Food Chemistry 375 (2022) 131887

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Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Fluorescence quenching by competitive absorption between solid foods:

Rapid and non-destructive determination of maize flour adulterated in
turmeric powder
Jing-Ya Xie , Jin Tan *, Shu-Hua Tang , Ying Wang
Tianjin Key Laboratory of Food Biotechnology, College of Biotechnology and Food Science, Tianjin University of Commerce, Tianjin 300134, People’s Republic of China

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

Keywords: Fluorescence quenching induced by competitive absorption between different components of solid foods was
Fluorescence quenching observed for the first time. By using front-face synchronous fluorescence spectroscopy (FFSFS) and fluorescence
Competitive absorption titration, competitive absorption between maize flour and turmeric powder was proven to occur between
Turmeric
phenolic acids in maize flour and curcumin in turmeric powder. FFSFS was applied for the rapid and non-
Maize
Adulteration
destructive determination of maize flour adulterated in turmeric powder. Prediction models were constructed
Front-face synchronous fluorescence by partial least square (PLS) regression based on unfolded total synchronous fluorescence spectra, and were
spectroscopy (FFSFS) validated by five-fold cross-validation and external validation, with the determination coefficient of prediction
(Rp2) greater than 0.95, root mean square error of prediction (RMSEP) < 6%, relative error of prediction (REP) <
15% and residual predictive deviation (RPD) greater than 5. The limit of detection (LOD) of maize flour was
approximately 9%. In addition, most relative errors for test samples were from − 20% to 20%.

1. Introduction component in curry. The bright orange-yellow color of turmeric origi­

Spices and herbs are important food ingredients that contribute
amazing aroma and taste to our daily meals. However, spices, especially
those in powder form, are among the several kinds of foods that are most
prone to adulteration (Danezis, Tsagkaris, Brusic, & Georgiou, 2016;
Oliveira, Cruz-Tirado, & Barbin, 2019). The major motivation of such
kind of food fraud is the high market demand and price of spices (Oli­
veira, Cruz-Tirado, & Barbin, 2019; Galvin-King, Haughey, & Elliott,
2018; Osman, Raman, Haider, Ali, Chittiboyina, & Khan, 2019). The
long and complex industry supply chain of powdered spices, which can
cross over many countries, makes them highly susceptible to food fraud
(Oliveira, Cruz-Tirado, & Barbin, 2019; Galvin-King, Haughey, & Elliott,
2018). For a long time, tremendous efforts have been continuously paid
to the authentication of various kinds of powdered spices (Mei, Zhao,
Xu, & Huang, 2021; Oliveira, Cruz-Tirado, & Barbin, 2019; Galvin-King,
Haughey, & Elliott, 2018; Osman, Raman, Haider, Ali, Chittiboyina, &
Khan, 2019; Reinholds, Bartkevics, Silvis, van Ruth, & Esslinger, 2015;
Kucharska-Ambrożej & Karpinska, 2020).
Turmeric (Curcuma longa L.) is an Indian perennial herb of the ginger
family with a large aromatic yellow rhizome. Prepared from processed
turmeric rhizomes, turmeric powder is an essential spice and the major
nates from curcuminoids (comprising curcumin (Cur), demethox­
ycurcumin and bisdemethoxycurcumin, among which Cur is the
predominant one), the main natural bioactive components in turmeric.
Cur molecule is composed of two aromatic rings containing o-methoxy
phenolic groups connected by a seven-carbon linker consisting of an
α,β-unsaturated β-diketone moiety (see the inset of Fig. 1). The content
of curcuminoids in turmeric rhizomes can be as high as 2–9% w/w
(Priyadarsini, 2014; Jayaprakasha, Rao, & Sakariah, 2002). While the
Cur concentrations in commercial turmeric powders are reported to be
1–6% w/w (Jayaprakasha, Rao, & Sakariah, 2002; Tayyem, Heath, Al-
Delaimy, & Rock, 2006). As turmeric powder is extensively traded in
its ground form, it has been persistently vulnerable to adulteration
(Osman, Raman, Haider, Ali, Chittiboyina, & Khan, 2019). Several
possible adulterants for turmeric powders are powders of other species
of Curcuma (Sasikumar, Syamkumar, Remya, & Zachariah, 2004; Chao
et al., 2020), foreign starch (Kar, Tudu, Jana, & Bandyopadhyay, 2019;
de Macêdo et al., 2021; Khodabakhshian, Bayati, & Emadi, 2021), maize
flour (Oh & Jang, 2020) and synthetic dyes such as Sudan dye (Chao
et al., 2020; Khodabakhshian, Bayati, & Emadi, 2021), metanil yellow
(Kar, Tudu, Bag, & Bandyopadhyay, 2018; Khodabakhshian, Bayati, &
Emadi, 2021) and lead chromate (Erasmus, van Hasselt, Ebbinge, & van

* Corresponding author.
E-mail address: tanjin@tjcu.edu.cn (J. Tan).

