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15 pages, 4163 KiB  
Article
3-Methyl-4-nitrophenol Exposure Deteriorates Oocyte Maturation by Inducing Spindle Instability and Mitochondrial Dysfunction
by Fan Chen, An-Feng Luo, Ming-Guo Li, Li-Xiang Zheng, Hao Gu, Chang-Fan Zhou, Wei Zeng, Adrian Molenaar, Hong-Yan Ren and Yan-Zhen Bi
Int. J. Mol. Sci. 2024, 25(7), 3572; https://doi.org/10.3390/ijms25073572 - 22 Mar 2024
Viewed by 1590
Abstract
3-methyl-4-nitrophenol (PNMC), a well-known constituent of diesel exhaust particles and degradation products of insecticide fenitrothion, is a widely distributed environmental contaminant. PNMC is toxic to the female reproductive system; however, how it affects meiosis progression in oocytes is unknown. In this study, in [...] Read more.
3-methyl-4-nitrophenol (PNMC), a well-known constituent of diesel exhaust particles and degradation products of insecticide fenitrothion, is a widely distributed environmental contaminant. PNMC is toxic to the female reproductive system; however, how it affects meiosis progression in oocytes is unknown. In this study, in vitro maturation of mouse oocytes was applied to investigate the deleterious effects of PNMC. We found that exposure to PNMC significantly compromised oocyte maturation. PNMC disturbed the spindle stability; specifically, it decreased the spindle density and increased the spindle length. The weakened spindle pole location of microtubule-severing enzyme Fignl1 may result in a defective spindle apparatus in PNMC-exposed oocytes. PNMC exposure induced significant mitochondrial dysfunction, including mitochondria distribution, ATP production, mitochondrial membrane potential, and ROS accumulation. The mRNA levels of the mitochondria-related genes were also significantly impaired. Finally, the above-mentioned alterations triggered early apoptosis in the oocytes. In conclusion, PNMC exposure affected oocyte maturation and quality through the regulation of spindle stability and mitochondrial function. Full article
(This article belongs to the Special Issue Transcriptional Regulation of Late Oogenesis and Early Embryogenesis)
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Figure 1

Figure 1
<p>PNMC exposure disturbs the meiotic maturation of oocytes. (<b>A</b>) Fully grown GV oocytes were exposed to PNMC at the indicated concentrations (0, 25, 50, and 100 nM) for 14 h. Control and 25 nM PNMC-treated groups normally attained meiotic maturation; however, most oocytes failed to accomplish PBE after treatment with 50 and 100 nM PNMC. Scale Bar = 100 µm. (<b>B</b>) The percentages of PBE in control (<span class="html-italic">n</span> = 206) and PNMC-exposed groups (25 nM, <span class="html-italic">n</span> = 255; 50 nM, <span class="html-italic">n</span> = 281; 100 nM, <span class="html-italic">n</span> = 196) are shown. (<b>C</b>) The oocytes were cultured for 24 h to investigate the effects of PNMC exposure on oocyte mortality. Cell death was prominent in the 50 nM PNMC-exposed oocytes, unlike in the control group. Scale Bar = 100 µm. (<b>D</b>) The proportion of cell death was analyzed in control (<span class="html-italic">n</span> = 195) and 50 nM PNMC-exposed (<span class="html-italic">n</span> = 188) oocytes. ns (not significant) means <span class="html-italic">p</span> ≥ 0.05; *** <span class="html-italic">p</span> &lt; 0.001.</p>
Full article ">Figure 2
<p>PNMC exposure causes spindle instability at the MI stage. (<b>A</b>) The representative images of spindle morphology and chromosome alignment in control and PNMC-exposed oocytes. After excluding the oocytes that did not accomplish GVBD at 2 h, the remaining control and PNMC-treated oocytes were immune-stained with α-tubulin after another 6 h culture (MI oocytes). α-tubulin, green; DNA, blue. Scale Bar = 20 µm. (<b>B</b>) The fluorescence intensity of spindle α-tubulin was quantified in control (<span class="html-italic">n</span> = 26) and PNMC-exposed (<span class="html-italic">n</span> = 29) oocytes. (<b>C</b>–<b>F</b>) Spindle length, width, and length/width ratio were quantified in control (<span class="html-italic">n</span> = 36) and PNMC-exposed (<span class="html-italic">n</span> = 38) groups. (<b>G</b>) Images delineating spindle morphology in control and PNMC-exposed MI oocytes after nocodazole treatment. α-tubulin, green; DNA, blue. Scale Bar = 20 µm. (<b>H</b>,<b>I</b>) The spindle fluorescence intensity and area were quantified in control (<span class="html-italic">n</span> = 28) and PNMC-exposed (<span class="html-italic">n</span> = 31) groups. * <span class="html-italic">p</span> &lt; 0.05, ** <span class="html-italic">p</span> &lt; 0.01.</p>
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<p>PNMC exposure disturbs spindle localization of Fignl1 in oocytes. (<b>A</b>–<b>C</b>) The mRNA levels of <span class="html-italic">KATNAL1</span>, <span class="html-italic">FIGNL1</span>, and <span class="html-italic">SPAST</span> were confirmed by qRT-PCR. The mRNA expressions of <span class="html-italic">SPAST</span> and <span class="html-italic">KATNAL1</span> were unaffected at the MI stage between control and PNMC-exposed groups; however, the level of <span class="html-italic">FIGNL1</span> was significantly inhibited after PNMC exposure. (<b>D</b>) Images illustrating the localization pattern of Fignl1 in control and PNMC-exposed MI oocytes. α-tubulin, green; Fignl1, red; DNA, blue. Scale Bar = 20 µm. (<b>E</b>) Quantitative analysis of the fluorescence intensity of Fignl1 in control (<span class="html-italic">n</span> = 28) and PNMC-exposed (<span class="html-italic">n</span> = 30) groups. * <span class="html-italic">p</span> &lt; 0.05, ** <span class="html-italic">p</span> &lt; 0.01.</p>
Full article ">Figure 4
<p>PNMC exposure disrupts the mitochondrial function in oocytes. (<b>A</b>) Control and PNMC-treated MI oocytes were labeled with MitoTracker Red to visualize mitochondrial distribution. Scale Bar = 5 µm. (<b>B</b>) ATP levels were determined in the control (<span class="html-italic">n</span> = 43) and PNMC-exposed (<span class="html-italic">n</span> = 39) groups. (<b>C</b>) MMP in the control and PNMC-exposed MI oocytes by JC-1 staining. The green signal represents inactive mitochondria and the red signal represents active mitochondria in oocytes. Scale Bar = 100 µm. (<b>D</b>) MMP was quantified in control (<span class="html-italic">n</span> = 30) and PNMC-exposed (<span class="html-italic">n</span> = 28) groups. ** <span class="html-italic">p</span> &lt; 0.01.</p>
Full article ">Figure 5
