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All content following this page was uploaded by Shima Jahangiri on 17 July 2019.
To cite this article: Abdolreza Mirmohseni, Khalil Farhadi & Shima Jahangiri (2019): Application
of polydimethylsiloxane/ acrylic resins coated quartz crystal nano balance sensor for detection
of glyphosate pesticide, International Journal of Environmental Analytical Chemistry, DOI:
10.1080/03067319.2019.1639687
Article views: 1
ARTICLE
1. Introduction
Pesticides are widely used compounds within the agricultural and residential sectors for
pest control. The term pesticide includes herbicide, insecticides, insect growth regulators,
termiticides, nematicide, molluscicide, piscicide, avicide, rodenticide, bactericide, insect
repellent, animal repellent, antimicrobial, fungicide, disinfectant (antimicrobial) and saniti-
zer [1,2]. Pesticides are considered as one of the main factors involved in environmental
contamination of today’s world [3]. Despite various advantages of pesticides, there are also
disadvantages mainly due to the toxicity towards humans and other species.
Organophosphorus compounds (OP) are a major group of pesticides with organic com-
pounds that contain phosphorus and are widely used in agriculture, vector control and for
domestic purposes [1]. Because of the widespread use of OP pesticides and high exposure of
the general population to these chemicals, there are high risks involved with potential
health impacts [4]. There are numerous techniques that could be used for the analyses of OP
pesticides including gas chromatography or high-performance liquid chromatography
(HPLC) coupled with mass spectroscopy (MS) [5–8], Electrochemical [9–11], immunochem-
ical [12,13] and biosensors [14,15]. Sinha et al. developed a sensitive GC-MS method for the
determination of chlorpyrifos in human blood samples [6]. Similarly, Rodrigues et al. devel-
oped a method based on solid-phase microextraction (SPME) coupled to GC-MS. They
determined residues of organophosphorus pesticides in cow’s milk [7].
In another study, Tan et al. used glassy carbon (GC) electrode and electrodeposited
thin film of organophosphorus – templated molecularly with imprinted porous silicate
on GC [8]. Parham et al. presented a carbon paste electrode based on modification with
ZrO2-nanoparticles for the determination of organophosphorus [9]. Garcés-García et al.
reported an Enzyme-linked immunosorbent assay (ELISA) method for the determination
of four (OP) pesticides in extra virgin olive oil [12]. Recently, there has been an increasing
interest in sensor-based technology for fast pesticide detection using easy and rapid
procedures [16]. Piezoelectric sensors have also been used for pesticide detection due to
their high sensitivity. Considering their small size, simplistic design and low manufactur-
ing cost, they could be a great alternative within the portable sensors market. Quartz
Crystal Nano Balance (QCN) is a sensitive mass sensor that contains a thin vibrating AT-
cut quartz wafer sandwiched between two metal excitation electrodes [15,17,18]. The
typical piezoelectric quartz crystal is shown below with a schematic of the shear
horizontal vibration Figure 1.
Sauerbrey’s equation is used to relate the frequency change (ΔF) to the mass load-
ing (Δm):
Analyte molecules
Metal electrode
Sensitive
coating
Electrical lead
Δm
Δf
where F0 (MHz) is the fundamental resonant frequency of the non-coated quartz crystal
(10 MHz), A is the electrode area (0.21 cm2). Using these constants, the below equation
can be obtained:
The selection of sensitive coating is an important step during design and operation
process of chemical QCN sensors. Polymers are extensively used as chemically sensitive
coating substance on quartz crystal electrodes and are especially acceptable for the
determination of environmental pollutants [17–19].
