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Food Control 130 (2021) 108326

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Food Control
journal homepage: www.elsevier.com/locate/foodcont

Impedimetric sensing of honey adulterated with high fructose corn syrup


Ta-Kang Huang a, Min-Chieh Chuang b, Yi Kung a, Bo-Chuan Hsieh a, *
a
Department of Biomechatronics Engineering, National Taiwan University, No. 1, Sec. 4, Roosevelt Rd., Taipei, 10617, Taiwan
b
Department of Chemistry, Tunghai University, Taichung, 40704, Taiwan

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

Keywords: Honey adulteration is a highlighted global issue in the modern food supply chain, the most commonly seen case
Honey adulteration is to cut honey with cheap and easily available sugar-based sweeteners, such as high fructose corn syrup (HFCS).
High fructose corn syrup To acquire a precise impedimetric response from such a high resistance sample, a low cell constant (13.9 cm− 1)
Impedance
electrochemical chamber composed of two identical bare gold electrodes was developed for investigating the
Label-free
Reagentless
impedimetric differences among pure honey, blended honey, and HFCS. Charge transfer resistance (RCT) and
logarithmic impedance (Log Z, in a broad frequency range of 101–105 Hz) were useful to discriminate all pure
honeys from blended honeys with good resolution and reproducibility (relative standard deviations of RCT and
Log Z were both less than 3% in triplicate tests). The data acquisition time for obtaining RCT and Log Z were only
3 min and 4 s, respectively, which means the proposed sensing approach is suitable for routine rapid screening
purpose.

1. Introduction distinguishing the isotopic δ13C feature from pure honey (Cabañero,
Recio, & Rupérez, 2006). Besides, low field nuclear magnetic resonance
Honey is one of the most famous natural products with its unique spectroscopy (Ribeiro et al., 2014), Fourier transform infrared spec­
flavor characteristics, high nutritional value, and medical benefits that troscopy (Gallardo-Velázquez, Osorio-Revilla, Loa, & Rivera-Espinoza,
has been widely consumed as food additive or traditional medicine in 2009), near-infrared spectroscopy (Kelly, Petisco, & Downey, 2006),
our daily life for centuries (Khan, Abadin, & Rauf, 2007; Al-Waili, Raman spectroscopy (Li, Shan, Zhu, Zhang, & Ling, 2012), ion mobility
Salom, & Al-Ghamdi, 2011; Eteraf-Oskouei & Najafi, 2013). In recent spectroscopy (Aliaño-González, Ferreiro-González, Espada-Bellido,
years, the worldwide climate change and pesticide abuse have signifi­ Barbero, & Palma, 2020), laser-induced breakdown spectroscopy
cantly influenced honeybee colonies and led to a considerable drop in (Peng et al., 2020), gas chromatography (Ruiz-Matute, Soria, Martí­
honey yields (Le Conte & Navajas, 2008; Jung & Cho, 2015). Because the nez-Castro, & Sanz, 2007), high performance liquid chromatography
supply of honey cannot meet market demand, it therefore has become an (Abdel-Aal et al., 1993), high performance anion exchange chroma­
attractive target of adulteration for commercial profits (Zábrodská & tography (He, Lei, & Sun, 2013), and electronic tongue (Sobrino-Gre­
Vorlov; Kendall et al., 2019). It has also been reported that the most gorio, Bataller, Soto, & Escriche, 2018) have also been established to
frequent way of adulteration is the addition of inexpensive sugar-based assess the adulteration with such a ubiquitous sweetener. Although the
sweeteners, such as corn syrup, invert sugar syrup, rice syrup, and high aforementioned methods were proven to be advantageous in high
fructose corn syrup (HFCS) (Siddiqui, Musharraf, Choudhary, & Rah­ sensitivity, precision, and accuracy; they are still too laborious, costly,
man, 2017; Li, Huang, Xia, Xiong, & Min, 2020; Naila, Flint, Sulaiman, and need data interpretation which are inapplicable to routine screening
Ajit, & Weeds, 2018; Song et al., 2020). Among these adulterants, HFCS purposes.
is relatively difficult to identify by conventional methods, since its main During the last decades, electrochemical and electrical impedance
chemical composition (e.g. fructose-to-glucose ratio) is very similar to spectroscopy (EIS) has been demonstrated as a promising tool to be
that of honey (Abdel-Aal, Ziena, & Youssef, 1993; Berriel & Perdomo, widespread applied in food related areas as a result of its distinct merits
2016; Wheeler & Robinson, 2014). of simplicity, cost-effectiveness, and high-throughput. For example, the
The most effective analytical technique for the issue of HFCS adul­ evaluation of fruit ripeness (Rehman, Abu Izneid, Abdullah, & Arshad,
teration is stable carbon isotope ratio mass spectrometry by 2011; Kuson & Terdwongworakul, 2013; Chowdhury, Bera, Ghoshal, &

* Corresponding author.
E-mail address: hsiehpc@ntu.edu.tw (B.-C. Hsieh).

