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Yanqun Tong, Liuxin Ding, Kuiguo Han, Xiaobo Zou, Shiyan Wang, Zhang
Wen, Yunxia Ye & Xudong Ren
To cite this article: Yanqun Tong, Liuxin Ding, Kuiguo Han, Xiaobo Zou, Shiyan Wang, Zhang
Wen, Yunxia Ye & Xudong Ren (2022) Detection of carbendazim in oranges with metal grating
integrated microfluidic sensor in terahertz, Food Additives & Contaminants: Part A, 39:9,
1555-1564, DOI: 10.1080/19440049.2022.2093983
CONTACT Yanqun Tong tongyanqun_99@163.com School of Mechanical Engineering, Jiangsu University, Zhenjiang, China
ß 2022 Jiangsu University
1556 Y. TONG ET AL.
Figure 1. (a) Schematic of the experimental system, diagram of metal grating detecting the sample by (b) transmission method
and (d) reflection method, the terahertz (c) transmission and (e) reflection spectrum of the sample.
uses the tablet method (Hua and Zhang 2010; cost, it is often used for sterilization of agricul-
Baek et al. 2016), which has limited sensitivity tural products such as cereals, vegetables and
and it is not easy to detect trace elements. fruits, etc. However, the use of high doses is
In order to improve the detection sensitivity, destructive to our liver and may cause liver can-
terahertz biosensors have been continuously cer (Peyre et al. 2014). This work proposes a
developed for pesticide residues. At present, tera- novel reflective metal grating integrated micro-
hertz biosensors are mostly made of metamateri- fluidic sensor to detect carbendazim, using
als, which are artificial electromagnetic materials affordable and effective laser surface microma-
in the sub-wavelength scale range. They have the chining technology to achieve the fabrication of
advantages of high sensitivity, fast response and metal grating with a high sensitivity of up to
label free detection (Xu et al. 2017; Qin et al. 8.773 GHz/mg L1. Compared with the traditional
2018; Liu 2020; Nie et al. 2020). To maximize the terahertz transmission sensor, the sensitivity is
interaction between light and analyte, the micro- improved about eight times, mainly because the
fluidic chip technology developed in recent years light-matter interaction in the microfluidic chan-
provides new ideas for the production of tera- nel is greatly enhanced. Moreover, the fabricated
hertz biosensors, by combining metamaterials sensor is used to detect carbendazim in orange.
and microfluidic chips for the detection of
different organic solutions (methanol-water, etha-
nol-water and isopropanol-water) and glucose Materials and methods
solutions in the terahertz band (Liang et al. 2018;
Experimental method design
Shih et al. 2018), detection of polystyrene beads
in isopropanol (IPA) solutions (Shih et al. 2017) System design
etc. Nowadays, metamaterials are often fabricated This experiment used the THz-TDS system as
by ultraviolet lithography, which is complicated shown in Figure 1(a). The system is composed of
and time-consuming. Metal grating surface plas- five parts, similar to the one described by Tong
mons (SPPs) also show phenomena of abnormal et al. (2020). Both adopt the commercial
transmission and local enhancement of light field TAS7400TS system produced by Advantest com-
(Dai et al. 2018). In recent years, the terahertz pany of Japan. The difference lies in our study
region has also been used for the detection of uses transmission and reflection modules. The
biological and chemical substances (Yoshida et al. terahertz beam focusing spot diameter on the
2007; Zhen et al. 2009), however there are sample is 1–2 mm approximately. To reduce the
few articles. system error caused by noise in the experimental
In the case of carbendazim pesticide, because results, the result of each measurement is the
of its broad-spectrum activity and low production average value after 128 scans.
FOOD ADDITIVES & CONTAMINANTS: PART A 1557
Figure 2. (a) Process flow including (1) nanosecond laser micromachining on aluminum foil to fabricate square hole arrays, (2)
metal grating glued on polyimide film with resin glue, (3) nanosecond laser micromachining on aluminum plate to make micro-
flow channel, (4) laser drilling to make the inlet and outlet and (5) package. (b) Schematic of nanosecond laser micromachining
system and (c) micrograph of the metal hole array. Photo images of (d) transmission-type metal grating sensor and (e) reflection-
type metal grating sensor.