https://doi.org/10.1016/j.foodchem.2021.131887
Received 17 September 2021; Received in revised form 2 December 2021; Accepted 15 December 2021
Available online 18 December 2021
0308-8146/© 2021 Elsevier Ltd. All rights reserved.
J.-Y. Xie et al.
Ruth, 2021; Paranthaman, Moses, & Anandharamakrishnan, 2021).
For food authentication, non-targeted fingerprinting techniques
including several vibrational spectroscopic techniques such as near-
infrared (NIR), infrared (IR) and Raman spectroscopies have been
demonstrated to be powerful alternatives to traditional targeted analysis
and microscopic identification (Reinholds, Bartkevics, Silvis, van Ruth,
& Esslinger, 2015; Kucharska-Ambrożej & Karpinska, 2020). Concern­
ing the authentication of turmeric powder, a number of spectroscopic
methods continue to be developed (Kar, Tudu, Bag, & Bandyopadhyay,
2018; Kar, Tudu, Jana, & Bandyopadhyay, 2019; Gad & Bouzabata,
2017; Chao et al., 2020; de Macêdo et al., 2021; Khodabakhshian,
Bayati, & Emadi, 2021; Erasmus, van Hasselt, Ebbinge, & van Ruth,
2021).
Except the aforementioned vibrational spectroscopic techniques,
fluorescence spectroscopy owning the renowned advantages of
simplicity, rapidity, selectivity and versatility has shown great potential
in the authentication of various kinds of foods and beverages (Karoui &
Blecker, 2011). It is especially worthy to mention that the front-face
geometry of fluorescence spectroscopy directly measures the fluores­
cent excitation and emission on the surface of samples, circumvents the
inner-filter effect happened in concentrated and opaque samples, and is
hence particularly suitable for bulk food samples (Boughattas, Le Fur, &
Karoui, 2019; Hassoun & Karoui, 2015; Sikorska et al., 2019; Lenhardt,
Zeković, Dramićanin, Dramićanin, & Bro, 2014; Włodarska, Pawlak-
Fig. 1. Contour maps for the total front-face synchronous fluorescence spectra in scope 1 (λex = 250–600 nm and Δλ = 30–200 nm) of (a) a typical turmeric powder
sample, (b) a typical maize flour sample, (c) pure solid Cur, (d) pure solid FA, (e) the turmeric powder spiked with 3% w/w Cur and (f) the maize flour spiked with
0.1% w/w FA. The molecular structures of Cur and FA are shown in insets.
2
Food Chemistry 375 (2022) 131887
Lemańska, Khmelinskii, & Sikorska, 2017; Zeković, Lenhardt, Dram­
ićanin, & Dramićanin, 2012). Our recent study in this field is the utili­
zation of front-face synchronous fluorescence spectroscopy (FFSFS) for
the analysis of free capsanthin in chili powders (Tan, Li, Li, Jiang, Tang,
& Wang, 2021). We have found that some native fluorophores in solid
foods can be employed for authentication purpose and our recent focus
shifts to the disclosing of some unusual fluorescent behaviors of certain
intrinsic fluorophores in solid food matrix.
Although the fluorescence spectroscopy of various kinds of foods has
been deeply investigated, the fluorescent property of turmeric has not
been revealed and utilized. Induced by diverse mechanisms, fluores­
cence quenching has become an important approach to inspect inter­
molecular interactions. It has been extensively studied both as a
fundamental phenomenon and as a source of information about
biochemical systems (Lakowicz, 2006). Herein, we examined the FFSFS
properties of turmeric powder, and maize flour, one of its potential
adulterants, and their binary blends at different ratios as well. The
fluorescence quenching between different components of solid foods
was observed for the first time and it was revealed to originate from the
competitive absorption between Cur in turmeric powder and phenolic
acids in maize flour. Based on such findings, we took full advantage of
the facility of FFSFS and the unique characteristics of competitive ab­
sorption induced fluorescence quenching to propose a novel strategy for
the rapid and non-destructive determination of maize flour adulterated
J.-Y. Xie et al.
in turmeric powder. To the best of our knowledge, neither the obser­
vation of fluorescence quenching between different components of solid
foods nor its application to food authentication has been reported.
2. Materials and methods
2.1. Chemicals and samples
Cur, ferulic acid (FA) and ethanol of analytical grade were obtained
from Guangfu fine chemical reagent co. (Tianjin, China). Stock solutions
of Cur and FA in ethanol were prepared and kept at 4 ◦ C in the dark, and
were stable within one week. Their working solutions at different con­
centrations for the study of their UV–visible absorption and fluorescence
spectroscopy were freshly prepared by the dilution of the stock solutions
with ethanol.
Six commercial brands of turmeric powder originating from Henan,
Shandong, Jiangsu, Yunan, Sichuan provinces of China and Myanmar,
two fresh raw turmeric rhizomes from Sichuan and Guangxi provinces of
China, and five commercial brands of maize flour from Henan, Shan­
dong, Liaoning and Heilongjiang provinces of China were purchased
from online markets. Owing to limited commercial availability espe­
cially under the background of COVID-19, these were almost all the
samples that we could collect. The authenticity of these samples was
guaranteed by the certified manufacturers and online sellers. All the
obtained samples were kept at 4 ◦ C in the dark.
Prior to analysis, the fresh raw turmeric rhizomes were dried and
ground into powders by an IKA M20 universal mill (IKA, Königswinter,
Germany). All the commercial and ground turmeric powders and maize
flours were passed through a sieve (mesh 180 µm) and dried in an oven.
Four turmeric powder samples and one maize flour sample were
randomly selected to build calibration models, while the other left
samples (four turmeric powders and four maize flours) were used to
simulate blind samples to estimate the real applicability of the method.
Binary blends containing turmeric powder and maize flour at
different ratios were prepared by mixing each brand of turmeric powder
and the maize flour in training set with the proportions of the maize
flour in the mixtures from 0 to 95% w/w. The steps were 1% and 5% in
the range of 1–3% and 5–95%, respectively (together 22 percentage
levels). All the obtained binary mixtures were thoroughly stirred and
vortexed to ensure homogeneity. Consequently, a total of 88 adulterated
turmeric powder samples were obtained (4 turmeric powders × 22
percentages). Besides, several blends with the proportions of maize flour
larger than 95% (98, 99 and 99.8%) were also formulated to fully
investigate the interaction between turmeric powder and maize flour.
These blends were not involved in model construction. To track the
fluorescent compounds in turmeric powder and maize flour, a turmeric
powder spiked with 3% Cur and a maize flour spiked with 0.1% FA were
also fabricated by adding aliquots of solid Cur and FA into a typical
turmeric powder and maize flour, respectively.
Two external test sets were formulated to evaluate the reliability of