https://doi.org/10.1016/j.foodcont.2021.108326
Received 3 October 2020; Received in revised form 27 May 2021; Accepted 7 June 2021
Available online 10 June 2021
0956-7135/© 2021 Elsevier Ltd. All rights reserved.
T.-K. Huang et al. Food Control 130 (2021) 108326

Chakraborty, 2017), the detection of artificial chemical additives in colorant was from Chulientop Ltd. (Yunlin, Taiwan). All samples and
juices (Nakonieczna, Paszkowski, Wilczek, Szypłowska, & Skierucha, food additives were stored in a dark place at room temperature
2016), the determination of herbicide in milk and tomato (Farahi et al., (20–25 ◦ C) prior to use. Deionized water (conductivity < 1 μS cm− 1) was
2015), the evaluation of fish freshness (Niu & Lee, 2000; Pérez-Esteve produced by a RDI pure water system (Sunway Scientific Co., Taipei,
et al., 2014), the assessment of cooking oil quality (Khaled, Aziz, & Taiwan).
Rokhani, 2014), the prediction of moisture content in fish (Chevalier,
Ossart, & Ghommidh, 2006), the determination of honey floral origin 2.2. Moisture content
(Scandurra, Tripodi, & Verzera, 2013), the assessment of beef meat
ageing (Damez, Clerjon, Abouelkaram, & Lepetit, 2008), the detection of A total of 1 g of honey or syrup sample was weighted and spread
food hazards (Chai & Oh, 2020), the measurement of yeast propagation evenly on the disposable aluminum sample pan (HA-D90, Mettler
during beer brewing (Brunauer, Spadiut, Gruber, & Slouka, 2020), and Toledo, Zurich, Switzerland). The moisture content was measured by a
the investigation of food-packaging interactions (Ciobotaru, Ciobotaru, halogen moisture analyzer (HG63, Mettler Toledo, Zurich, Switzerland)
Vaireanu, & Benga, 2018) were extensively developed by EIS-based at 120 ◦ C for 10 min. Each sample was analyzed in triplicate and the
techniques. Briefly, the principle of EIS is based on the application of average value was reported.
AC voltage (with a small sinusoidal perturbation at fixed frequency) to
an electrochemical cell (generally composed of two-, three-, or
2.3. Viscosity
four-electrode configurations) containing the analyte being investi­
gated, the corresponding AC current response at the same frequency is
A total of 20 g of honey or syrup sample was transferred into a small
monitored and converted it into complex impedance. The above process
sample adaptor with circulating water jacket for temperature control
is repeated throughout numerous frequencies for constructing a Nyquist
(SSA-18/13 R, AMETEK Brookfield, MA, U.S.A.). Viscosity was
plot (where for each frequency, real part of impedance (ZRe) is plotted
measured using a rotational viscometer (DV2TLV, AMETEK Brookfield,
versus imaginary part of impedance (ZIm)). By fitting the Nyquist curve
MA, U.S.A.) with No. SC4-18 spindle at 25 ◦ C at a shear rate of 6 rpm for
to an appropriate equivalent circuit model, the impedimetric charac­
10 min. Each sample was analyzed in triplicate and the average value
teristics of the analyte could be resolved precisely (Grossi & Riccò, 2017;
was reported.
Aguedo, Lorencova, Barath, Farkas, & Tkac, 2020; Strong, Richards,
Torres, Beck, & La Belle, 2021). However, honey is a viscous object with
its extremely high resistance, precise data acquisition is incapable of 2.4. EIS measurement
reaching under conventional EIS system configurations mainly attrib­
uted to the impedance mismatching problem. Our previous study has In a cylindrical glass vessel, a total of 20 g of honey or syrup sample
constructed an electrochemical cell with low cell constant composed of was mixed with 5 g of deionized water (80% sample solution, w/w) and
two screen-printed carbon paste electrodes which was successfully degassed under ultrasonic bath (T760DH, Elma, Germany) working at
applied to measure the impedance of a high resistance sample, biodiesel, 40 kHz, 170 W for 30 s. As shown in Fig. 1, two bare gold electrodes (2.0
for its quality control (Kung, Hsieh, Cheng, Huang, & Chen, 2012). mm in diameter, embedded in a 6.35 mm outside diameter plastic rod;
Similar strategies have also been adopted for impedimetric sensing of CHI101, CH Instruments, Inc., TX, U.S.A.) were put in parallel and fasten
honey-related issues (Scandurra et al., 2013; Paszkowski, Wilczek, by a rubber O-ring to ensure a fixed cell constant of 13.9 cm− 1, the gold
Szypłowska, Nakonieczna, & Skierucha, 2014). electrode pair was then gently immersed into the sample solution to
In this paper, the moisture content (by moisture analyzer) and vis­ avoid bubbles attached to electrode surfaces. EIS measurement was
cosity (by rotational viscometer) of pure honey, blended honey, and scanned from 1 MHz down to 1 Hz with an unbiased 100 mV sinusoidal
HFCS were firstly obtained for comparing the general physical charac­ signal by using an Autolab PGSTAT-30 system equipped with an FRA2-
teristics among three kinds of commercial products. The differences of module, data acquisition and equivalent circuit model analysis were
EIS characteristics (by electrochemical impedance analyzer) were then done with the NOVA 1.10.3 software package (Eco Chemie B. V.,
extensively investigated with a low cell constant electrochemical Utrecht, Netherlands). The temperature of sample solution was
chamber consisted of two identical bare gold electrodes. To evaluate the
feasibility of utilizing EIS for examining honey adulteration, the in­
fluences of food additives included in the blended honeys were also
evaluated. Finally, a statistical analysis of the impedimetric sensing re­
sults was performed to assess the reliability of discriminating honey
adulterations.

