliable model (Al-
Mbaideen & Benaissa, 2011; Mantanus et al., 2010). Fig.3 shows
the RMSECV and R
2
values plotted as a function of PLS factors for
determining adulteration in the LRP with rst derivative (9 pts)
as the pre-processing technique. As seen from Fig. 3, RMSECV value
decreases sharply with initial four PLS factors. However, RMSECV
value remains relatively stable (3.56 to 2.47) from 4 to 15 PLS fac-
tors. Thus, the optimal number of PLS factors was set as 4.
3.3.2. External validation
In order to verify the accuracy of the established PLS model, the
external validation of the method was carried out with the valida-
tion set. All samples in the validation set were predicted by the
optimal PLS model obtained by retraining on all of the 209 samples
and the results were shown in Fig. 4. The optimal PLS model with 4
PLS factors yielded satisfactory performance with a high value of R
2
(0.9810) and a satisfactory value of SDR (5.47) in external valida-
tion. It is clear that the mid-infrared (MIR) spectroscopy combined
with PLS method is a powerful technique to quantitatively authen-
ticate LRP adulterated with potato starch and sweet potato starch.
3.4. Analytical characteristics of this method
PCA was carried out by adding low adulteration proportions
(from 9% to 0.5%, w/w) to the calibration set one after another.
After PCA analysis, all low adulteration proportions (from 9% to
1%) could be distinguished from LRP (100%) except 0.5% adultera-
tion proportion. Therefore, the limit of detection (LOD) of this
method was 1%. R
2
c
and it remained stable during the addition of
low adulteration proportion (from 9% to 3%) to calibration set.
However, R
2
c
decreased dramatically and was lower than 0.9 after
the addition of 2% adulteration proportion to calibration set. Thus,
it was reasonable to say that the limit of quantication (LOQ) of
this method was 3%. The intra-assay relative standard deviation
(RSD) measured on each proportion prepared by three replicates
was relatively low (2.95.5%); and the inter-assay precision evalu-
ated on each proportion prepared by 10 laboratory personnel pro-
vided RSD values in the range of 11.013.5%. Adulteration
proportion and MIR predicted values (Table 2) were in agreement,
with a recovery between 92.3% and 101.5%. Consequently, this
method had a very good level of repeatability and sensitivity.
4. Conclusions
It can be concluded that Fourier transform mid-infrared (FT-
MIR) combined with partial least squares (PLS) can be applied in
monitoring the adulteration of LRP with potato starch and sweet
potato starch. The raw spectra at frequencies of 5004000 cm
1
were similar, with small differences in absorbance intensity among
LRP, potato starch and sweet potato starch. However, the poor ana-
lytical differences in the IR spectra were amplied by applying the
derivative pre-treatment on the original data. The successful appli-
cation of the optimal model proved the ability of the chemometric
techniques applied on IR spectra for qualitative and quantitative
determination of LRP adulterated potato and sweet potato starch.
The dis-advantages of the work reported here are still obvious
compared with traditional methods, for example, (1) sample pre-
treatment before MIR spectra collection and calibration building
is relatively complex; (2) MIR equipment is expensive.
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Table 2
Analytical characteristics of the proposed method.
Parameters LRP concentration (%)
a
12 24 68 78 93
LOD (%)
b
1
LOQ (%)
c
3
Recovery (%)
d
92.6 5.4 92.3 6.9 98.5 1.6 97.6 3.8 101.5 1.5
Intra-assay RSD (%)
e
5.5 5.4 2.9 3.6 4.0
Inter-assay RSD (%)
f
13.5 13.5 12.1 11.0 13.2
a
LRP, lotus root powder.
b
Limit of detection (LOD) was determined as the lowest adulteration proportion added to the calibration set, which could be distinguished from LRP (100%) after PCA
analysis.
c
Limit of quantication (LOQ) was determined as the lowest adulteration proportion added to the calibration set, which possessed the R
2
c
of the model up to the
requirement for quantitative analysis (R
2
P0.90).
d
Recovery was calculated from following equation: (proportion found in sample/proportion spiked in sample) 100%.
e
Intra-assay relative standard deviation (RSD) was measured on each proportion in three replicates.
f
Inter-assay relative standard deviation (RSD) was evaluated on each proportion prepared by 10 laboratory personnel.
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