the built models. Nine spiked turmeric powder samples were prepared
from four turmeric powder and one maize flour samples that were used
to build the calibration models. Different proportions of maize flour
were added into the turmeric powder samples. Spiked proportions were
diverse to cover high, medium and low levels from 12 to 82%. In
addition, simulated blind samples were fabricated by the left four
turmeric powder and four maize flour samples that were not involved in
model construction. Eight pairs of turmeric powder and maize flour
were selected randomly and 32 samples at four spiked levels from low to
high (10, 20, 50 and 95%) were obtained (8 pairs × 4 levels). All the
spiked samples were mixed homogeneously, scanned by FFSFS and
predicted by the PLS models, paralleled to model calibrations. Three
replicates were performed for each sample.
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Food Chemistry 375 (2022) 131887
2.2. Instrumentation
Fluorescence spectra were acquired by an FS5 spectrofluorometer
(Edinburgh, Livingston, Scotland, Britain) with a 150 W xenon lamp
source for excitation. The slit widths for excitation and emission were 1
and 2 nm, respectively. The front-face geometry by an SC-10 front-face
sample holder at room temperature (25 ◦ C) was used for spectra
acquisition. For solid samples, 50 mg of samples were mounted in the
sample holder. The incidence angle of the excitation radiation was 30◦
which was fixed by the holder. Excitation and emission were scanned
simultaneously with a constant wavelength interval (Δλ) between
excitation wavelength (λex) and emission wavelength (λem). Owing to
the limitation of the wavelength scanning range of the instrument
(230–870 nm), the spectra with larger than 870 nm λex and Δλ combined
is not available and hence two scan scopes were individually scanned.
The range of scope 1 was λex = 250–600 nm and Δλ = 30–200 nm, and
that of scope 2 was λex = 300–450 nm and Δλ = 30–300 nm. For both the
two scopes, the steps for λex and Δλ were 1 and 10 nm, respectively.
Fluorescence intensities were plotted as a function of λex. To minimize
measurement error, three spectra were measured for each sample suc­
cessively and the average of the three measurements was used for
further analysis. The obtained spectral data were pretreated by Savitz­
ky–Golay smoothing through seven points as an embedded default
function in the FS5 spectrofluorometer software “Fluoracle” (Edinburgh,
Livingston, Scotland, Britain). For solution samples, a 5 × 10 mm fused-
quartz cuvette was used for measurement, instead of the solid sample
holder. Except for this, the other instrument parameters were the same
as the above case of solid samples.
UV–visible absorption spectra were recorded by a U4600 spectro­
photometer (Hitachi, Tokyo, Japan). The slit width and scanning speed
were 2 nm and 2400 nm/min, respectively.
2.3. Multivariate calibration and validation
Prior to multivariate calibration, several commonly used spectral
data pretreatments including peak or area normalization, standard
normal variate (SNV), multiplicative scatter correction (MSC), first (1st)
and second (2nd) derivative preprocesses were tested. PLS regression
was performed by Unscrambler X (CAMO, Oslo, Norway).
PLS prediction models for maize flour in turmeric powder were
constructed. Four unadulterated turmeric powder samples with three
replicated measurements and 88 adulterated samples constituted the
calibration set (n = 100). All the PLS quantitative models were validated
by both five-fold cross-validation and external validation. For five-fold
cross-validation, all the samples were split into five segments of same
size. Then a given segment was left out to be used as an evaluation set
while the remaining four segments were used to yield a classification
rule. This process was repeated for five times until each group was left
out once. The corresponding root mean square error of calibration
(RMSEC), coefficient of determination for calibration (R2c), root mean
square error of cross-validation (RMSECV) and coefficient of determi­
nation for cross-validation (R2cv) were calculated. The optimal number
of PLS latent variables was decided by plotting the RMSECV versus the
number of components and determining the minimum of the plot. For
external validation, 41 turmeric powder samples spiked with various
proportions (10–95%) of maize flour were prepared and injected into a
test set, which was then used to evaluate the predictive ability of the
built models. The root mean square error of prediction (RMSEP) and
corresponding coefficient of determination for prediction (R2p) were
determined. The relative error of prediction (REP) was calculated as the
percentage ratio of the RMSEP to the mean of the actual content values.
The standard error of prediction (SEP), residual predictive deviation
(RPD) and range error ratio (RER) which are the ratio of the standard
deviation of reference values and the range of reference values to
RMSEP, respectively, were also determined. As there is no well-defined
method to estimate the limit of detection (LOD) in multivariate
J.-Y. Xie et al.
calibration, LOD were calculated according a literature method at the
95% confidence level (Allegrini & Olivieri, 2014; Márquez, Ruisánchez,
& Callao, 2019). For external test samples, relative error was calculated
as the average percentage of the difference between the predicted and
the actual values to the actual values.
2.4. Fluorescent titration test
For fluorescent titrations, a set of 10 mL mixture solutions in ethanol
were prepared by fixing FA at a constant concentration (5.2 × 10-3 mol/
L) and adding various volumes of stock solution of Cur to the mixture (its
final concentration was 8.1 × 10-6–2.7 × 10-4 mol/L). The mixture was
then diluted to volume with ethanol, mixed thoroughly and scanned by
spectrofluorometer. As the FA concentration was relatively high, the
front-face geometry was also employed for the fluorescent titration test
in solution state, to circumvent the concentration induced quenching
and peak distortion encountered by the traditional right-angle fluores­
cence when facing highly concentrated solutions. The λex was set at 364
nm and the λem range was 370–800 nm. The other instrument parame­
ters were set the same as those in section 2.2.
Analogously, to perform the fluorescent titration of FA to Cur, a set of
10 mL mixture solutions in ethanol were prepared by fixing Cur at a
constant concentration (2.7 × 10-5 mol/L) and adding various volumes
of stock solution of FA to the mixture (its final concentration was 2.6 ×
10-4–2.1 × 10-2 mol/L). The following procedures were parallel to the
fluorescent titration of Cur to FA as aforementioned.
3. Results and discussion
3.1. FFSFS of turmeric powder and maize flour
The FFSFS properties of turmeric powder and maize flour were first