<p>PNMC treatment induced the increased ROS levels in mouse oocytes. (<b>A</b>) ROS levels were assessed by DCFH-DA (green) staining. Representative images of ROS production in the control and PNMC-exposed MI oocytes. Scale Bar = 50 µm. (<b>B</b>) ROS levels were quantified in the control (<span class="html-italic">n</span> = 46) and PNMC-exposed (<span class="html-italic">n</span> = 38) groups. (<b>C</b>–<b>F</b>) The mRNA levels of antioxidant genes were evaluated by qRT-PCR. * <span class="html-italic">p</span> &lt; 0.05, ** <span class="html-italic">p</span> &lt; 0.01 and *** <span class="html-italic">p</span> &lt; 0.001.</p>
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<p>PNMC exposure blocks the expression of mitochondrial-related genes. (<b>A</b>–<b>D</b>) The relative mRNA levels of mitochondrial respiratory complexes, including <span class="html-italic">SDHA</span>, <span class="html-italic">UQCRC2</span>, and <span class="html-italic">ATP5A1</span>, were significantly decreased in PNMC-exposed oocytes. (<b>E</b>–<b>H</b>) The relative mRNA levels of genes related to mitochondrial dynamics, <span class="html-italic">DRP1</span>, <span class="html-italic">FIS1</span>, <span class="html-italic">MFN1</span>, and <span class="html-italic">OPA1</span>, were sharply reduced in PNMC-exposed oocytes. (<b>I</b>–<b>L</b>) The mtDNA, <span class="html-italic">ATP6</span> and <span class="html-italic">CYTB</span>, were significantly down-regulated after PNMC exposure. * <span class="html-italic">p</span> &lt; 0.05, ** <span class="html-italic">p</span> &lt; 0.01 and *** <span class="html-italic">p</span> &lt; 0.001.</p>
Full article ">Figure 7
<p>PNMC treatment triggers early apoptosis in oocytes. (<b>A</b>) Early apoptosis in the control and PNMC-exposed MI oocytes was evaluated by Annexin-V assay. Annexin-V, green; Scale Bar = 100 µm. (<b>B</b>) The proportion of the oocytes with Annexin-V positive signal was quantified in the control (<span class="html-italic">n</span> = 187) and PNMC-exposed (<span class="html-italic">n</span> = 194) oocytes. (<b>C</b>–<b>E</b>) qRT-PCR for the mRNA levels of <span class="html-italic">BAX</span>, <span class="html-italic">BCL-2</span>, and <span class="html-italic">CASPASE3</span> in the control and PNMC-exposed oocytes. ** <span class="html-italic">p</span> &lt; 0.01 and *** <span class="html-italic">p</span> &lt; 0.001.</p>
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14 pages, 2710 KiB  
Article
NH2-MIL-125(Ti)/Reduced Graphene Oxide Enhanced Electrochemical Detection of Fenitrothion in Agricultural Products
by Zaixi Shu, Yue Zou, Xuyue Wu, Qi Zhang, Yafang Shen, Anhong Xiao, Shuo Duan, Fuwei Pi, Xiaodan Liu, Jiahua Wang and Huang Dai
Foods 2023, 12(7), 1534; https://doi.org/10.3390/foods12071534 - 4 Apr 2023
Cited by 10 | Viewed by 2364
Abstract
The abuse of organophosphate pesticides causes serious threats to human health, which threatens approximately 3 million people and leads to more than 2000 deaths each year. Therefore, it is necessary to determine the residue of fenitrothion (FT) in environmental and food samples. Herein, [...] Read more.
The abuse of organophosphate pesticides causes serious threats to human health, which threatens approximately 3 million people and leads to more than 2000 deaths each year. Therefore, it is necessary to determine the residue of fenitrothion (FT) in environmental and food samples. Herein, we developed a non-enzymatic electrochemical sensor with differential pulse voltammetry signal output to determine FT in model solutions and spiked samples. Delicately, the sensor was designed based on the fabrication of hydrothermally synthesized titanium-based metal-organic frameworks (MOFs) material (NH2-MIL-125(Ti))/reduced graphene oxide (RGO) (NH2-MIL-125(Ti)/RGO) nanocomposites for better target enrichment and electron transfer. The peak response of differential pulse voltammetry for FT under optimized conditions was linear in the range of 0.072–18 μM with the logarithm of concentrations, and the detection limit was 0.0338 μM. The fabricated sensor also demonstrated high stability and reproducibility. Moreover, it exhibited excellent sensing performances for FT in spiked agricultural products. The convenient fabrication method of NH2-MIL-125(Ti)/RGO opens up a new approach for the rational design of non-enzymatic detection methods for pesticides. Full article
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Figure 1
<p>SEM images of (<b>A</b>) NH<sub>2</sub>-MIL-125(Ti) and (<b>B</b>) NH<sub>2</sub>-MIL-125(Ti)/RGO; (<b>C</b>) XRD patterns, (<b>D</b>) TGA analysis, (<b>E</b>) Raman spectra and (<b>F</b>) FTIR spectra of GO, NH<sub>2</sub>-MIL-125(Ti) and NH<sub>2</sub>-MIL-125(Ti)/RGO. (<b>G</b>) CV and (<b>H</b>) DPV curves in 0.1 M PBS at different modified GCEs.</p>
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<p>(<b>A</b>) CVs and (<b>B</b>) EIS of different GCEs in 5 mM Fe(CN)<sub>6</sub><sup>3−/4−</sup> containing 0.1 M KCl; (<b>C</b>) Plot of Q~<span class="html-italic">t</span> and (<b>D</b>) Q~<span class="html-italic">t</span><sup>1/2</sup> curves of different GCEs; (<b>E</b>) CV and (<b>F</b>) DPV responses of different GCEs for 3.6 mM FT in 0.1 M PBS.</p>
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<p>(<b>A</b>) DPVs of 360 μM FT in different pH; (<b>B</b>) Variation of peak potential and current of 360 μM FT with pH; (<b>C</b>) CVs of NH<sub>2</sub>-MIL-125(Ti)/RGO/GCE in PBS containing 360 μM of FT at different scan rates: (50, 75, 100, 150, 200, 250, 300, 350, 400, 450, and 500 mV/s); (<b>D</b>) Linear relationship between the peak current and scan rate; (<b>E</b>) Effect of absorption time of FT solution (360 μM) on the reduction peak current; (<b>F</b>) Effect of loading amount of NH<sub>2</sub>-MIL-125(Ti)/RGO on the reduction peak current of 360 μM FT.</p>
Full article ">Figure 4
<p>(<b>A</b>) Differential pulse voltammogram of different FT concentrations at NH<sub>2</sub>-MIL-125(Ti)/RGO/GCE. (<b>B</b>) Calibration curve between peak current (µA) and the logarithm of FT concentrations (μM) (<span class="html-italic">n</span> = 3).</p>
Full article ">Scheme 1
<p>Schematic diagram of materials, NH<sub>2</sub>-MIL-125(Ti)/RGO/GCE preparation process, and detection mechanism.</p>
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23 pages, 2364 KiB  
Article
Insecticide Use against Desert Locust in the Horn of Africa 2019–2021 Reveals a Pressing Need for Change
by Wim C. Mullié, Adam Prakash, Alexander Müller and Elena Lazutkaite
Agronomy 2023, 13(3), 819; https://doi.org/10.3390/agronomy13030819 - 10 Mar 2023
Cited by 7 | Viewed by 9437
Abstract
The desert locust upsurge in the Horn of Africa over 2019–2021 led to a total of 1.6 million ha being treated with broad-spectrum organophosphate and pyrethroid insecticides in Ethiopia and Kenya, while insect growth regulators and the entomopathogenic fungus Metarhizium acridum were applied [...] Read more.