2. Materials and methods

2.1. Samples and food additives

Seventy-one authentic unifloral honey samples including 48 pure


longan honeys and 23 pure litchi honeys were bought from local su­
permarkets in the springtime during the period from 2016 to 2018, all of
the 71 pure honey products have certified labels proven by Taiwan
Beekeepers Association (longan and litchi trees generally blossom be­
tween March and May in Taiwan, honey bees collect nectar from the
flowers and transform it into honey in few days, beekeepers harvest its
honey once or twice a week in general). Twenty-six commercial blended
honey samples (mainly mixed syrups with pure honey, honey flavor and
caramel colorant according to the ingredients labels) and 9 commercial
high fructose corn syrup samples were also purchased from local su­
permarkets during the period from 2016 to 2018. Honey flavor was
obtained from Shiono Koryo Kaisha Ltd. (Osaka, Japan). Caramel Fig. 1. Schematic diagram of the EIS measurement setup.

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T.-K. Huang et al. Food Control 130 (2021) 108326

controlled at 25 ◦ C throughout the experiment with a thermostatic water


bath (D-606, Deng Yng, Taipei, Taiwan). All the EIS tests were con­
ducted in triplicate and the average value was obtained.

2.5. Statistical analysis

A one-way ANOVA followed by Tukey’s post-hoc test (v.26 SPSS


statistics, IBM) was conducted to assess the statistical significance of the
impedimetric sensing results among pure honey, blended honey, and
HFCS. A p-value of less than 0.001 was considered statistically
significant.

3. Results and discussion

3.1. Moisture content and viscosity

The moisture contents found in the certified 71 pure honeys ranged


from 15.73% to 18.43% which were well within the quality criteria
(≤20%) according to the European Union Council Directive (European
Commission, 2014). Although the 9 HFCS samples possessed generally
higher values of 21.14–22.19%, the 26 blended honeys still showed a
consistency (16.09–17.89%) similar to the pure ones. This phenomenon
suggested that the manufacturers well imitated the rheological behavior
of pure honey to achieve a natural pouring characteristic and a satis­
factory mouthfeel with some post-concentration processes for the
Fig. 2. (a) Nyquist diagram of the experimental EIS result of one pure honey
commercial blended products. A positive correlation with viscosity data
sample (open circle, Pure#47, Table S1) with a simulated spectrum fitted by the
also indicated the aforementioned conjecture, where the average vis­ conventional Randles model (dashed line) and another simulated spectrum
cosities of pure honeys, blended honeys, and HFCS samples were 4468 fitted by a modified Randles model (solid line); (b) conventional Randles
± 958, 3856 ± 713, and 855 ± 121 cP, espectively (see Supplementary model; (c) modified Randles model in which the Warburg impedance (W) is
Tables). For further understanding of the features of honey samples used replaced by a constant phase element (CPE). Each datum is the average of three
in this work, other physicochemical properties including sugar content, repetitive experiments with relative standard deviation less than 2%.
pH value, electrical conductivity, color intensity, turbidity, proline
content, and gluconate content of the same honey samples can be found 3.3. EIS characteristics of pure honey, blended honey and HFCS
in the documented article (Chen et al., 2018).
Fig. 3 demonstrates the typical Nyquist spectra of three types of
3.2. Selection of equivalent circuit model samples, in which pure honey (○, Pure#47, Table S1) exhibited much
smaller size of semicircle than both blended honey (■, Blended#12,
Fig. 2a shows a typical Nyquist curve of one pure honey sample Table S2) and HFCS (△, HFCS#5, Table S3). Because honey is well-
(open circle, Pure#47, Table S1), which consists of a semicircle pattern known to be abundant in natural antioxidants such as phenols, flavo­
at high frequency region with an oblique line at low frequency region. noids, and vitamins (León-Ruiz, Vera, González-Porto, & San Andrés,
Such experimental impedance spectra are generally explained by the
conventional Randles equivalent circuit model (Fig. 2b) which consists
of a solution resistance (RS), a double layer capacitance (CD), a charge
transfer resistance (RCT) and a Warburg impedance (W). However, an
unacceptable fitting (dashed line in Fig. 2a) between the simulated and
experimental spectrum was observed, especially in the low frequency
Warburg diffusion area. It may be attributed to the non-ideal diffusion
behavior of ionic species in such a viscous medium, like honey
(54.8–75.6 cP for 80% (w/w) honey). Contrarily, a satisfactory fitting
(solid line in Fig. 2a) was achieved by introducing a constant phase
element (CPE) into the Randles model instead of the Warburg imped­
ance (Fig. 2c). CPE is a frequency-dependent component which has been
widely used in simulating the non-ideal properties of electrochemical
interfaces. The impedance of a CPE is given below:

ZCPE = 1 / Y(jω)n

where Y is the magnitude of CPE, n is an empirical constant (typically


ranging from 0 to 1). The CPE behaves as a capacitor, a Warburg
element, and a resistor when n = 1, 0.5, and 0, respectively. (Hsu, Yen,
Jeng, & Chien, 2006). For obtaining a more accurate fit of experimental
data, the modified Randles equivalent circuit model (Fig. 2c) was Fig. 3. Typical Nyquist diagrams of pure honey (○, Pure#47, Table S1),
selected for the following experiments. To our best knowledge, this is the blended honey (■, Blended#12, Table S2), and HFCS (△, HFCS#5, Table S3).
first work to propose the simply modified Randles model for solving the Applied voltage: 0 V; amplitude: 100 mV; frequency range: 1 MHz - 1 Hz. Each
inaccuracy of impedimetric sensing of honey which possesses a datum is the average of three repetitive experiments with relative standard
non-ideal diffusion manner. deviation less than 3%.

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T.-K. Huang et al. Food Control 130 (2021) 108326

2013; Ciulu, Spano, Pilo, & Sanna, 2016), some of these compounds are
electrochemically active species which are prone to generating ex­
change currents at electrode interface by means of a small perturbation
potential of 100 mV in the present work (e.g. myricetin, quercetin,
fisetin, etc. (Yang, Kotani, Arai, & Kusu, 2001)), and thus the lowest RCT
value was obtained (80 ± 23 kΩ in Table 1, N = 71). everal studies also
showed that honey has a rich organic acids profile, mainly consists of
gluconic, formic, lactic, acetic, citric, and malic acid (Cherchi, Spa­
nedda, Tuberoso, & Cabras, 1994; Mato, Huidobro, Simal-Lozano, &
Sancho, 2006); these components can act as supporting electrolytes to
reduce the Ohmic drop effect and to suppress the migration of electro­
active substances towards the polarized electrodes that resulted in an
increase of electrochemical current density (Tsierkezos & Ritter, 2012).
Consequently, the lack of both electrochemically active species and
supporting electrolytes in HFCS severely hampered the interfacial
electron transfer process, which led to its high RCT nature (refer to
Table 1).
As displayed by the simulated impedance data in Table 1, the values
of n performed in the three types of sample solutions were all slightly
greater than 0.8 which again implied the non-ideal diffusion behavior of Fig. 4. Nyquist diagrams of honey (Pure#47, Table S1), adulterated honeys
the electrochemically active species in such viscous environments. In with HFCS, and HFCS (HFCS#5, Table S3). Adulteration ratio: 0% (○); 25% (■);
50% (+); 75% (◆); 100% (△). Experimental conditions are the same as Fig. 3.
addition, RCT was found to be the most recognizable equivalent circuit
Each datum is the average of three repetitive experiments with standard de­
element to pure honeys, where the average RCT values of blended honey
viation less than 3%.
(629 ± 175 kΩ, N = 26) and HFCS (718 ± 154 kΩ, N = 9) were 7.9 and
9.0 times higher than that of pure honey, respectively. The nearness
between the RCT values of blended honey and HFCS further suggested Table 2
that the major ingredient of blended honey is highly possible to be HFCS. Effect of adulteration ratio on the simulated impedance results.
Adulteration ratio (%) 0 (honey) 25 50 75 100 (HFCS)
3.4. Effect of adulterated honey with HFCS on impedimetric sensing
RCT (kΩ) 78 101 164 342 770
Log Z at 101 Hz 5.20 5.30 5.41 5.63 5.94
As from Fig. 4, the size of semicircle increased gradually by elevating Log Z at 102 Hz 4.94 5.04 5.23 5.53 5.90
the adulteration ratio of HFCS. This phenomenon was in accordance Log Z at 103 Hz 4.89 5.01 5.20 5.51 5.89
with the aforementioned inference: the higher the adulteration ratio, the Log Z at 104 Hz 4.89 5.01 5.20 5.51 5.89
Log Z at 105 Hz 4.86 4.96 5.13 5.34 5.53
lower the content of electrochemically active species and supporting
electrolytes in the sample solution which caused an obvious rise in the RCT and Log Z values were obtained from Figs. 4 and 5, respectively.
RCT value (refer to the simulated impedance results in Table 2). The
significant difference of RCT value between 75% adulterated honey (342
kΩ in Table 2) and blended honey (629 kΩ in Table 1) further indicated
the commercial blended honeys might contain no more than 25% pure
honey. Fig. 5 illustrates the Bode plot (corresponding to the data of
Fig. 4) of logarithmic impedance magnitude (Log Z) versus frequency,
there were evident Log Z differences for discriminating the adulteration
ratio even in a such wide frequency range of 101–105 Hz (detailed data
are presented in Table 2).