investigated and compared. The FFSFS contour map of a typical
turmeric powder in scope 1 is shown in Fig. 1a. Generally, its emission in
scope 1 can be divided into two major regions (A and B): region A (λex =
350–500 nm and Δλ = 60–200 nm) and region B (λex = 500–600 nm and
Δλ = 30–100 nm). Region A can be attributed to the typical fluorescence
emission of Cur monomer (Nong et al., 2016). Its emission center at λex
= 440 nm and Δλ = 110 nm is in well agreement with the UV–vis ab­
sorption and fluorescence excitation and emission spectra of Cur in
ethanol solution (Fig. S1). On the contrary, region B could not be found
in any literature on the study of Cur fluorescence in solution state.
Considering the molecular structure of Cur (see the inset of Fig. 1c), the
relatively longer λex but smaller stokes shift of this band, and the fact
that this band can only be observed when Cur is in relatively high levels
(which will be shown later), it may be ascribed to the so-called aggre­
gation-induced emission (AIE) and J-aggregate formation (JAF) (Mei
et al., 2014). The highly concentrated solid state of Cur renders the
possibility of AIE and JAF. We have recently observed a similar fluo­
rescent phenomenon of capsanthin, the predominant carotenoid in chili
based on such AIE and JAF (Tan, Li, Li, Jiang, Tang, & Wang, 2021).
These findings suggest that the AIE and JAF behaviors of conjugated
polyenes containing both hydroxyl and ketone moieties are not partic­
ular cases.
All the eight turmeric samples presented similar emission patterns
(Fig. S2), though slight difference existed in the band position and in­
tensity between them. These “in-group” variances can be related to the
varied profiles of Cur groups and their micro-environments in these
turmeric samples, stemming from the differences of these samples in
botanical cultivars, growing, harvest or post-harvest conditions, and etc.
However, the maximal intensities of regions A and B were generally
analogous among these samples, indicating the not large sample-to-
sample variances in the total quantity of Cur and the composition of
its monomers and aggregates.
The contour map of maize flour (Fig. 1b) can also be roughly sepa­
rated into two isolated regions (C and D) according to λex and Δλ. Region
4
Food Chemistry 375 (2022) 131887
C (λex = 250–300 nm and Δλ = 30–100 nm) is the most intense band
which is largely attributed to aromatic amino acids of proteins, mainly
tryptophan (Karoui, Cartaud, & Dufour, 2006; Zandomeneghi, 1999;
Zeković, Lenhardt, Dramićanin, & Dramićanin, 2012). In addition, some
phenolic acids such as vanillic and p-hydroxybenzoic acids also fluoresce
in this region (Sergiel, Pohl, Biesaga, & Mironczyk, 2014). Considering
the fact that turmeric powder shows very weak tryptophan emission and
the content of protein in maize flour is 8–11%, among which protein
tryptophan is approximately 50 mg/100 g flour (Comai, Bertazzo, Bai­
loni, Zancato, Costa, & Allegri, 2007), tryptophan in maize flour may
serve as an important indice for adulteration. However, turmeric pow­
der also has protein, though in a very limited quantity. Besides, as
protein is widely spread in many other kinds of foods, the interference
from other foods may also be an important issue. That is, the sensitivity
and selectivity of the solely tryptophan based strategy may not be
satisfactory. The second less intensive band (region D) with λex ranging
in 300–400 nm is mainly due to the emissions of other phenolic acids
including ferulic and chlorogenic acids (Sergiel, Pohl, Biesaga, & Mir­
onczyk, 2014; Włodarska, Pawlak-Lemańska, Khmelinskii, & Sikorska,
2017; Zandomeneghi et al., 2000). The possible emission of cereal flours
in the Cur typical emission regions (A and B) is primarily ascribed to
flavonoids. Since maize flour only contains traces of flavonoids at most
(6.06 mg/kg, Nikolić et al., 2019), it is virtually non-fluorescent in these
regions, resulting no interference to the Cur emission. The contour maps
of all the five collected maize flour samples are shown in Fig. S3.
Compared with the tryptophan emissions (region C) which presented
relatively large variation, the contents of phenolic acids in these flours
(region D) were not severely deviated from each other (Fig. S3f).
The FFSFS spectra of pure solid Cur were scanned to demonstrate
that the main emissions of turmeric powder originate from Cur. As
shown in Fig. 1c, pure solid Cur also presented an A + B two regions
emission. The emission patterns are generally in consistence with those
of the turmeric powders. However, the ratio between the intensities of
the two regions were distinct from that of the turmeric powders
(Fig. 1a), with a slight shift of band center locations. For pure Cur, region
B showed much intensive fluorescence than region A, suggesting the
strong AIE effect in pure Cur. While in turmeric powders, as the Cur
concentrations are as low as 1–6% w/w, the monomer emission (region
A) was the dominant one.
FA, which is always the principal phenolic acid in maize flour, was
selected as the typical representative phenolic acid to be investigated. Its
molecular structure is depicted in the insets of Fig. 1d. Interestingly, one
Cur molecule can be regarded as the combination of two FA molecules.
FA showed a long-range fluorescent emission at λex = 300–400 nm,
which is in agreement with the range of region D of maize flour,
although its band shape cannot be clearly discerned in the map of maize
flour. It is not strange considering that the region D of maize flour is
attributed to the combined emissions of multiple phenolic acids and
other minor components that emitting in this range.
To further verify the existence of the two compounds in samples and
the fluorescence emission attributions, the turmeric powder spiked with
3% Cur (Fig. 1e) and the maize flour spiked with 0.1% FA (Fig. 1f) were
also studied. These two spiked concentrations were set to be similar to
the intrinsic levels of Cur in turmeric powder and FA in maize flour. As
can be seen from the comparison between Fig. 1a and 1e, the further
increase of Cur in turmeric powder did not rise the intensity of region A,
while only slightly strengthened the emission in region B. This result
indicates that the Cur monomers in turmeric powder may have a satu­
rated value. The over-saturated Cur monomers would aggregate and
emit in region B. This is to some extent confirmed by the observation of
Fig. S2. The eight turmeric powder samples did not show large deviation
in the intensities and shapes of region A. The major difference among
them was the intensities and shapes of region B (Fig. S2i). Compared
with Cur, the FA spiked in maize flour yielded a much clearer positive
effect. The addition of 0.1% FA increased the maximal emission of re­
gion D of maize flour, while in the meantime the band shape of region D
J.-Y. Xie et al. Food Chemistry 375 (2022) 131887