The desert locust upsurge in the Horn of Africa over 2019–2021 led to a total of 1.6 million ha being treated with broad-spectrum organophosphate and pyrethroid insecticides in Ethiopia and Kenya, while insect growth regulators and the entomopathogenic fungus Metarhizium acridum were applied in Somalia. Environmental monitoring was largely absent, with limited surveys conducted in Kenya and Ethiopia. Overdosing of fenitrothion of a 960 g/L formulation in Kenya led to non-target mortality, including birds and honeybees. In Ethiopia, chlorpyrifos and malathion applications coincided with a honey production decline of 78% in 2020 compared to pre-upsurge levels. The use of M. acridum on nearly 253,000 ha was a breakaway from previous campaigns, in which its successful application in Somalia against both hopper bands and swarms shows that the persistent and pervasive use of organophosphate insecticides can no longer be justified. Furthermore, future procurement of organophosphate insecticides and possibly insect growth regulators could become increasingly problematic due to measures enacted by the European Union. It is recommended that the complementary impact of M. acridum and bird predation on locusts should be considered in an integrated management approach for both swarm and hopper control. Full article
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<p>Monthly surface area treated (ha) from August 2019 to December 2021. Data are from the FAO Locust Hub [<a href="#B22-agronomy-13-00819" class="html-bibr">22</a>].</p>
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<p>DL treatments from October 2019 to December 2021. Treatment data for Kenya are incomplete. Landcover in 10 m × 10 m resolution tile size 3 × 3 degrees [<a href="#B31-agronomy-13-00819" class="html-bibr">31</a>].</p>
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<p>Dose rates of fenitrothion (g a.i./ha) in Kenya, January–April 2021, after 111 aerial treatments on 19,222 ha. The recommended dose rate is 400 g/ha. Data from the FAO SWARMS, detailed by FAO field operations officer [<a href="#B25-agronomy-13-00819" class="html-bibr">25</a>].</p>
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<p>Beehives and honey production in Ethiopia, 2010–2020. Source: FAOSTAT [<a href="#B72-agronomy-13-00819" class="html-bibr">72</a>].</p>
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<p>Densities of acridids in the first month following sprays with either chlorpyrifos, fenitrothion or <span class="html-italic">M. acridum</span>.</p>
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18 pages, 792 KiB  
Article
Simultaneous Analysis of Mycotoxins, Potentially Toxic Elements, and Pesticides in Rice: A Health Risk Assessment Study
by Mohammad Hashem Yousefi, Esmaeel Abbasi, Milad Hadidi, Seyedenayat Hashemi, Amir Hossein Ghadimi, Saeed Yousefinejad, Hossein Arfaeinia, Abbas Yousefinejad, Przemysław Łukasz Kowalczewski, Agnieszka Tomkowiak, Saeid Hosseinzadeh and Amin Mousavi Khaneghah
Toxins 2023, 15(2), 102; https://doi.org/10.3390/toxins15020102 - 20 Jan 2023
Cited by 6 | Viewed by 2912
Abstract
Rice is a widely consumed food worldwide; however, it can be a source of pollutants, such as potentially toxic elements (PTEs), mycotoxins, and pesticides. Sixty rice samples imported from Pakistan (PAK), India (IND), and Thailand (THAI), as well as domestic Iranian (IRN) rice, [...] Read more.
Rice is a widely consumed food worldwide; however, it can be a source of pollutants, such as potentially toxic elements (PTEs), mycotoxins, and pesticides. Sixty rice samples imported from Pakistan (PAK), India (IND), and Thailand (THAI), as well as domestic Iranian (IRN) rice, were collected from Bushehr, Iran, and investigated for the contamination of PTEs, including arsenic (As), lead (Pb), cadmium (Cd), and nickel (Ni); pesticides, including chlorpyrifos, trichlorfon, diazinon, fenitrothion, and chlorothalonil; mycotoxins, such as aflatoxin B1 (AFB1), zearalenone (ZEN), ochratoxin A (OTA), and deoxynivalenol (DON); and molds. Estimated daily intake (EDI) and hazard quotient (HQ) of pollutants and hazard index (HI) and incremental lifetime cancer risk (ILCR) of rice types for the Iranian adult population were calculated. The content of PTEs in Iranian rice was not higher than Iran’s national standard limits. In contrast, other types of rice (imported) had at least one PTE above the permissible level. OTA content was below the detection limit, and all other mycotoxins were within the allowable range in all rice types. Thai rice was the only group without pesticides. The HI order of rice types was as follows: HIPAK = 2.1 > HIIND = 1.86 > HIIRN = 1.01 > HITHAI = 0.98. As was the biggest contributor to the HI of Iranian and Thai rice, and diazinon in the HI of Pakistani and Indian rice. The calculation of ILCR confirmed that the concentrations of Ni and Pb in Pakistani and Ni and As in Indian, Thai, and Iranian rice were not acceptable in terms of lifetime carcinogenic health risks. Full article
(This article belongs to the Section Mycotoxins)
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Graphical abstract

Graphical abstract
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<p>HI values of rice brands.</p>
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<p>Shares of individual pollutants (%) in HI of different rice brands.</p>
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11 pages, 2072 KiB  
Communication
An Electrochemical Sensor Based on Electropolymerization of β-Cyclodextrin on Glassy Carbon Electrode for the Determination of Fenitrothion
by Rong Wang, Shulong Wang, Caihong Qin, Qiyang Nie, Yougang Luo, Qi-Pin Qin, Ruijuan Wang, Baiquan Liu and Dongxiang Luo
Sensors 2023, 23(1), 435; https://doi.org/10.3390/s23010435 - 30 Dec 2022
Cited by 7 | Viewed by 2051
Abstract
An electrochemical sensor enabled by electropolymerization (EP) of β-cyclodextrin on glassy carbon electrode (β-CDP/GCE) is built for the determination of fenitrothion (FNT). The effects of the EP cycles, pH value, and enrichment time on the electrochemical response of FNT were studied. With the [...] Read more.