3.5. Effect of honey flavor and caramel colorant on impedimetric sensing

The addition of 2% and 4% honey flavor into HFCS sample (HFCS#5,


Table S3) led to a slight rise in the RCT value of 22 kΩ and 63 kΩ,
respectively. The more the honey flavor added, the larger the difference
in RCT value between pure honey and adulterated sample was per­
formed. It is therefore advantageous to our EIS-based system for

Table 1
Impedance analysis of pure honeys, blended honeys and HFCS samples based on
the modified Randles equivalent circuit model of Fig. 2c. Detailed data are
Fig. 5. Bode plots of honey (Pure#47, Table S1), adulterated honeys with
shown in the Supplementary Tables.
HFCS, and HFCS (HFCS#5, Table S3). Adulteration ratio: 0% (○); 25% (■); 50%
Sample type RS (Ω) RCT (kΩ) CD (pF) CPE (+); 75% (◆); 100% (△). Experimental conditions are the same as Fig. 3. Each
Y n datum is the average of three repetitive experiments with standard deviation
(nMho) less than 3%.
Pure honey (N = 680 ± 80 ± 23 7.47 ± 270 ± 0.84 ±
71) 181 0.22 20 0.01 checking adulteration with the existence of this artificial ingredient.
Blended honey (N 751 ± 629 ± 7.30 ± 246 ± 0.84 ± With gradually spiking caramel colorant into HFCS sample (HFCS#5,
= 26) 209 175 0.21 29 0.01
Table S3), it was revealed that 0.02%–0.15% were appropriate amounts
HFCS (N = 9) 803 ± 718 ± 6.98 ± 187 ± 0.82 ±
249 154 0.25 26 0.02
to mimic the appearances of 71 collected pure honey samples (between

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T.-K. Huang et al. Food Control 130 (2021) 108326