IPG-HP-100 pulsed fiber laser produced by IPG Since the designed sensor was a metal grating
Company. Its laser power can be adjusted from structure, the incident terahertz wave excited
0 W to 100 W, the wavelength is 1064 nm, the SPPs in the metal microstructure (Wang et al.
pulse width is approximately 100 ns, and the 2018). To study the variation of the performance
focus spot diameter is 50 lm. The maximum area of metal grating under different structural param-
that can be scanned is 100 mm 100 mm. The eters, numerical simulation was used to demon-
two-dimensional mobile platform was used to strate the dependence of transmission spectrum
control the laser focal length and the position of on the period p and the side length 2a.
the sample material to ensure that the material Transmission was defined as T ¼ Esamp =Eref ,
surface was in the focal position. In this experi- where Esamp and Eref were frequency-domain
ment, the square side length a 80 lm and the amplitudes of the samples and reference signals,
period p 140 lm were set. The production respectively. Under the condition that the side
effect is shown in Figure 2(c), in which the total length of the square was 80 lm, the period
size of the metal grating is 8 mm 8 mm. The increased from 130 lm to 170 lm, and the trans-
transmissive and reflective sensors are shown in mission peak was red-shifted and the bandwidth
Figure 2(d,e), these two devices are manufactured was narrowed (Figure 3(a)). Under the condition
according to the steps described in Figure 2(a). of a period of 140 lm, the side length of the
The metal microstructure was bonded with the square hole was increased from 60 lm to 100 lm,
polyimide film through epoxy resin glue. The the transmission peak also had red-shifted and
reflective sensor was achieved by using water- the band width became wider (Figure 3(b)). It
proof tape to assemble the cover layer and the shows that the transmission spectrum characteris-
substrate together. tics of the metal hole array can be modulated by
changing the size of the structural unit. In this
Sample collection
experiment, we selected a whole array of nar-
rower bandwidth and higher transmittance (a
For the presented study, oranges were chosen to 80 lm, p 140 lm).
verify whether this method is feasible for the In order to characterize the spectral response
determination of carbendazim in actual agricul- of the metal grating, media with different relative
tural products, and the experimental samples was permittivity er were loaded on the surface of the
from the local Food and Drug Administration metal grating and the microfluidic channel dur-
(FDA). Because of the complex composition of ing simulation. The corresponding transmission
actual samples, simple processing was required and reflection spectra are shown in Figure 3(c,d),
before spectral detection. Firstly, chopped and respectively. As the permittivity of the analyte
homogenized the orange sample to obtain a pasty increases from 1 to 2.8, the transmission peak
sample. Then, placed a 20 g paste sample in a shifts to low frequencies in both transmission
centrifuge tube and diluted it with 20 mL acetone. and reflection modes. According to the sensor
pffiffiffiffi
The mixture was centrifuged at 5000 rpm for sensitivity S ¼ Df =D er , the relationship
10 min to extract the supernatant. between the resonant frequency of the sensor and
the dielectric constant of the medium was fitted,
Results and discussion with the results shown in Figure 3(e,f). The the-
oretical sensitivities of the sensor in transmission
Mechanism of metal grating sensor
mode and reflection mode are 641.2 GHz/RIU
This work used the finite-difference-time-domain and 1178.9 GHz/RIU, respectively, which are
method in CST Microwave Studio software to excellent sensing performances. Figure 4(a) shows
numerically simulate the designed metal grating the electric field distribution of the metal grating
sensor. In the simulation, the electrical conduct- at the resonance frequency of 1.815 THz when
ivity of the aluminum material was set to a lossy the electric field of the incident terahertz wave
metal with r ¼ 3.56 107 S/m, the metal grating was along the x-axis. The strong electric field was
substrate was selected as low-loss polyimide. distributed on the edge of the square hole,
FOOD ADDITIVES & CONTAMINANTS: PART A 1559
Figure 3. The dependences of transmission spectrum on (a) the period p and (b) the side length a of the square, (c) transmission
spectra by transmission method and (d) reflection spectra by reflection method of samples with different permittivity, fit diagram
of the frequency shift of the resonance peak and the permittivity of the sensor e in transmission mode and f reflection mode.