The QCN technique has been used in the past for the detection of organophosphorus
and carbamate pesticides [17,20–34]. In an experimental study, Reddy et al. used a two-
enzyme system (acetylcholine-esterase and choline oxidase) on the quartz crystal electrodes
for the determination of carbaryl and dichlorvos [22]. The designed sensor showed
a reasonable detection limit (accurate to 1 ppm), however enzyme immobilization at the
surface of the sensor were observed. In another study, Mirmohseni et al. used 75% phenyl
(OV25) modified quartz crystal to determine the concentration of telone (soil fumigant) in
the air [35]. The results obtained showed linear response in the range of 2.4–48 mg/L with
the correlation coefficients above 0.99% and the sensitivity factors in the range of 9.0512 Hz/
mg L−1. In a study conducted by Liu et al., a selective quartz crystal microbalance was
designed by mixing polyvinyl chloride and molecularly imprinted polymer microspheres
(MIPMs) immobilized in situ, on a piezoelectric quartz crystal for the detection of endosulfan
[36]. The results obtained included a detection limit (LDL) of 5.59 ng mL−1, and a recovery in
the range of 96.0–104.1%within water samples. In a study published by Ozkutuk et al.,
a sensor based on the modification of molecular-imprinted coating was developed for the
detection of paraoxon. The paraoxon selective coating were formed on QCM electrode
surface by using a new metal–chelate interaction based on pre-organized monomer and the
paraoxon recognition activity of the molecular memories were further investigated [16]. The
study also included the measurement of binding interaction of QCM sensor, selectivity
experiments and analytical performance of quartz crystal microbalance with a detection
limit of 0.06 μM.
Pan et al. reported the characterization of a multi-wall carbon nanotube/poly
(amidoamine) dendrimer (MWCNT-PAMAM) hybrid material and its application for
the fabrication of a piezoelectric immunosensing platform [38]. The immunosensors
were used for the determination of a carbamate pesticide-metolcarb. In the study, it
was also found that the proposed methodology allows sequential-specific detection
limit with a value of 0.019 mg/L.
High Fundamental Frequency Quartz Crystal Microbalance sensor (HFF-QCM) was
used by Montoya et al. for pesticide detection in honey [31]. This immunosensor showed
high sensitivity with a detection limit of 0.118 µg/L without sample pre-treatment. Gupta
et al. used imprinted polymer modified quartz crystal to determine the atrazine in
wastewater [32]. The linearity range was obtained as 0.08–1.5 nM. The detection limit
of the atrazine was calculated as 0.028 nM. With the studies published by Fang et al.,
a sensor based on MIP was developed for detection of metolcarb in foods. The sensor
showed a linear relationship between frequency shift and concentration of metolcarb
ranging from 5 g/L to 70 g/L with a detection limit of 2.309 g/L [33].
4 A. MIRMOHSENI ET AL.
This paper presents a high sensitivity, low cost, reproducable and simple method
for determination of trace amounts of glyphosate in water samples. Glyphosate
(N-phosphonomethyl glycine) acts as an enzyme inhibitor and is only active on
growing plants [4]. This enzyme is essential in the biosynthesis of three aromatic
amino acids, phenylalanine, tyrosine and tryptophan [39]. Glyphosate is used to
control annual weeds and grasses that compare with crops [39–41]. The main
degradation product of glyphosate in soil and water is aminomethylphosphonic
acid (AMPA) [41]. The ‘Lethal Dose, 50%’ (LD50) reported from animal studies on
these agents is greater than 4000 mg/kg for glyphosate [39,41]. The maximum
contaminant level (MCL) of glyphosate for safe drinking water issued by the US
Environmental Protection Agency (EPA) is 0.7μg/ml [42]. Various analytical methods
have been developed for the detection and determination of glyphosate in water
samples including gas chromatography (GC) [42] or high-performance Liquid chro-
matography (HPLC) [43,44]. GC/MS methods [45–47] Liquid chromatography coupled
to electrospray tandem mass spectrometry (LC/MS) [44,45,48] Capillary electrophor-
esis (CE) [47], ion chromatography (IC) [49]. Communal et al. have used exchange ion
resin purification and derivatization to determine glyphosate and aminomethylpho-
sphonic acid residues in water [45]. The study reported a limit of quantification of
0.05 μg/L for each compound. In another study, Hernandez et al. reported a method
for determination of glyphosate, glufosinate and aminomethylphosphonic acid
(AMPA) residues in water and soil samples [44,45,48]. This process involved
a derivatization step and detection based on liquid chromatography coupled to
electrospray tandem mass spectrometry (LC-ESI-MS/MS). The LOD for all the three
compounds were as low as 5 ng/L, in water, and 5 g/kg, in soil.