An electrochemical sensor enabled by electropolymerization (EP) of β-cyclodextrin on glassy carbon electrode (β-CDP/GCE) is built for the determination of fenitrothion (FNT). The effects of the EP cycles, pH value, and enrichment time on the electrochemical response of FNT were studied. With the optimum conditions, good linear relationships between the current of the reduction peak of the nitroso derivative of FNT and the concentration are obtained in the range of 10–150 and 150–4000 ng/mL, with a detection limit of 6 ng/mL (S/N = 3). β-CDP/GCE also exhibits a satisfactory applicability in cabbage and tap water, with recovery values between 98.43% and 112%. These outstanding results suggest that β-CDP/GCE could be a new effective alternative for the determination of FNT in real samples. Full article
(This article belongs to the Section Chemical Sensors)
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Figure 1
<p>(<b>a</b>) The chemical structure of β-CD; (<b>b</b>) multicycle CV curves of β-CD (6 mM in phosphate buffer solution, pH = 6.80) on GCE with potential from −2.0 to 2.0 V, scan rate of 100 mV/s and 10 cycles. Inset: the first CV curve of β-CD on GCE.</p>
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<p>(<b>a</b>) The chemical structure of FNT and its electrochemical behavior; (<b>b</b>) CV curves of FNT (2 μg/mL in acetate buffer solution, pH = 5.00) on GCE and β-CDP/GCE with potential from 0.6 to −1.0 V, scan rate of 50 mV/s, and 2 cycles; (<b>c</b>) the third-step DPV curves of FNT (2 μg/mL in acetate buffer solution, pH = 5.00) on GCE (black line) and β-CDP/GCE (red line); (blue line) the third-step DPV curve of S-β-CDP/GCE (soaked in acetate buffer solution with 2 μg/mL FNT for 90 s, taken out, and rinsed with acetate buffer solution) in blank (without FNT) acetate buffer solution (pH = 5.00). DPV parameters: potential increment of 13 mV, amplitude of 50 mV, pulse width of 60 ms, sampling width of 20 ms, pulse period of 500 ms, and potential from 0.6 to −0.9 V.</p>
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<p>(<b>a</b>) The third-step DPV curves of FNT (2 μg/mL in acetate buffer solution, pH = 5.00) on β-CDP/GCE prepared with different EP cycles; (<b>b</b>) the variation in <span class="html-italic">I</span><sub>pc,2</sub> with EP cycles; (<b>c</b>) the third-step DPV curves of FNT (2 μg/mL in acetate buffer solution with different pH) on β-CDP/GCE; (<b>d</b>) the variation in <span class="html-italic">I</span><sub>pc,2</sub> and <span class="html-italic">E</span><sub>c,2</sub> with pH. DPV parameters: potential increment of 13 mV, amplitude of 50 mV, pulse width of 60 ms, sampling width of 20 ms, pulse period of 500 ms, and potential from 0.6 to −0.9 V.</p>
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<p>(<b>a</b>) The third-step DPV curves of FNT with different concentrations (10, 50, 75, 100, 200, 500, 750, 1000, 1250, 1500, 1750, 3000, 4000 ng/mL in acetate buffer solution, pH = 5.00) on β-CDP/GCE; (<b>b</b>) the calibration curve for <span class="html-italic">I</span><sub>pc,2</sub> versus concentration of FNT.</p>
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12 pages, 1644 KiB  
Article
Sustainable Proposal for Regulating Organophosphate Pesticides in Wastewater Treatment Plants in South Korea
by Hong-Duck Ryu, Hyeyeol Han, Ji-Hyoung Park and Yong Seok Kim
Sustainability 2022, 14(19), 11979; https://doi.org/10.3390/su141911979 - 22 Sep 2022
Cited by 1 | Viewed by 1922
Abstract
Organophosphate pesticides (OPs) are highly toxic; their presence in surface waters is a matter of great concern. To the best of our knowledge, OPs in wastewater from agrochemical manufacturing facilities (AMFs) and influents and effluents from agrochemical wastewater treatment plants (AWWTPs) have not [...] Read more.
Organophosphate pesticides (OPs) are highly toxic; their presence in surface waters is a matter of great concern. To the best of our knowledge, OPs in wastewater from agrochemical manufacturing facilities (AMFs) and influents and effluents from agrochemical wastewater treatment plants (AWWTPs) have not been previously investigated. Therefore, we investigated the presence of 8 OPs (5 of which are regulated under the Water Environment Conservation Act (WECA)) in 15 AMFs and 13 AWWTPs detected through surface water monitoring and proposed measures for effectively regulating these OPs in AWWTPs. Five OPs (chlorpyrifos, diazinon, dichlorvos, EPN, and fenitrothion) were detected in the AMF and AWWTP influents; three (methyldemeton, parathion, and phenthoate) were not. Of the five detected OPs, chlorpyrifos, dichlorvos, and fenitrothion are not currently regulated via effluent limitations for WWTPs under WECA; thus, additional regulations are required. The most effective process configuration for the removal of these OPs was biological treatment through activated sludge processes, followed by activated carbon adsorption. In the system, 100% OP removal from the AWWTP influents was observed. This treatment technology can be implemented in AWWTPs to minimize the presence of OPs in surface waters, thereby protecting human health and aquatic life. Full article
(This article belongs to the Section Pollution Prevention, Mitigation and Sustainability)
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<p>Average organophosphate pesticide (OP) concentrations in (<b>a</b>) agrochemical manufacturing facility (AMF) wastewater, (<b>b</b>) agrochemical wastewater treatment plant (AWWTP) influent, and (<b>c</b>) AWWTP effluent. Error bars indicate the standard deviation.</p>
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<p>Average removal of organophosphate pesticides (OPs) observed in the agrochemical wastewater treatment plant (AWWTP) influents. Error bars indicate standard deviation.</p>
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<p>Removal of six individual organophosphate pesticides (OPs) (chlorpyrifos, diazinon, dichlorvos, EPN, fenitrothion, and parathion) using four unit processes. The literature cited for each unit process is as follows: (<b>a</b>) flocculation [<a href="#B24-sustainability-14-11979" class="html-bibr">24</a>,<a href="#B31-sustainability-14-11979" class="html-bibr">31</a>], (<b>b</b>) biological removal [<a href="#B8-sustainability-14-11979" class="html-bibr">8</a>,<a href="#B9-sustainability-14-11979" class="html-bibr">9</a>,<a href="#B35-sustainability-14-11979" class="html-bibr">35</a>], (<b>c</b>) chemical oxidation [<a href="#B25-sustainability-14-11979" class="html-bibr">25</a>,<a href="#B27-sustainability-14-11979" class="html-bibr">27</a>,<a href="#B34-sustainability-14-11979" class="html-bibr">34</a>,<a href="#B36-sustainability-14-11979" class="html-bibr">36</a>,<a href="#B37-sustainability-14-11979" class="html-bibr">37</a>,<a href="#B38-sustainability-14-11979" class="html-bibr">38</a>,<a href="#B39-sustainability-14-11979" class="html-bibr">39</a>,<a href="#B40-sustainability-14-11979" class="html-bibr">40</a>,<a href="#B41-sustainability-14-11979" class="html-bibr">41</a>,<a href="#B42-sustainability-14-11979" class="html-bibr">42</a>,<a href="#B43-sustainability-14-11979" class="html-bibr">43</a>,<a href="#B44-sustainability-14-11979" class="html-bibr">44</a>], and (<b>d</b>) activated carbon adsorption [<a href="#B6-sustainability-14-11979" class="html-bibr">6</a>,<a href="#B28-sustainability-14-11979" class="html-bibr">28</a>,<a href="#B29-sustainability-14-11979" class="html-bibr">29</a>,<a href="#B30-sustainability-14-11979" class="html-bibr">30</a>,<a href="#B31-sustainability-14-11979" class="html-bibr">31</a>,<a href="#B32-sustainability-14-11979" class="html-bibr">32</a>,<a href="#B33-sustainability-14-11979" class="html-bibr">33</a>,<a href="#B34-sustainability-14-11979" class="html-bibr">34</a>,<a href="#B45-sustainability-14-11979" class="html-bibr">45</a>,<a href="#B46-sustainability-14-11979" class="html-bibr">46</a>,<a href="#B47-sustainability-14-11979" class="html-bibr">47</a>,<a href="#B48-sustainability-14-11979" class="html-bibr">48</a>,<a href="#B49-sustainability-14-11979" class="html-bibr">49</a>,<a href="#B50-sustainability-14-11979" class="html-bibr">50</a>].</p>
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<p>Concentrations of: (<b>a</b>) chlorpyrifos and (<b>b</b>) dichlorvos in national monitoring sites (NMSs) of South Korean rivers. AA-EQS and MAC-EQS indicate environmental quality standards in the EU, expressed as an annual average and maximum allowable concentration, respectively.</p>
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<p>Application concept schematics of an agrochemical wastewater treatment plant (AWWTP) for treating organophosphate pesticide (OP)-containing wastewater. (1) Activated sludge reactor, (2) settler, and (3) activated carbon adsorption column.</p>
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12 pages, 3080 KiB  
Article
Quantum Chemical Approach to the Adsorption of Chlorpyrifos and Fenitrothion on the Carbon-Doped Boron Nitride Nanotube Decorated with Tetrapeptide
by Chien-Lin Lee and Chia Ming Chang
Crystals 2022, 12(9), 1285; https://doi.org/10.3390/cryst12091285 - 11 Sep 2022
Cited by 2 | Viewed by 2089
Abstract
In the present study, four materials based on boron nitride nanotubes—namely pristine BNNT, C-doped BNNT, tetrapeptide/BNNT, and tetrapeptide/C-doped BNNT—were examined to evaluate adsorption of the organophosphorus pesticides chlorpyrifos and fenitrothion. Through a quantum chemical approach to the molecular and electronic structures, the impacts [...] Read more.