Figure 4. (a) Simulated electric field distributionat the resonant frequency for the metal grating, the electric field distribution per-
pendicular to the metal grating by (b) transmission method and (c) reflection method.
indicating that the electric field distribution in z-direction. The transmissive electric field was
this area is highly confined. Figure 4(b,c) show mainly concentrated above the hole, which was
the electric field distribution of the transmissive relatively divergent and had a smaller overlap
and reflective metal grating sensors in the area with the analyte (white dotted line), resulting
1560 Y. TONG ET AL.
in lower sensitivity. In contrast, the higher sensi- at the first two concentrations only slightly red-
tivity of the reflective sensor benefited from the shifted, while the transmission peak frequency
new integration of metal grating and microflui- changed most drastically at the last three higher
dic, where the cavity resonance and the analyte concentrations, from 1.781 THz at 1 mg/L to
(white dashed line) had the greatest overlap, 1.772 THz at 10 mg/L. This is because the carben-
which resulted in a greater resonance frequency dazim concentration has a positive correlation
shift (Hu et al. 2016). with its refractive index (Ye et al. 2021). When
the refractive index of the analyte increases, the
Detect carbendazim by transmission method
effective refractive index of the gap plasma
decreases, and the resonance frequency decreases
Figure 5(a) shows the measured and simulated resulting in a redshift. As the concentration of
transmission spectra of the metal grating. The the analyte increases, the larger the frequency
highest transmission peak frequency of the meas- shift of transmission peak. The results show that
ured transmission spectrum was 1.791 THz, while the combination of metal grating and THz-TDS
the simulated highest transmission peak fre- can detect trace amounts of carbendazim.
quency was 1.818 THz. Due to problems such as
the external environment and the precision of the
Detection of carbendazim by the
square hole production, the measured transmis-
reflection method
sion peak presented a narrower band width than
the simulated transmission peak. As mentioned Figure 5(d) shows the reflection spectra of differ-
above, the designed metal grating was very sensi- ent concentrations of carbendazim solutions.
tive to the dielectric constant of the medium. When the concentration of carbendazim in the
When the dielectric constant of the solution microfluidic channel gradually changed from
around the metal grating changed, the position of 0 mg/L to 10 mg/L, the two resonant peaks of the
the resonance peak also changed. In order to sensor could be observed to be redshifted simul-
investigate the sensitivity of the transmissive and taneously, and the experimental results were in
reflective sensors, we compared the experimental good agreement with the simulation results. The
results of transmissive and reflective sensors. frequency of the two resonance peaks in the
Figure 5(b) shows the transmission spectra of reflection spectrum was further studied with
carbendazim solutions with different concentra- the change of carbendazim concentration in the
tions, and the transmission peaks has shifted sig- microfluidic channel, and the results are shown
nificantly. In the concentration range of 0 mg/L in Figure 5(e), the curve fitting of the resonant
to 10 mg/L, the transmission peak redshifted (to a peak at low frequency was y ¼ 0.0009x2 –
longer wavelength) as the concentration 0.0155x þ 1.0699, R2 ¼ 0.96; the curve fitting of
increased, which was similar to the simulation the resonant peak at high frequency was
results. When the concentration of carbendazim y ¼ 0.0011x2 – 0.0184x þ 1.5183, R2 ¼ 0.93. As
in the sample changed from 0 mg/L to 10 mg/L, the concentration of carbendazim increased, the
the peak position of the resonance peak shifted frequency shift values of the two resonance peaks
from 1.789 THz to 1.772 THz. also increased. The maximum frequency shift of
For further study, Figure 5(c) shows the rela- the resonance peak at low frequency was
tionship between the transmission peak frequency 30.5 GHz, and the corresponding concentration
and carbendazim concentration. The curve fitting changed from 0.5 mg/L to 1 mg/L. At the same
was y ¼ 0.0002x2 – 0.0034x þ 1.7872, R2 ¼ 0.94. time, the resonance peak at high frequency also
As the increase of carbendazim concentration, got the maximum frequency shift in this concen-
the frequency shift value increased, and the max- tration range, reaching 26.7 GHz. As the concen-
imum frequency shift value of the resonance tration gradually increased from 0 mg/L to
peak was 13.4 GHz, and the corresponding con- 10 mg/L, the resonance peak at low frequency
centration changed from 5 mg/L to 10 mg/L. On shifted by 70.6 GHz and the resonance peak at
the other hand, the transmission peak frequency high frequency shifted by 87.7 GHz, which
FOOD ADDITIVES & CONTAMINANTS: PART A 1561
Figure 5. Spectra and sensitivity of transmission and reflection sensors. (a) Transmission spectrum of metal grating, (b) transmis-
sion spectra of carbendazim solutions of different concentrations, (c) the variation of resonance frequency of transmission peak
with the concentration of carbendazim, (d) reflectance spectra of carbendazim solutions of different concentrations, (e) the vari-
ation of the resonance frequencies of each reflection peak with the concentration of carbendazim and (f) sensitivity of each reson-
ance peak of the sensor.