pale yellow and dark brown). Excess amounts of caramel colorant were Declaration of competing interest
then adopted for EIS measurements, where 0.2% and 0.25% of spiking
resulted in a RCT decrease of 126 kΩ and 166 kΩ, respectively. However, The authors declare that they have no known competing financial
the RCT level of overly stained HFCS (604 kΩ for the 0.25% of spiking) interests or personal relationships that could have appeared to influence
was still far higher from that of all the pure honeys (the highest RCT of the work reported in this paper.
pure honey was 139 kΩ in this study, Pure#71, Table S1), the influence
of such food additive is not evident to the proposed impedimetric Acknowledgements
sensing method.
This research was financially supported by the Ministry of Science
3.6. Statistical analysis and Technology of Taiwan under Contract No. MOST 106-2311-B-002-
024.
The group comparisons among pure honey, blended honey, and
HFCS were analyzed by a one-way ANOVA followed by Tukey’s post-hoc
Appendix A. Supplementary data
test. The RCT values of pure honey samples were significantly different
(p < 0.001) as compared to both of the blended honey and HFCS sam­
Supplementary data to this article can be found online at https://doi.
ples, contrarily, there was statistically similarity to the groups of
org/10.1016/j.foodcont.2021.108326.
blended honey and HFCS (P > 0.05). These phenomena showed that the
reliability of utilizing impedimetric sensing approach for discriminating
References
honey adulteration with high fructose corn syrup. Besides, the loga­
rithmic impedance signal (Log Z, for example at 103 Hz) also demon­ Abdel-Aal, E.-S. M., Ziena, H. M., & Youssef, M. M. (1993). Adulteration of honey with
strated sufficient resolution in discriminating pure honeys from blended high-fructose corn syrup: Detection by different methods. Food Chemistry, 48(2),
honeys. However, not only the composition of natural honey but also the 209–212. https://doi.org/10.1016/0308-8146(93)90061-J
Aguedo, J., Lorencova, L., Barath, M., Farkas, P., & Tkac, J. (2020). Electrochemical
adulterants existed in blended honey are highly changeable, it is still
impedance spectroscopy on 2D nanomaterial MXene modified interfaces:
necessary to collect more pure and blended samples for further reli­ Application as a characterization and transducing tool. Chemosensors, 8(4), 127.
ability test. https://doi.org/10.3390/chemosensors8040127
Al-Waili, N. S., Salom, K., & Al-Ghamdi, A. A. (2011). Honey for wound healing, ulcers,
and burns; data supporting its use in clinical practice. Science World Journal, 11,
3.7. Reusability 766–787. https://doi.org/10.1100/tsw.2011.78
Aliaño-González, M. J., Ferreiro-González, M., Espada-Bellido, E., Barbero, G. F., &
The reusability of the constructed impedimetric sensing system was Palma, M. (2020). Novel method based on ion mobility spectroscopy for the
quantification of adulterants in honeys. Food Control, 114, Article 07236. https://
conducted after sequentially rinsing with deionized water and ethanol to doi.org/10.1016/j.foodcont.2020.107236
remove the non-specific adsorption of honey proteins on the surface of Berriel, V., & Perdomo, C. (2016). Determination of high fructose corn syrup
gold electrode. It was exhibited that this system can be reused with concentration in Uruguayan honey by 13C analyses. Lebensmittel-Wissenschaft und
-Technologie- Food Science and Technology, 73, 649–653. https://doi.org/10.1016/j.
relative standard deviations of both RCT and Log Z values less than 3% lwt.2016.07.004
(n = 3 for all pure honeys, blended honeys, HFCSs, and HFCS- Brunauer, G. C., Spadiut, O., Gruber, A., & Slouka, C. (2020). Yeast propagation control:
adulterated samples). Moreover, the data acquisition time for obtain­ Low frequency electrochemical impedance spectroscopy as an alternative for cell
counting chambers in brewery applications. Chemosensors, 8(2), 27. https://doi.org/
ing full impedance spectrum was about 3 min (scanning frequency range 10.3390/chemosensors8020027
in this work: 1 MHz - 1 Hz), it could be effectively reduced to only few Cabañero, A. I., Recio, J. L., & Rupérez, M. (2006). Liquid chromatography coupled to
seconds (1–4 s) if a single frequency between 101 - 105 Hz was desig­ isotope ratio mass spectrometry: A new perspective on honey adulteration detection.
Journal of Agricultural and Food Chemistry, 54(26), 9719–9727. https://doi.org/
nated for employing EIS measurement.
10.1021/jf062067x
Chai, C., & Oh, S.-W. (2020). Electrochemical impedimetric biosensors for food safety.
4. Conclusions Food Science and Biotechnology, 29(7), 879–887. https://doi.org/10.1007/s10068-
020-00776-w
Chen, R. L. C., Hou, Y.-T., Cheng, T.-J., Lai, Y.-J., Tsai, S.-T., & Hsieh, B.-C. (2018).
This study demonstrates a label-free and reagentless impedimetric Development of preliminary rapid screening index for honey adulteration based on
sensing approach for identifying HFCS-adulterated honeys by a very the physicochemical property analysis. Taiwanese Journal of Agricultural Chemistry
simple electrochemical cell configuration only composed of two tightly and Food Science, 56(5), 121–127. https://doi.org/10.6578/TJACFS.201810_56
(5).0002
parallel bare gold electrodes. A modified Randles equivalent circuit Cherchi, A., Spanedda, L., Tuberoso, C., & Cabras, P. (1994). Solid-phase extraction and
model is also presented to acquire more accurate impedance data by high-performance liquid chromatographic determination of organic acids in honey.
substituting a constant phase element for the commonly used Warburg Journal of Chromatography A, 669(1–2), 59–64. https://doi.org/10.1016/0021-9673
(94)80336-6
impedance. Both of the RCT and Log Z values are proven to be potential Chevalier, D., Ossart, F., & Ghommidh, C. (2006). Development of a non-destructive salt
indices for rapid screening fake honeys within few minutes. The pro­ and moisture measurement method in salmon (Salmo salar) fillets using impedance
posed EIS-based sensor is suitable for high viscous and high resistance technology. Food Control, 17(5), 342–347. https://doi.org/10.1016/j.
foodcont.2004.11.009
sample, further applications in other food industrial areas are also ex­ Chowdhury, A., Bera, T. K., Ghoshal, D., & Chakraborty, B. (2017). Electrical impedance
pected. Besides, our experimental setup is very simple which is therefore variations in banana ripening: An analytical study with electrical impedance
readily available to develop a miniaturized device by incorporating a spectroscopy. Journal of Food Process Engineering, 40(2), Article e12387. https://doi.
org/10.1111/jfpe.12387
commercial integrated circuit chip designed for complex impedance
Ciobotaru, I.-A., Ciobotaru, I.-E., Vaireanu, D.-I., & Benga, F.-M. (2018). Food-packaging
measurement to achieve real-time field analysis of honey adulteration. interactions investigated by electrochemical impedance spectroscopy. Journal of
Food Process Engineering, 41(1), Article e12615. https://doi.org/10.1111/jfpe.12615
Ciulu, M., Spano, N., Pilo, M. I., & Sanna, G. (2016). Recent advances in the analysis of
CRediT authorship contribution statement
phenolic compounds in unifloral honeys. Molecules, 21(4), 451. https://doi.org/
10.3390/molecules21040451
Ta-Kang Huang: Investigation, Writing – original draft. Min-Chieh Damez, J.-L., Clerjon, S., Abouelkaram, S., & Lepetit, J. (2008). Beef meat electrical
Chuang: Resources, Writing – review & editing. Yi Kung: Methodology, impedance spectroscopy and anisotropy sensing for non-invasive early assessment of
meat ageing. Journal of Food Engineering, 85(1), 116–122. https://doi.org/10.1016/j.
Writing – original draft. Bo-Chuan Hsieh: Conceptualization, Project jfoodeng.2007.07.026
administration, Supervision, Writing – review & editing. Eteraf-Oskouei, T., & Najafi, M. (2013). Traditional and modern uses of natural honey in
human diseases: A review. Iranian Journal of Basic Medical Sciences, 16(6), 731–742.
https://doi.org/10.22038/IJBMS.2013.988
European Commission. (2014). Directive 2014/63/EU of the European parliament and of
the Council of 15 may 2014, amending Council directive 2001/110/EC relating to