In the present study, four materials based on boron nitride nanotubes—namely pristine BNNT, C-doped BNNT, tetrapeptide/BNNT, and tetrapeptide/C-doped BNNT—were examined to evaluate adsorption of the organophosphorus pesticides chlorpyrifos and fenitrothion. Through a quantum chemical approach to the molecular and electronic structures, the impacts of C doping and tetrapeptide modification on boron nitride nanotubes are clarified. The results reveal that the tetrapeptide decoration does have the potential for differential sensing of chlorpyrifos and fenitrothion, but the improvement in the adsorption characteristics is slightly inferior to that of the C doping method. Nanosensors, such as C-doped BNNT and tetrapeptide/C-doped BNNT, are used to monitor chlorpyrifos and fenitrothion in solution phase, respectively. This quantum chemistry investigation has paved the way for the design of differential sensing devices for organophosphorus pesticides. Full article
(This article belongs to the Special Issue Feature Papers in Macromolecular Crystals)
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<p>Non-covalent interaction between pesticides (chlorpyrifos (chl) and fenitrothion (fen)) and carbon-doped armchair (5,5) boron nitride nanotube (BN55-CC1) without (<b>A</b>,<b>B</b>) and decorated with tetrapeptide (4pep) (<b>C</b>,<b>D</b>).</p>
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<p>Equilibrium structures of pesticides ((<b>A</b>) chlorpyrifos (chl) and (<b>B</b>) fenitrothion (fen)) adsorbed on carbon-doped armchair (5,5) boron nitride nanotube (BN55-CC1) decorated with tetrapeptide (4pep).</p>
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<p>Electrostatic potential of pesticides (chlorpyrifos (chl) and fenitrothion (fen)) adsorbed on carbon-doped armchair (5,5) boron nitride nanotube (BN55-CC1) without (<b>A</b>,<b>B</b>) and decorated with tetrapeptide (4pep) (<b>C</b>,<b>D</b>).</p>
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<p>Frontier molecular orbital electrophilic susceptibility of pesticides (chlorpyrifos (chl) and fenitrothion (fen)) adsorbed on carbon-doped armchair (5,5) boron nitride nanotube (BN55-CC1) without (<b>A</b>,<b>B</b>) and decorated with tetrapeptide (4pep) (<b>C</b>,<b>D</b>).</p>
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10 pages, 452 KiB  
Article
Organophosphate Insecticides Resistance in Field Populations of House Flies, Musca domestica L.: Levels of Resistance and Acetylcholinesterase Activity
by Yasser Abobakr, Faisal I. Al-Hussein, Alaa E. Bayoumi, Ali A. Alzabib and Ali S. Al-Sarar
Insects 2022, 13(2), 192; https://doi.org/10.3390/insects13020192 - 11 Feb 2022
Cited by 8 | Viewed by 3129
Abstract
The house fly, Musca domestica L., is an important medical and veterinary pest associated with humans and livestock. Management of house flies has relied extensively on chemical control. In this study, we report on the resistance of house fly field-collected populations to diazinon [...] Read more.
The house fly, Musca domestica L., is an important medical and veterinary pest associated with humans and livestock. Management of house flies has relied extensively on chemical control. In this study, we report on the resistance of house fly field-collected populations to diazinon and fenitrothion OP insecticides in Riyadh, Saudi Arabia. The diazinon and fenitrothion median lethal dose (LD50) values against adult female M. domestica field-collected populations were significantly higher than those of the laboratory (LAB) strain. Different levels of resistance were detected in all field-collected populations toward the two OP insecticides. The resistance ratios for diazinon ranged from 62.47 to 309.78, while there were 53.08 to 261.24 for fenitrothion in the eight field-collected populations. The specific activity of acetylcholinesterase (AChE) in all field populations was significantly (p < 0.05) higher than that in the LAB strain. In vitro diazinon and fenitrothion median inhibitory concentration (IC50) values of LAB strain AChE activity were significantly (p < 0.05) lower than those for field-collected populations. This study found high levels of resistance in the house fly field-collected populations to diazinon and fenitrothion. Replacing these two insecticides and any other OPs with novel ones that have different modes of action is an urgent need in the insect-vector control programs in Riyadh, Saudi Arabia. An altered AChE enzyme of M. domestica field populations might be partially responsible for the developed resistance. Monitoring of insecticide resistance development in M. domestica populations and a better understanding of its mechanisms are needed to design operative management strategies for controlling the house flies. Full article
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<p>Chemical structure of: (<b>a</b>) diazinon; (<b>b</b>) fenitrothion.</p>
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11 pages, 256 KiB  
Article
First Evaluation of Field Evolved Resistance to Commonly Used Insecticides in House Fly Populations from Saudi Arabian Dairy Farms
by Abdulwahab M. Hafez
Insects 2021, 12(12), 1120; https://doi.org/10.3390/insects12121120 - 14 Dec 2021
Cited by 7 | Viewed by 2726
Abstract
The house fly, Musca domestica L. (Diptera: Muscidae), is one of the major vectors of several pathogens that affect humans and animals. We evaluated the toxicity of eight insecticides commonly used for house fly control using five field populations collected from dairies in [...] Read more.
The house fly, Musca domestica L. (Diptera: Muscidae), is one of the major vectors of several pathogens that affect humans and animals. We evaluated the toxicity of eight insecticides commonly used for house fly control using five field populations collected from dairies in Riyadh, Saudi Arabia. Among the five tested pyrethroids, non to moderate resistance was found in adults of both sexes compared to a susceptible strain. Resistance ratios ranged from 0.5- to 7-fold for alpha-cypermethrin, 2- to 21-fold for deltamethrin, 4- to 19-fold for bifenthrin, 1- to 9-fold for cyfluthrin, and 1- to 8-fold for cypermethrin. Among the three tested organophosphates, low to moderate resistance was found among adult flies compared to the susceptible strain, and the resistance ratios ranged from 4- to 27-fold for fenitrothion, 2- to 14-fold for chlorpyrifos, and 3- to 12-fold for malathion. The median lethal times for the tested insecticides were 3–33 h for alpha-cypermethrin, 3–24 h for deltamethrin, 5–59 h for bifenthrin, 1–7 h for cypermethrin, 0.3–7 h for cyfluthrin, 6–36 h for fenitrothion, 2–21 h for chlorpyrifos, and 3–34 h for malathion. This study presents baseline data pertaining to registered public health insecticides, and the results will assist future studies monitoring insecticide resistance, and the planning of effective integrated vector management programs. Full article
(This article belongs to the Collection Pesticide Chemistry and Toxicology)
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13 pages, 994 KiB  
Article
Endocrine Disruption, Cytotoxicity and Genotoxicity of an Organophosphorus Insecticide
by Afifa Belaid, Nosra Methneni, Emna Nasri, Sarra Bchir, Roel Anthonissen, Luc Verschaeve, Véronique Le Tilly, Vincenzo Lo Turco, Giuseppa Di Bella, Hedi Ben Mansour and Nezar H. Khdary
Sustainability 2021, 13(20), 11512; https://doi.org/10.3390/su132011512 - 18 Oct 2021
Cited by 5 | Viewed by 2162
Abstract
In the present study, a battery of biological tests undertaken in vitro and in vivo was used to evaluate the toxic potential of an organophosphorus insecticide, namely Fenitrothion. The cytotoxic effect of pesticide was evaluated with the MTT assay against two human cancer [...] Read more.