showed the resonance peak frequency shift at concentrations in Orange A, Orange B and
high frequency was large. As can be seen from Orange C were found to be 2.382 ± 0.003,
Figure 5(c,e), when the concentration increased 2.121 ± 0.003 and 2.249 ± 0.003 mg/kg. The
from 0 to 0.5 mg/L, the transmission peak shifted National standard GB 26130-2010 of the People’s
in frequency, so the microfluidic sensor could Republic of China stipulates that the maximum
detect carbendazim solutions with concentrations residue limit of carbendazim in oranges is 5 mg/
as low as 0.5 mg/L. kg. Next the concentration of carbendazim in
We calculated the sensitivity corresponding to oranges was determined by the metal grating sen-
the resonance peak of each sensor, and the result sors. The results are summarized in Table 1. The
is shown in Figure 5(f). The sensitivity of the carbendazim concentration of Orange A deter-
designed transmissive metal grating sensor was mined using the transmissive sensor was
1.717 GHz/mg L1 (the resonance peak shift in 2.242 ± 0.032 mg/kg, with a relative error of 5.8%.
unit concentration), the sensitivity at the low fre- The carbendazim determined at low and high fre-
quency of the reflective metal grating sensor
quency using the reflective sensor was
reached 7.057 GHz/mg L1 and the sensitivity at
2.256 ± 0.028 mg/kg and 2.264 ± 0.027 mg/kg, and
the high frequency reached 8.773 GHz/mg L1.
the relative errors were 5.2% and 4.9%, respect-
Therefore, the reflective sensor had higher sensi-
ively. Compared with Orange B and Orange C,
tivity than the transmissive sensor, and when
the relative error was smaller. The relative error
used in the detection of carbendazim, a more
obvious resonance peak frequency shift could for each orange sample in the transmissive sensor
be observed. was generally greater than that of the reflective
sensor, and the relative error detected by the
high frequency in the reflective sensor was the
Real sample analysis smallest, the sensitivity was the highest. The
Orange samples from the local FDA were ana- experimental results showed that the metal gra-
lyzed by LC-MS, and the carbendazim ting reflective sensor had high accuracy for the
1562 Y. TONG ET AL.
determination of carbendazim. Therefore, this domain was designed. The highly confined elec-
method was feasible to determine the carbenda- tromagnetic field in the microfluidic channel can
zim in samples of fruit such as oranges. significantly enhance the interaction between the
analyte and the terahertz wave and improve the
Matrix effect evaluation sensitivity of terahertz detection. The square hole
array metal grating used in the experiment was
The experimental samples were divided into fabricated by nanosecond laser micromachining
orange matrix group (B) and acetone solvent technology, which has the advantages of simple
group (A). The oranges without carbendazim processing, low cost and has good sensitivity to
were determined as the experimental samples of the surrounding sample environment. The results
Group B, and the carbendazim powder was show that with an increase in concentration of
added to acetone and the orange base solution to carbendazim, the peak positions of the two res-
prepare two groups of 1.0, 1.5, 2.0, 2.5 mg/kg onance peaks in the reflection spectrum gradually
samples to be tested. Each analysis was repeated redshift. The sensitivity of the peak at low fre-
five times. The relative ratio method was used to quency and high frequency reaches 7.057 GHz/
evaluate the matrix effect (ME) with the formula mgL1 and 8.773 GHz/mgL1 respectively.
below Compared with the traditional terahertz transmis-
MEð%Þ ¼ a=b 100 sive sensor, the sensitivity is increased by about
eight times. The method was applied to the
Where a and b are the response values of car-
determination of carbendazim in oranges, and
bendazim in orange matrix and acetone solvent.
the relative error was less than 5.3%. It has been
The measurement results are shown in
shown that the metal grating integrated micro-
Table 2. It can be seen that the matrix effect
fluidic sensor combined with terahertz time-
(ME, %) at the measured carbendazim concentra-
domain spectroscopy technology can improve the
tion level was between 104.3% and 112.3%, which
sensitivity of sample detection. It can also achieve
is a weak enhancement matrix effect, and the
rapid detection and analysis at trace levels, which
matrix effect is not obvious. Therefore, the tera-
has potentially broad application in the research
hertz microfluidic sensor used to detect the con-
fields of trace analysis, biosensors and
tent of carbendazim in oranges has good food safety.
accuracy and reliability.
Disclosure statement
Conclusions
TThe authors declare that they have no known competing
In summary, a novel metal grating integrated financial interests or personal relationships that could have
microfluidic sensor in the terahertz frequency appeared to influence the work reported in this paper.
FOOD ADDITIVES & CONTAMINANTS: PART A 1563
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