5
T.-K. Huang et al. Food Control 130 (2021) 108326

honey. Official Journal of the European Communities, L164, 1–5. https://eur-lex.eu Naila, A., Flint, S. H., Sulaiman, A. Z., Ajit, A., & Weeds, Z. (2018). Classical and novel
ropa.eu/eli/dir/2014/63/oj. approaches to the analysis of honey and detection of adulterants. Food Control, 90,
Farahi, A., El Gaini, L., Achak, M., El Yamani, S., El Mhammedi, M. A., & Bakasse, M. 152–165. https://doi.org/10.1016/j.foodcont.2018.02.027
(2015). Interaction study of paraquat and silver electrode using electrochemical Nakonieczna, A., Paszkowski, B., Wilczek, A., Szypłowska, A., & Skierucha, W. (2016).
impedance spectroscopy: Application in milk and tomato samples. Food Control, 47, Electrical impedance measurements for detecting artificial chemical additives in
679–685. https://doi.org/10.1016/j.foodcont.2014.08.005 liquid food products. Food Control, 66, 116–129. https://doi.org/10.1016/j.
Gallardo-Velázquez, T., Osorio-Revilla, G., Loa, M. Z., & Rivera-Espinoza, Y. (2009). foodcont.2016.01.044
Application of FTIR-HATR spectroscopy and multivariate analysis to the Niu, J., & Lee, J. Y. (2000). A new approach for the determination of fish freshness by
quantification of adulterants in Mexican honeys. Food Research International, 42(3), electrochemical impedance spectroscopy. Journal of Food Science, 65(5), 780–785.
313–318. https://doi.org/10.1016/j.foodres.2008.11.010 https://doi.org/10.1111/j.1365-2621.2000.tb13586.x
Grossi, M., & Riccò, B. (2017). Electrical impedance spectroscopy (EIS) for biological Paszkowski, B., Wilczek, A., Szypłowska, A., Nakonieczna, A., & Skierucha, W. (2014).
analysis and food characterization: A review. Journal of Sensors and Sensor Systems, 6, A low-frequency sensor for determination of honey electrical properties in varying
303–325. https://doi.org/10.5194/jsss-6-303-2017 temperature conditions. Journal of Food Engineering, 138, 17–22. https://doi.org/
He, J. Z., Lei, M., & Sun, P. L. (2013). Study on LOD of Chinese honey adulterated with 10.1016/j.jfoodeng.2014.04.004
HFCS by HPAEC-PAD. Advanced Materials Research, 718–720, 281–287. https://doi. Peng, J., Xie, W., Jiang, J., Zhao, Z., Zhou, F., & Liu, F. (2020). Fast quantification of
org/10.4028/www.scientific.net/AMR.718-720.281. honey adulteration with laser-induced breakdown spectroscopy and chemometric
Hsu, N.-Y., Yen, S.-C., Jeng, K.-T., & Chien, C.-C. (2006). Impedance studies and methods. Foods, 9, 341. https://doi.org/10.3390/foods9030341
modeling of direct methanol fuel cell anode with interface and porous structure Pérez-Esteve, E., Fuentes, A., Grau, R., Fernández-Segovia, I., Masot, R., Alcañiz, M.,
perspectives. Journal of Power Sources, 161(1), 232–239. https://doi.org/10.1016/j. et al. (2014). Use of impedance spectroscopy for predicting freshness of sea bream
jpowsour.2006.03.076 (Sparus aurata). Food Control, 35(1), 360–365. https://doi.org/10.1016/j.
Jung, C., & Cho, S.-K. (2015). Relationship between honeybee population and honey foodcont.2013.07.025
production in korea: A historical trend analysis. Korean Journal of Apiculture, 30(1), Rehman, M., Abu Izneid, B. A. J. A., Abdullah, M. Z., & Arshad, M. R. (2011). Assessment
7–12. https://doi.org/10.17519/apiculture.2015.04.30.1.7 of quality of fruits using impedance spectroscopy. International Journal of Food
Kelly, J. D., Petisco, C., & Downey, G. (2006). Potential of near infrared transflectance Science and Technology, 46(6), 1303–1309. https://doi.org/10.1111/j.1365-
spectroscopy to detect adulteration of Irish honey by beet invert syrup and high 2621.2011.02636.x
fructose corn syrup. Journal of Near Infrared Spectroscopy, 14(2), 139–146. https:// Ribeiro, R. de O. R., Mársico, E. T., Carneiro, C. da S., Monteiro, M. L. G., Júnior, C. C., &
doi.org/10.1255/jnirs.599 Jesus, E. F. O. de (2014). Detection of honey adulteration of high fructose corn syrup
Kendall, H., Clark, B., Rhymer, C., Kuznesof, S., Hajslova, J., Tomaniova, M., et al. by low field nuclear magnetic resonance (LF 1H NMR). Journal of Food Engineering,
(2019). A systematic review of consumer perceptions of food and authenticity: A 135, 39–43. https://doi.org/10.1016/j.jfoodeng.2014.03.009
European perspective. Trends in Food Science & Technology, 94, 79–90. https://doi. Ruiz-Matute, A. I., Soria, A. C., Martínez-Castro, I., & Sanz, M. L. (2007). A new
org/10.1016/j.tifs.2019.10.005 methodology based on GC-MS to detect honey adulteration with commercial syrups.