was not disturbed. The above results demonstrate that the main emis­
sion of turmeric powder and the region D of maize flour should originate
from Cur and some phenolic acids represented by FA, respectively.
3.2. Fluorescence quenching between maize flour and turmeric powder
The FFSFS contour maps in scope 1 (λex = 250–600 nm and Δλ =
30–200 nm) of the binary blends of maize flour and turmeric powder at
different ratios can be found in Fig. S4. Except the scope 1 involving the
regions A–D of the two samples, a scope 2 of large stokes shift (λex =
300–450 nm and Δλ = 30–300 nm) presenting the regions A, D and a
new region E of short-wavelength excitation but large Δλ was also
scanned and shown in Fig. 2. For comparison purpose, the emission of
pure turmeric powder and maize flour in this scope are also presented.
As can be seen in Fig. 2h, in addition to the Cur typical emission in re­
gion A, turmeric powder also showed an emission of relatively shorter
wavelength excitation but large Δλ (200–300 nm), which can also be
found in the spectra of pure Cur in scope 2. This large Stokes shift may be

Fig. 2. Contour maps for the total front-face synchronous fluorescence spectra of a typical maize flour sample spiked with different proportions of a turmeric powder
sample in scope 2 (λex = 300–450 nm and Δλ = 200–300 nm).