In a study conducted by Cai et al., a polymer anion-exchange column was used to
determine the glyphosate concentration [49] and a detection limit of 0.7 μg/L was
obtained. Tables 1 and 2 summarise the methods used to detect glyphosate in biological
and environmental materials. Despite the advantages of these methods, there are still
challenges that remain including the time-consuming development steps such as sam-
ple extraction, pre-concentration step, derivatization procedures, expensive and specia-
lized equipment required [39–42]. To date, different polymer-coated quartz electrodes
have been successfully considered for the detection of various chemicals [50]. Polymers
with low glass transition temperatures (TG) are advisable for acoustic wave sensor
applications [51]. Here, we present a detailed study on the development of a sensitive,
Table 1. Analytical methods for determination of glyphosate and metabolites in biological materials.
Sample matrix Preparation method Analytical method Limit of detection (μg/L) Recovery (%) Reference
Cows Vortex mix GC-MS 35 ± 50 91 [29]
urine ELISA kits ELISA 27 ± 42
Human Vortex mix GC-MS 5.4 ± 11.5 91 [30]
urine ELISA kits ELISA 9 ± 15
Urine Fortification GC–NPD, HPLC 2–200 56 [30]
Extraction
Extract Cleanup
GC-MS = Gas Chromatography Mass Spectroscopy.
ELISA = enzyme-linked immunosorbent assay.
GC-NPD = Gas Chromatography with a Nitrogen-Phosphorus Detector.
HPLC = high-performance liquid chromatography
INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 5
simple and rapid method for the measurement of glyphosate in water. Considering the
benefits of quartz crystal nano balance techniques, a mixture of polydimethylsiloxane/
acrylic resin was used for the detection of glyphosate in water.
2. Experimental
2.1. Reagents and chemicals
All chemicals were purchased from Merck (Germany) and used without any further
purification. Acrylic resin was supplied by Taak resin Co (Iran). Glyphosate was purchased
from Kimiya Gohare Khak Co (Iran). Polydimethylsiloxane was purchased from Sigma
Aldrich (USA).
2.2. Instrumentation
AT-cut quartz crystals (10 MHz) with gold electrodes on both sides were purchased from
International Crystal Manufacturer (ICM, Oklahoma, USA). A homemade apparatus
described in our previous work was employed as shown in Figure 2 [52]. A Hamilton
syringe was used for the injection of the organic compounds. A flowmeter (Azmoon
Motamam) was used to adjust the flow rate of N2. Polymer thickness was measured
using a digital thickness meter (Guanglu Instruments Co., Ltd).
The flow was adjusted at the rate of (7L/min) throughout all experiments. The
temperature variation (at the range 20–500°C) will not affect frequency measurements
since the crystal is AT-cut. The effect of temperature variation was minimized by the use
of AT cut crystal plates.
6 A. MIRMOHSENI ET AL.
Analyte
Computer
Oscillator
Crystal
Cell
Analyte
isobutyl ketone solutions. After each coating, the polymer-coated electrode was
exposed to a constant concentration of glyphosate and the frequency shift of the crystal
was recorded in Figure 3. It was found that the coating thickness depended on the
polymer concentration. The response of the polydimethylsiloxane/acrylic resin coated
QCN showed an increase with an increase in deposited mass below 0.25% w/v, but
above 0.25% w/v, the response tended to level off.