In the present study, a battery of biological tests undertaken in vitro and in vivo was used to evaluate the toxic potential of an organophosphorus insecticide, namely Fenitrothion. The cytotoxic effect of pesticide was evaluated with the MTT assay against two human cancer cell lines: Hep-2 and MDA-MB-231. Genotoxicity was also studied using the bacterial VITOTOX® assay. The estrogenic effect was tested using the recombinant yeasts (YES) assay. Likewise, bioluminescence assays using V. fischeri and D. magna immobilization were performed. The results showed that Fenitrothion exhibits a variable cytotoxic effect depending on the dose as well as the studied cell lines, and no genotoxicity was observed in the tested sample. However, an estrogenic effect was recorded when investigating Fenitrothion using the recombinant yeasts (YES) assay. Analogously, acute toxicity was observed for both organisms and at all tested concentrations of Fenitrothion. Overall, these results underline the crucial importance of in vitro and in vivo bioassays in monitoring toxicity of pesticides. Full article
(This article belongs to the Section Environmental Sustainability and Applications)
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<p>Cytotoxic effect of different concentrations of Fenitrothion on the cell lines Hep-2 and MDA-MB-231.</p>
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<p>Findings of the VITOTOX<sup>®</sup> test for both bacterial strains (Genox and Cytox) exposed to different concentrations of Fenitrothion in the presence and absence of S9 mix.</p>
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<p>Estrogenic activity of the E2 reference molecule and that of Fenitrothion determined with the yeast estrogen screen (YES) assay.</p>
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15 pages, 2563 KiB  
Article
Novel DNA Aptameric Sensors to Detect the Toxic Insecticide Fenitrothion
by Kien Hong Trinh, Ulhas Sopanrao Kadam, Jinnan Song, Yuhan Cho, Chang Ho Kang, Kyun Oh Lee, Chae Oh Lim, Woo Sik Chung and Jong Chan Hong
Int. J. Mol. Sci. 2021, 22(19), 10846; https://doi.org/10.3390/ijms221910846 - 7 Oct 2021
Cited by 25 | Viewed by 3551
Abstract
Fenitrothion is an insecticide belonging to the organophosphate family of pesticides that is widely used around the world in agriculture and living environments. Today, it is one of the most hazardous chemicals that causes severe environmental pollution. However, detection of fenitrothion residues in [...] Read more.
Fenitrothion is an insecticide belonging to the organophosphate family of pesticides that is widely used around the world in agriculture and living environments. Today, it is one of the most hazardous chemicals that causes severe environmental pollution. However, detection of fenitrothion residues in the environment is considered a significant challenge due to the small molecule nature of the insecticide and lack of molecular recognition elements that can detect it with high specificity. We performed in vitro selection experiments using the SELEX process to isolate the DNA aptamers that can bind to fenitrothion. We found that newly discovered DNA aptamers have a strong ability to distinguish fenitrothion from other organophosphate insecticides (non-specific targets). Furthermore, we identified a fenitrothion-specific aptamer; FenA2, that can interact with Thioflavin T (ThT) to produce a label-free detection mode with a Kd of 33.57 nM (9.30 ppb) and LOD of 14 nM (3.88 ppb). Additionally, the FenA2 aptamer exhibited very low cross-reactivity with non-specific targets. This is the first report showing an aptamer sensor with a G4-quadruplex-like structure to detect fenitrothion. Moreover, these aptamers have the potential to be further developed into analytical tools for real-time detection of fenitrothion from a wide range of samples. Full article
(This article belongs to the Section Molecular Biology)
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<p>Illustrative scheme of the in vitro selection, SELEX process. The in vitro selection process begins with 1015 different ssDNA molecules and incubation with the target of interest, fenitrothion. Molecules that do not bind to fenitrothion are removed. Molecules that bind to fenitrothion are eluted, collected and amplified and reloaded after strand separation. It completes one round of an in vitro selection cycle.</p>
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<p>Secondary structures prediction of five candidate aptamers using Mfold web server [<a href="#B36-ijms-22-10846" class="html-bibr">36</a>]. (<b>A</b>) FenA, (<b>B</b>) FenA2, (<b>C</b>) FenA3, (<b>D</b>) FenA4, and (<b>E</b>) FenA5. Where Fen means fenitrothion, A means aptamer, and the number represents the number of the sequence.</p>
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<p>The experimental analysis of FAM sensors showing the quenching efficiency and measurement of <span class="html-italic">K<sub>d</sub></span><sub>,eff1</sub> and <span class="html-italic">K<sub>d</sub></span><sub>,eff2</sub> values for FenA1-FAM, FenA2-FAM, and FenA5-FAM sensors. (<b>A</b>) FenA1-FAM quenching; (<b>B</b>) FenA1-FAM sensor testing; (<b>C</b>) FenA2-FAM quenching; (<b>D</b>) FenA2-FAM sensor testing; (<b>E</b>) FenA5-FAM quenching; and (<b>F</b>) FenA5-FAM sensor testing. The dabcyl quencher was used in this assay (<a href="#app1-ijms-22-10846" class="html-app">Figure S4</a>).</p>
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<p>The chemical structure of fenitrothion and three other organophosphate insecticides; non-specific targets, namely malathion, paraoxon, and parathion, used to compare binding specificities of selected aptamers.</p>
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<p>Experimental evaluation of the recognition specificity FAM-sensor: (<b>A</b>) FenA1-FAM, (<b>B</b>) FenA2-FAM, and (<b>C</b>) FenA5-FAM against its positive target —fenitrothion (green), and its negative targets—malathion (red), parathion (blue), and paraoxon (black).</p>
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<p>Evaluation of the binding potential of ssDNA aptamers with ThT. (<b>A</b>) Lighting up with ThT (green line represents FenA2; whereas the red, blue, aqua-blue, the black lines represent FenA1, FenA3, FenA4, and FenA5 ssDNA aptamers). Only FenA2 showed significant improvement in fluorescence upon binding with ThT, and other aptamers had much less affinity for ThT. (<b>B</b>) The FenA2-ThT sensor testing using different concentrations of fenitrothion. The <span class="html-italic">K<sub>d</sub></span> obtained using this method was 33.57 nM (9.307 ppb) and LOD was 14.00 nM (3.881 ppb).</p>
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<p>Recognition specificity of FenA2-ThT sensor against other organophosphate insecticides. The signal of FenA2-ThT in the presence of fenitrothion (green line with filled circles); in the presence of malathion (red line with squares); in the presence of parathion (blue line with inverted triangles); and in the presence of paraoxon (black lines with triangles).</p>
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<p>Label-free detection of fenitrothion using FenA2 sensor and ThT dye in plant tissue extracts. (<b>A</b>) Optimization of ThT fluorescence lighting: Measurement of ThT fluorescence upon binding with FenA2 aptamer using various dilutions of plant extracts. The fluorescence signal shown is of: (1) 1× buffer only; (2) 8 µM ThT dye only; (3) 1 µM FenA2 aptamer only; (4) 1 µM FenA2: 8 µM ThT in the 1× plant extract dilution; (5) 1 µM FenA2: 8 µM ThT in the 10× plant extracted dilution; (6) 1 µM FenA2: 8 µM ThT in the 100× plant extracted dilution; (7) 1 µM FenA2: 8 µM ThT in the 1000× plant extracted dilution; (8) 1 µM sensor: 8 µM ThT in 1× SB buffer. (<b>B</b>) FenA2 Sensor testing for analysis of fenitrothion in plant extract. The fluorescence signal shown is of: (1) 1× buffer only; (2) 8 µM ThT; (3) 1 µM FenA2 Aptamer only; (4) 1 µM FenA2: 8 µM ThT in the 1000× plant extract dilution; and (5) 1 µM FenA2: 8 µM ThT with 50 nM fenitrothion spiked in the 1000× plant extract dilution.</p>
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20 pages, 9340 KiB  
Article
Synthesis and Decontamination Effect on Chemical and Biological Agents of Benzoxonium-Like Salts
by Aneta Markova, Michaela Hympanova, Marek Matula, Lukas Prchal, Radek Sleha, Marketa Benkova, Lenka Pulkrabkova, Ondrej Soukup, Zuzana Krocova, Daniel Jun and Jan Marek
Toxics 2021, 9(9), 222; https://doi.org/10.3390/toxics9090222 - 15 Sep 2021
Cited by 5 | Viewed by 2810
Abstract
Benzoxonium chloride belongs to the group of quaternary ammonium salts, which have been widely used for decades as disinfectants because of their high efficacy, low toxicity, and thermal stability. In this study, we have prepared the C10-C18 set of benzoxonium-like [...] Read more.