5
J.-Y. Xie et al. Food Chemistry 375 (2022) 131887

ascribed to the formation of intramolecular hydrogen bonds in Cur
molecule and the consequent excited state intramolecular proton
transfer (ESIPT), which lowers the energy of excited state and hence
enlarges the energy loss between excitation and emission (Mei, Leung,
Kwok, Lam, & Tang, 2015).
As shown in Figs. 2 and S4, the Cur monomer emission (region A)
emerged along with the addition of turmeric powder, even as the
addition level is as low as 0.2% (w/w). With the further increase of
turmeric powder to 2%, the intensity of this emission remained the
same, and then gradually decreased to a lower gratitude with the further
addition of turmeric powder. Meanwhile, along with the gradual
weakening of region A, the Cur aggregate emission (region B) appeared
and strengthened. This is reasonable as the formation of Cur aggregates
will diminish the amount of Cur monomers. On the other hand, when the
added turmeric powder is in the range of 0.2–5%, the tryptophan
emission (region C) of maize flour was not significantly affected, as the
maize flour accounts for 95–99.8% in the mixtures. However, the
phenolic acids emission (region D) showed an obvious quenching effect,
not in proportion to the decrease of maize flour proportion (99.8% to
95%). In the meantime, the Cur ESIPT emission (region E) can still not
observed in scope 2. With the further addition of turmeric powder from
5% to 95%, region D almost disappeared while region E gradually
emerged. Considering the fact that the excitation wavelength range of
regions D and E are nearly the same (300–400 nm), such ebb and flow of
the two regions is assumed to be attributed to the fluorescence
quenching induced by competitive absorption, that is, phenolic acids
and Cur share the total excitation energy, and the increase of one of
them will absorb more energy and reduce the portion of another.
3.3. Competitive absorption between ferulic acid and curcumin
To prove that competitive absorption takes place between FA and
Cur, the fluorescence titration tests in solution state were performed.
Prior to fluorescence titrations, the UV–vis absorption, fluorescence
excitation and emission spectra of FA and Cur in ethanol solution were
scanned and presented in Fig. S1. The absorption spectra of FA and Cur
had a partial overlap in the range of 300–400 nm, and the molar ab­
sorption coefficients (ε) of FA and Cur at λ = 364 nm (the maximal λex of
FA) were calculated to be 900 and 2.23 × 104 L/mol∙cm, respectively. It
should be noted that FA at high (5.2 × 10-3 mol/L) and low concen­
tration (1.55 × 10-5 mol/L) showed distinct fluorescent excitations. The
excitation spectra of FA at 1.55 × 10-5 mol/L overlapped its absorption
spectra. However, the excitation spectra of FA at 5.2 × 10-3 mol/L
showed a 30–60 nm bathochromic shift. As the ε of Cur at λ = 364 nm is
much larger than that of FA (~25-fold), to quench the fluorescence of
Curcumin at normal concentrations (10-6–10-5 mol/L), the

Fig. 3. (a) The fluorescence emission spectra of FA solution (5.2 × 10-3 mol/L) with the addition of different concentrations of Cur (8.1 × 10-6–2.7 × 10-4 mol/L) at
λex = 364 nm. (b) The Cur concentration dependent response of fluorescence intensity at 409 nm and the corresponding linear fitting using Stern-Volmer equation. (c)
The emission spectra of Cur solution (2.7 × 10-5 mol/L) with the addition of different concentrations of FA (2.6 × 10-4–2.1 × 10-2 mol/L) at λex = 364 nm. (d) The FA
concentration dependent response of fluorescence intensity at 540 nm and the corresponding linear fitting using Stern-Volmer equation.