As shown in Figure 3, as the concentration of polymer increased, the frequency shift
increased since more polymer molecules deposited. However, in the concentrated
solution, the frequency shift decreased for the values greater than 0.25% w/v, con-
centrated polymer solution was not evenly spread over gold electrode. Thicker solution
tends to be localized at the edge area of the electrode. Narrower sensitivity distributions
and less mass sensitivity beyond the electrode edges have been reported pre-
viously [54].
Various amount of polydimethylsiloxane/acrylic resin mixture was applied over gold
film electrode. Therefore, the films obtained by using (10μl of polydimethylsiloxane/
acrylic resin Solution (0.25% w/v)) was considered as the optimum mass and used in all
the sensing studies (~5000 nm in thickness). With the similar experiment, at the surface
of gold-coated quartz electrode, a frequency shift of 10 kHz was obtained for the
thickness of 5000nm. The observed behaviour implied that there is a limit of adsorption
of molecules in a small area of adsorbent and an excessive coating is unnecessary for
a QCN sensor. Furthermore, overcoating the sensor would disturb the resonance stability
and occasionally cause failure within the quartz crystal oscillation [15,53].
Figure 3. The effect of polymer concentration of casting solution on frequency changes modified
quartz crystal electrode.
8 A. MIRMOHSENI ET AL.
Figure 4. Typical frequency changes of modified quartz crystal electrode in exposure to 4.4 mg/L of
Glyphosate in water samples. Polymer films were cast from a 0.25% (w/v) solutions and ΔF coating =
10,000 Hz: (a) Sample injection and (b) N2 Purge.
INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 9
Figure 6. Calibration curves for determination of Glyphosate using modified quartz crystal electrode.
(Exposure time: 750 s).
Table 3. Analytical characteristic parameters for the determination of Glyphosate by modified quartz
crystal electrode.
Sensitivity factor Linear calibration
Compound R2a (Hz/mg L−1) LODb (mg/L) R.S.D (%) (n = 6) range (mg/L)
Glyphosate 0.98 70.73 1.28 4.14 0.2–8.6
a. Square correlation coefficient.
b. limit of detection.
c. Relative standard deviation
10 A. MIRMOHSENI ET AL.
Figure 7. Reproducibility test for frequency changes of modified quartz crystal electrode exposed to
4.4 mg/L Glyphosate: (a) Glyphosate injection and (b) Glyphosate desorption by purging N2 through
the cell.
INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 11
3.7. Interference
The major cationic constituents of water are calcium, magnesium and sodium, while the
most common anions include chloride, sulfate and bicarbonate [37]. To mimic the effect
of these salts, the interference of major salts (NaCl, NaHCO3, CaSO4 and MgSO4) in water
tested. The frequency shifts of a modified quartz crystal electrode upon exposure to
10 mg/L glyphosate in water, was obtained. The frequency shifts of the same electrode
in exposure to each of interferents in a 10-fold excess concentration (100 mg/L) were
also recorded (Table 4). It was found that no major interference (except NaCl) was
involved in the performance of the sensor. It is presumed that chloride anion react
with siloxane polymer caused the major interference. It should be noted that changes in
frequency of less than 5 Hz were considered as ‘no response’.
4. Conclusions
In this study, a novel and inexpensive method of detection were developed for rapid
and quantitative detection of glyphosate levels in water. The method, based on the
modified quartz crystal electrode demonstrated a high sensitivity and selectivity
towards glyphosate.
A linear response (R2 = 0.98) was obtained for the sensor within glyphosate concen-
trations of 0.8–9.6 mg/L. The reproducibility of the sensor was confirmed by obtaining
a RSD value of 4.14%. The LOD of the sensor for was found to be 1.28 mg/L. The
modified quartz-coated electrode also showed several advantages including low cost of
manufacturing, ease of design and preparation, storage stability, and re-using capability
without significant loss in activity.
Acknowledgments
This paper is published as part of a research project supported by the university of Tabriz research
affairs office.
Disclosure statement
No potential conflict of interest was reported by the authors.
12 A. MIRMOHSENI ET AL.
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