Benzoxonium chloride belongs to the group of quaternary ammonium salts, which have been widely used for decades as disinfectants because of their high efficacy, low toxicity, and thermal stability. In this study, we have prepared the C10-C18 set of benzoxonium-like salts to evaluate the effect of their chemical and biological decontamination capabilities. In particular, biocidal activity against a panel of bacterial strains including Staphylococcus aureus in biofilm form was screened. In addition, the most promising compounds were successfully tested against Francisella tularensis as a representative of potential biological warfare agents. From a point of view of chemical warfare protection, the efficiency of BOC-like compounds to degrade the organophosphate simulant fenitrothion was examined. Notwithstanding that no single compound with universal effectiveness was identified, a mixture of only two compounds from this group would be able to satisfactorily cover the proposed decontamination spectrum. In addition, the compounds were evaluated for their cytotoxicity as a basic safety parameter for potential use in practice. In summary, the dual effect on chemical and biological agents of benzoxonium-like salts offer attractive potential as active components of decontamination mixtures in the case of a terrorist threat or chemical or biological accidents. Full article
(This article belongs to the Special Issue Chemical and Biological Threats, Hazard Potential and Countermeasures)
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<p>Dependency of conductivity on concentration. The curve was divided into three parts: lower and upper linear parts, and a transition section. The equation of the line and the coefficient of determination were calculated for both linear parts. The CMC value was determined at the intersection of both axes [<a href="#B38-toxics-09-00222" class="html-bibr">38</a>].</p>
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<p>Dependency of log CMC on length of alkyl chain.</p>
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<p>Commercially used compounds at pH 11. The influence of QAS structure on the decontamination effect (rate constant) at pH 11; DTMA (<span class="html-italic">N</span>-dodecyl-<span class="html-italic">N</span>,<span class="html-italic">N</span>,<span class="html-italic">N</span>-trimethylammonium chloride), BAC (<span class="html-italic">N</span>-benzyl-<span class="html-italic">N</span>,<span class="html-italic">N</span>-dimethyl-<span class="html-italic">N</span>-dodecylammonium chloride), DHEMA (<span class="html-italic">N,N</span>-bis(hydroxyethyl)-<span class="html-italic">N</span>-dodecyl-<span class="html-italic">N</span>-methylammonium chloride) and <b>5b</b> (<span class="html-italic">N</span>-benzyl-<span class="html-italic">N</span>,<span class="html-italic">N</span>-bis(2-hydroxyethyl)dodecan-1-aminium chloride; green color highlights the positive moiety to increase the decontamination effect. The decrease in activity at high concentrations is due to an excess of surfactant. This so-called empty micelle effect has been previously described [<a href="#B42-toxics-09-00222" class="html-bibr">42</a>].</p>
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<p>MIC and MBC values of tested compounds for G+ and G- bacterial strains. MIC values were determined after 24 and 48 h of incubation, MBC was determined after 24 h of incubation. The results for BACs had been published elsewhere [<a href="#B31-toxics-09-00222" class="html-bibr">31</a>,<a href="#B38-toxics-09-00222" class="html-bibr">38</a>]. <span class="html-italic">N</span> means that MIC or MBC was higher than the highest soluble concentration of the compound. Abbreviations: STAU = <span class="html-italic">S. aureus</span>, MRSA = methicillin-resistant <span class="html-italic">S. aureus</span>, STEP = <span class="html-italic">S. epidermidis</span>, VRE = vancomycin-resistant <span class="html-italic">Enterococcus,</span> ESCO = <span class="html-italic">E. coli,</span> KLPN- = <span class="html-italic">K. pneumoniae,</span> KLPN+ = extended-spectrum <span class="html-italic">β</span>-lactamase-producing <span class="html-italic">K. pneumoniae</span>, PSAE MR = multidrug-resistant <span class="html-italic">P. aeruginosa</span>.</p>
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<p>Susceptibility testing against <span class="html-italic">Francisella tularensis</span> LVS. The remaining ratio of living LVS after 5 min exposure is expressed as mean ± SEM (<span class="html-italic">n</span> = 3).</p>
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<p>MBEC values and MBC values established for <span class="html-italic">S. aureus.</span> MBC and MBEC values were determined after 24 h of incubation for BAC and <b>5b-d</b> series by broth microdilution method and MBEC assay respectively. Results are expressed as the mean ± SD (<span class="html-italic">n</span> = 3).</p>
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<p>Two-step preparation of benzoxonium-like salts.</p>
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14 pages, 4195 KiB  
Article
ZrO2 Nanoparticles and Poly(diallyldimethylammonium chloride)-Doped Graphene Oxide Aerogel-Coated Stainless-Steel Mesh for the Effective Adsorption of Organophosphorus Pesticides
by Xiudan Hou, Rong Ding, Shihai Yan, Haiyan Zhao, Qingli Yang and Wei Wu
Foods 2021, 10(7), 1616; https://doi.org/10.3390/foods10071616 - 13 Jul 2021
Cited by 11 | Viewed by 2844
Abstract
A novel sorbent based on the ZrO2 nanoparticles and poly(diallyldimethylammonium chloride)-modified graphene oxide aerogel-grafted stainless steel mesh (ZrO2/PDDA-GOA-SSM) was used for the extraction and detection of organophosphorus pesticides (OPPs). Firstly, the PDDA and GO composite was grafted onto the surface [...] Read more.