6
J.-Y. Xie et al. Food Chemistry 375 (2022) 131887

concentration of FA needs to be two magnitudes higher (~10-3 mol/L). Table 1

Thus, to circumvent the concentration induced quenching and peak PLS statistics for the determination of maize flour adulterated in turmeric
distortion encountered by the traditional right-angle fluorescence when powder using unfolded total front-face synchronous fluorescence spectra of
facing highly concentrated solutions, the front-face geometry was also different regions (scope 1: λex = 250–600 nm and Δλ = 30–200 nm; scope 2: λex
employed for the fluorescent titration test in solution state. Both highly = 300–450 nm and Δλ = 200–300 nm).
concentrated FA and moderately concentrated Cur can be excited by the Parameter PLS for maize flour content
excitation light with λex = 300–400 nm. As the Cur excitation spectra Scope 1 Scope 2
also covered the FA emission range (400–500 nm), whether they can
No. of LVa 5 5
form a system of fluorescence resonance energy transfer (FRET) needs to R2cb 0.981 0.987
be verified. If FRET occurs between FA (donor) and Cur (acceptor), the RMSEC (%)c 4.3 3.6
existence of Cur can also quench the fluorescence of FA, while its own R2cvd 0.973 0.974
fluorescence can be enhanced by the excitation of FA. RMSECV (%)e 5.1 5.1
R2pf 0.973 0.960
The concentration-dependent fluorescence responses of FA/Cur on RMSEP (%)g 4.2 5.1
each other are depicted in Fig. 3. The excitation wavelength was set at REP (%)h 10.7 13.5
364 nm, which is the maximal λex of FA. Clear fluorescence quenching Prediction bias (%) 0.02 0.03
effects can be observed in pace with the increase of FA/Cur concentra­ SEP (%)i 3.5 4.1
RPDj 5.9 5.2
tion, along with the generated isoemissive points at λem = 460 nm. As
RERk 22.2 18.2
can be seen in Fig. 3a, the emission of FA at a constant concentration LOD (%)l 8.0 9.2
gradually decreased along with the addition of Cur while the Cur a
No. of LV, number of latent variables.
emission enhanced with the excitation at 364 nm. Fig. 3a can also be b
R2c, determination coefficient of calibration.
regarded as typical titration spectra of FRET, in which the addition of c
RMSEC, root mean square error of calibration.
acceptor quenches the fluorescence of donor. However, if FRET does d
R2cv, determination coefficient of five-fold cross-validation.
occur between FA and Cur, the addition of FA to Cur at a constant e
RMSECV, root mean square error of five-fold cross-validation.
concentration should also strengthen the Cur emission at the maximal f
R2p, determination coefficient of prediction.
λex of FA. Actually, the reverse is true. As can be observed in Fig. 3c, the g
RMSEP, root mean square error of prediction.
addition of FA significantly reduced the Cur emission. This solid evi­ h
REP (%), relative error of prediction.
i
dence demonstrates that the fluorescence quenching between FA and SEP, standard error of prediction.
j
Cur is caused by competitive absorption, instead of FRET. Sharing the RPD, ratio of the SD of reference values to RMSEP.
k
same excitation light, the co-existing FA and Cur competitively absorb RER, ratio of the range of reference values to RMSEP.
l
the excitation energy, producing the final fluorescence quenching re­ LOD, limit of detection.
sults compared to the solely existing cases.
A Stern-Volmer quench equation was then used to analyze the were comparable with those of calibration, indicating that there is no
fluorescence titration data. As shown in Fig. 3b and 3d, the titration data severe overfitting. As RPD values larger than 2.5 and RER values greater
showed good linearity in the fitting by the Stern-Volmer equation. The than 10 indicate a good model (Kar, Tudu, Jana, & Bandyopadhyay,
Stern-Volmer quenching constants (KS) of FA and Cur were calculated to 2019), the RPD larger than 5 and the RER around 20 both demonstrates
be (379 ± 17) L/mol and (1.77 ± 0.09) × 104 L/mol, respectively. These the superiority and applicability of the model. Additionally, the rela­
two values are dependent on the ε of FA and Cur at 364 nm, which are tively small REP (<15%) shows the method is of acceptable precision.
900 and 2.23 × 104 L/mol∙cm, respectively. The LODs of the method were calculated to be 8.0% and 9.2% for
The quenching effect originating from the competitive absorption scopes 1 and 2, respectively. The relatively high LOD values are due to
between FA and Cur on each other can be observed from another angle. either the repeatability of FFSFS measurements or the natural variations
The fluorescence intensities of the two compounds solely at different of turmeric powders in the contents of Cur. According to the European
concentrations were compared with those of them in the co-existence of Spice Association (ESA, 2018), the maximum levels of extraneous matter
the other (Fig. S5). Clearly, the co-existing FA or Cur adversely affected in herbs and spices are 2% and 1% w/w, respectively. At current stage,
the fluorescence of each other. The co-existing foreign molecules the LOD of the proposed FFSFS–PLS strategy cannot meet the require­
partake the consumption of excitation energy and reduce the portion of ment of ESA. It may be regarded as an alternative method for the rapid
the native ones. screening of turmeric powder adulteration with maize flour at relatively
large proportions. Further efforts can be paid to the lowering of LODs, by
3.4. PLS for determination of maize flour in turmeric powder reducing the spectral measurement errors or enlarging the turmeric
sample diversity.
Pure maize flours normally present yellow colors of varied shades. To assess the real applicability of the method, in addition to the
Generally, their yellowish color is slightly paler than the bright orange- turmeric powders and maize flours that were used in the training sets,
yellow color of pure turmeric powders. However, as long as the pro­ those samples that were not involved in the calibration of the models
portion of maize flour in the maize–turmeric binary blends does not were also used to prepared simulated blind samples. The prediction of
exceed 50%, the dissimilarity between the adulterated turmeric powders these blind samples by the built PLS model gave satisfactory results as
and the 100% pure genuine ones is quite difficult to discern by naked- shown in Fig. 4 and Table 2. As expected, the prediction errors of the
eyes. Nevertheless, as different degrees of competitive absorption oc­ simulated blind samples were inferior to those for the external test
curs between the adulterants and targets at various ratios, the whole samples which were prepared by the turmeric powder and maize flour
range of the adulterant proportions (0–100%) was studied, instead of samples that were used for construction of models, especially for those
solely the range in which the adulterant is not sensory evident (0–50%). samples of lower spiked proportions (no more than 20%). The absolute
Among the several spectral data pretreatments, SNV gave the best values of relative errors and the variances of three replicate measures for
results. Table 1 lists the PLS parameters and Fig. 4 shows the PLS cali­ the simulated blind samples were both larger than those for the external
bration and validation results based on the spectral data of scopes 1 and test samples. This result is predictable as the external samples bring
2. Generally, the data of the two scopes produced analogous PLS per­ unknown variables that the model has not been trained to recognize.
formance. For calibration, five-fold cross-validation and external vali­ Besides, it should be noted that scope 2 presents significantly better
dation, the R2 values were in the range of 0.96–0.99. The RMSEs were results than scope 1 when facing the challenging range (no more than
3.6–5.1%, and all the RMSEs of cross-validation and external validation 20%). Actually, it is reasonable considering the difference of the