Khaled, A. Y., Aziz, S. A., & Rokhani, F. Z. (2014). Development and evaluation of an Journal of Agricultural and Food Chemistry, 55(18), 7264–7269. https://doi.org/
impedance spectroscopy sensor to assess cooking oil quality. International Journal of 10.1021/jf070559j
Environmental Science and Development, 5(3), 299–302. https://doi.org/10.7763/ Scandurra, G., Tripodi, G., & Verzera, A. (2013). Impedance spectroscopy for rapid
IJESD.2014.V5.496 determination of honey floral origin. Journal of Food Engineering, 119(4), 738–743.
Khan, F. R., Abadin, Z. U. I., & Rauf, N. (2007). Honey: Nutritional and medicinal value. https://doi.org/10.1016/j.jfoodeng.2013.06.042
International Journal of Clinical Practice, 61(10), 1705–1707. https://doi.org/ Siddiqui, A. J., Musharraf, S. G., Choudhary, M. I., & Rahman, A. (2017). Application of
10.1111/j.1742-1241.2007.01417.x analytical methods in authentication and adulteration of honey. Food Chemistry, 217,
Kung, Y., Hsieh, B.-C., Cheng, T.-J., Huang, C.-K., & Chen, R. L. C. (2012). Impedimetric 687–698. https://doi.org/10.1016/j.foodchem.2016.09.001
sensing of the biodiesel contents in diesel fuels with a carbon paste electrode pair. Sobrino-Gregorio, L., Bataller, R., Soto, J., & Escriche, I. (2018). Monitoring honey
Fuel, 102, 724–728. https://doi.org/10.1016/j.fuel.2012.06.023 adulteration with sugar syrups using an automatic pulse voltammetric electronic
Kuson, P., & Terdwongworakul, A. (2013). Minimally-destructive evaluation of durian tongue. Food Control, 91, 254–260. https://doi.org/10.1016/j.foodcont.2018.04.003
maturity based on electrical impedance measurement. Journal of Food Engineering, Song, X., She, S., Xin, M., Chen, L., Li, Y., Heyden, Y. V., et al. (2020). Detection of
116(1), 50–56. https://doi.org/10.1016/j.jfoodeng.2012.11.021 adulteration in Chinese monofloral honey using 1H nuclear magnetic resonance and
Le Conte, Y., & Navajas, M. (2008). Climate change: Impact on honey bee populations chemometrics. Journal of Food Composition and Analysis, 86, 103390. https://doi.
and diseases. Revue Scientifique et Technique (International Office of Epizootics), 27(2), org/10.1016/j.jfca.2019.103390
499–510. https://doi.org/10.20506/RST.27.2.1819 Strong, M. E., Richards, J. R., Torres, M., Beck, C. M., & La Belle, J. T. (2021). Faradaic
León-Ruiz, V., Vera, S., González-Porto, A. V., & San Andrés, M. P. (2013). Analysis of electrochemical impedance spectroscopy for enhanced analyte detection in
water-soluble vitamins in honey by isocratic RP-HPLC. Food Analytical Methods, 6(2), diagnostics. Biosensors and Bioelectronics, 177, 112949. https://doi.org/10.1016/j.
488–496. https://doi.org/10.1007/s12161-012-9477-4 bios.2020.112949
Li, Y., Huang, Y., Xia, J., Xiong, Y., & Min, S. (2020). Quantitative analysis of honey Tsierkezos, N. G., & Ritter, U. (2012). Influence of concentration of supporting
adulteration by spectrum analysis combined with several high-level data fusion electrolyte on electrochemistry of redox systems on multi-walled carbon nanotubes.
strategies. Vibrational Spectroscopy, 108, 103060. https://doi.org/10.1016/j. Physics and Chemistry of Liquids, 50(5), 661–668. https://doi.org/10.1080/
vibspec.2020.103060 00319104.2012.663496
Li, S., Shan, Y., Zhu, X., Zhang, X., & Ling, G. (2012). Detection of honey adulteration by Wheeler, M. M., & Robinson, G. E. (2014). Diet-dependent gene expression in honey
high fructose corn syrup and maltose syrup using Raman spectroscopy. Journal of bees: Honey vs. sucrose or high fructose corn syrup. Scientific Reports, 4(1), 5726.
Food Composition and Analysis, 28(1), 69–74. https://doi.org/10.1016/j. https://doi.org/10.1038/srep05726
jfca.2012.07.006 Yang, B., Kotani, A., Arai, K., & Kusu, F. (2001). Estimation of the antioxidant activities
Mato, I., Huidobro, J. F., Simal-Lozano, J., & Sancho, M. T. (2006). Rapid determination of flavonoids from their oxidation potentials. Analytical Sciences, 17(5), 599–604.
of nonaromatic organic acids in honey by capillary zone electrophoresis with direct https://doi.org/10.2116/analsci.17.599
ultraviolet detection. Journal of Agricultural and Food Chemistry, 54(5), 1541–1550. Zábrodská, B., & Vorlová, L. (2014). Adulteration of honey and available methods for
https://doi.org/10.1021/jf051757i detection - a review. Acta Veterinaria Brno, 83(10), S85–S102. https://doi.org/
10.2754/avb201483s10s85

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