7
J.-Y. Xie et al. Food Chemistry 375 (2022) 131887

Fig. 4. PLS predicted versus actual contents of maize flours adulterated in turmeric powder based on unfolded total front-face synchronous fluorescence spectra (a,
scope 1; b, scope 2) under optimal conditions as shown in Table 1. The parameters for cross-validation (R2cv and RMSECV) and prediction (R2p, RMSEP, REP and
RPD) listed in insets are calculated from five-fold cross-validation and external validation, respectively. Blue triangles with error bars (mean ± s; n = 3) represent
simulated blind samples (Table 2). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

long as the proportions of the adulterant is above the LODs of the

Table 2
method.
Results for the analysis of external test and simulated blind samples (mean ± s; n
Although the developed method showed good reliability, it should be
= 3). External test samples were prepared by the four turmeric powder and one
pointed out that the determination of maize flour is actually the assay of
maize flour samples that were used to build the calibration models. Contrarily,
simulated blind samples were fabricated by the left four turmeric powder and phenolic acids in maize flour. Thus, other exterior samples containing
four maize flour samples that were not involved in model construction. Relative phenolic acids will definitely result in positive interference to the assay,
error was calculated as the average percentage of the difference between the and the total contents and profiles of phenolic acids in a maize flour play
predicted and the actual values to the actual values. a vital role in the analytical merits of the method. Fortunately, as can be
Sample Actual Scope 1 Scope 2 seen in Fig. S3, the fluorescence intensities of the phenolic acid bands
value are similar among different maize flour samples, the influence of such
Predicted Relative Predicted Relative
(%)
value (%) error (%) value (%) error (%)
variable on analysis is not significant. This can also be proven by the
acceptable results of the prediction of simulated blind samples as
External test 12.0 12.7 ± 1.3 5 12.2 ± 2.1 1
aforementioned. Of course, whether this strategy is universal needs to be
sample 13.0 16.8 ± 1.7 29 14.0 ± 2.9 7
17.0 16.5 ± 1.2 –3 16.0 ± 1.0 –6 further checked by the collection of more maize flour samples as much
28.0 26.7 ± 1.0 –5 24.8 ± 1.3 –12 as possible.
32.0 25.6 ± 1.6 –20 25.8 ± 1.6 –19
49.0 48.0 ± 3.2 –2 44.4 ± 3.6 –9 4. Conclusion
57.0 55.1 ± 1.6 –4 51.1 ± 2.6 –10
78.0 75.0 ± 2.3 –4 70.2 ± 0.3 –10
82.0 76.7 ± 1.9 –6 86.7 ± 1.9 5 In conclusion, this study achieved the fast and non-invasive detection
Simulated 10.0 20.4 ± 7.6 103 13.6 ± 5.7 36 of turmeric powder adulteration with maize flour. The FFSFS emissions
blind 20.0 26.4 ± 8.2 32 19.3 ± 7.7 –3 of turmeric powder were primarily ascribed to Cur. After the adultera­
sample 50.0 54.4 ± 11.4 9 57.2 ± 10.8 14
tion by maize flour, competitive absorption induced fluorescence
95.0 100 ± 10 6 94.3 ± 13.2 –1
quenching could have taken place between phenolic acids such as FA in
maize flour and Cur in turmeric powder in solid state. The emission of
information the two scopes reflect. Scope 1 only focuses on the intrinsic phenolic acids and the ESIPT band of curcumin shared the excitation
fluorescence of Cur monomer (region A) and aggregates (region B) in energy. The most valuable merits of this strategy are convenience,
turmeric powders and tryptophan (region C) and phenolic acids (region rapidity and non-destructive detection. It opens new opportunities for
D) in maize flours. Contrarily, scope 2 supplements the important in­ the application of fluorescence spectroscopy and multivariate analysis.
formation on competitive absorption induced fluorescence quenching The fluorescence quenching phenomena induced by competitive ab­
(Cur ESIPT band, region E), in addition to the phenolic acids (region D) sorption between other kinds of fluorophores in solid foods are worthy
and Cur monomer (region A). When the maize flour is at low concen­ of investigation and future potential applications can be the component
trations in turmeric powders, the intrinsic fluorescence of phenolic acids analysis of other solid food blends from different botanical origins.
is rather obscure, not to mention their quenched fluorescence. In these
cases, the quenching of Cur ESIPT band (region E) can play a more Funding
important role, as it has a strong intensity which is more sensitive to
fluorescence quenching. Hence, after comprehensive consideration of all This research did not receive any specific grant from funding
these cases, scope 2 which can reflect the competitive absorption agencies in the public, commercial, or not-for-profit sectors.
induced fluorescence quenching clearly, is more recommended for
analysis. Nevertheless, as the majority of the calculated relative errors CRediT authorship contribution statement
for test samples were from − 20% to 20%, the proposed method is reli­
able for the accurate determination of maize flour in turmeric powder as Jing-Ya Xie: Conceptualization, Investigation, Software,

8
J.-Y. Xie et al.
Visualization. Jin Tan: Conceptualization, Methodology, Visualization,
Writing – original draft. Shu-Hua Tang: Methodology, Writing – review
& editing. Ying Wang: Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.foodchem.2021.131887.
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