A novel sorbent based on the ZrO2 nanoparticles and poly(diallyldimethylammonium chloride)-modified graphene oxide aerogel-grafted stainless steel mesh (ZrO2/PDDA-GOA-SSM) was used for the extraction and detection of organophosphorus pesticides (OPPs). Firstly, the PDDA and GO composite was grafted onto the surface of SSM and then freeze-dried to obtain the aerogel, which efficiently reduced the accumulation of graphene nanosheets. It integrated the advanced properties of GOA with a thin coating and the three-dimensional structural geometry of SSM. The modification of ZrO2 nanoparticles brought a selective adsorption for OPPs due to the combination of the phosphate group as a Lewis base and ZrO2 nanoparticles with the Lewis acid site. The ZrO2/PDDA-GOA-SSM was packed into the solid-phase extraction (SPE) cartridge to extract OPPs. According to the investigation of different factors, the extraction recovery was mainly affected by the hydrophilic-hydrophobic properties of analytes. Effective extraction and elution parameters such as sample volume, sample pH, rate of sample loading, eluent, and eluent volume, were also investigated and discussed. Under the optimal conditions, the linearity of phoxim and fenitrothion was in the range of 1.0–200 μg L−1, and the linearity of temephos was in the range of 2.5–200 μg L−1. The limits of detection were ranged from 0.2 to 1.0 μg L−1. This established method was successfully applied to detect OPPs in two vegetables. There was no OPP detected in real samples, and results showed that the matrix effects were in the range of 46.5%–90.1%. This indicates that the ZrO2/PDDA-GOA-SSM-SPE-HPLC method could effectively extract and detect OPPs in vegetables. Full article
(This article belongs to the Special Issue Emerging Detection Techniques for Contaminants in Food Science)
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<p>Preparation of the ZrO<sub>2</sub>/PDDA-GOA-modified SSM and the response signal.</p>
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<p>Photographs of the bare SSM and ZrO<sub>2</sub>/PDDA-GOA-modified SSM (<b>a</b>) and SEM images of ZrO2/PDDA-GOA-modified SSM with different magnifications (<b>b</b>,<b>c</b>).</p>
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<p>Characterization of extraction materials: XPS analysis (<b>a</b>), FT-IR spectrum (<b>b</b>), and TGA analysis (<b>c</b>).</p>
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<p>Effect of extraction and desorption conditions on the extraction performance: volume of sample (<b>a</b>), rate of sample loading (<b>b</b>), sample pH (<b>c</b>), type of eluent (<b>d</b>), volume of eluent (<b>e</b>); as well as the adsorption capacity-concentration profiles of analytes (<b>f</b>).</p>
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<p>Comparison of extraction performance of different sorbents for analytes: (<b>a</b>) different prepared sorbent; (<b>b</b>) commercial sorbents.</p>
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<p>The variation tendency of different affecting factor.</p>
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<p>Chromatograms of pakvchoi (<b>A</b>) and chives (<b>B</b>), and samples (line <b>a</b>) spiked with standard solutions of 20 μg L<sup>−1</sup> (line <b>b</b>), 40 μg L<sup>−1</sup> (line <b>c</b>), and 100 μg L<sup>−1</sup> (line <b>d</b>) by the proposed method.</p>
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16 pages, 1683 KiB  
Article
Paternal Fenitrothion Exposures in Rats Causes Sperm DNA Fragmentation in F0 and Histomorphometric Changes in Selected Organs of F1 Generation
by Nur Afizah Yusoff, Izatus Shima Taib, Siti Balkis Budin and Mahaneem Mohamed
Toxics 2021, 9(7), 159; https://doi.org/10.3390/toxics9070159 - 5 Jul 2021
Cited by 7 | Viewed by 3189
Abstract
The adverse effects of maternal pesticides exposure on the progeny is very well established. However, the impact of paternal exposure to pesticides such as Fenitrothion (FNT) on the histomorphometry of progeny’s organs in unexposed mothers are much less well studied. Therefore, this study [...] Read more.
The adverse effects of maternal pesticides exposure on the progeny is very well established. However, the impact of paternal exposure to pesticides such as Fenitrothion (FNT) on the histomorphometry of progeny’s organs in unexposed mothers are much less well studied. Therefore, this study aims to evaluate the effects of paternal FNT exposure on the sperm quality of the parent rat and its effects on the histomorphometry of the progeny’s organs. Randomly, male Sprague Dawley rats (n = 24) categorized as F0 were distributed equally into three groups namely Control, FNT-10, and FNT-20. Control received 1 mL/kg corn oil while FNT-10 and FNT-20 received 10 mg/kg and 20 mg/kg of FNT, respectively, via oral force feeding for 28 consecutive days. At the end of the study, male rats were mated with unexposed female rats and the male rats were sacrificed to obtain sperm for sperm characterization and DNA damage evaluation. Meanwhile, the rats’ progeny (F1) namely pControl, pFNT-10, and pFNT-20 were left to grow until postnatal day 70 before being sacrificed to obtain the matured organs for histology and morphometric analysis. Our results showed that both doses of FNT reduced sperm quality and caused DNA fragmentation in F0 rats compared with the control group (p < 0.05). The number of Leydig cells as well as the diameter of the seminiferous tubules and glomerulus of the pFNT-20 group had significantly decreased (p < 0.05) compared with the pControl group. The Bowman’s space of the pFNT-20 group had significantly increased (p < 0.05) compared with the pFNT-10 and pControl groups. Therefore, paternal exposure to FNT reduced the sperm quality and increased sperm DNA fragmentation in F0 male Sprague Dawley rats and altered the histology and morphometry of the selected organs in the F1 progeny. Full article
(This article belongs to the Section Toxicology)
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Figure 1

Figure 1
<p>Comparison of normal and abnormal sperm morphology, 40×. (<b>a</b>) Shows normal sperm morphology; hook head and long tail. (<b>b</b>) Shows abnormal tailless sperm. (<b>c</b>) Sperm with coiled tail. (<b>d</b>,<b>e</b>) Depicts a bend at a point on the sperm tail and abnormally developed sperm head such as pin and amorphous. (<b>f</b>) Cephalocaudal bending. Sperm was stained with a Diff-Quik staining kit.</p>
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<p>Sperm nuclear DNA fragmentation using the acridine orange test. Sperm smears were stained with freshly prepared acridine orange and viewed using a fluorescent microscope (oil immersion) and a 460 nm filter (scale bar: 20 µm). (<b>a</b>) Control, 100×; (<b>b</b>) sperm heads with green fluorescence, 100×; (<b>c</b>) FNT-10, 100×; (<b>d</b>) sperm heads with yellow fluorescence, 100×; (<b>e</b>) FNT-20, 100×; (<b>f</b>) sperm heads with dark orange fluorescence, 100×. Sperm heads with green fluorescence (white arrow) indicate intact DNA while sperm heads with yellow (yellow arrow) and dark orange fluorescence (red arrow) indicate fragmented DNA.</p>
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<p>Gross anomalies observed in F1 progeny of <span class="html-italic">p</span>FNT-20 rats. (<b>a</b>) Defective foot. (<b>b</b>) Short tail. (<b>c</b>) No tail.</p>
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<p>Heart, liver, and renal cross section of rats stained with H&amp;E. (Magnification: 40×). Normal myocardiocyte (MC) is characterized by a single nucleus (N). The myofibril (M) is arranged in an orderly manner with the presence of striation on MC in both male and female groups. Myocardiocyte cells (MC) are connected between each other through an intercalated disc (ID) that is located in the end of MC. The cubical shape of the hepatocyte cell (SH) looks normal along the central vein (CV) and sinusoid (S). The Kupffer cell (SK) in star shape in S was observed in all groups. However, CV was smaller in <span class="html-italic">p</span>FNT-20 compared with other groups. Normal glomerulus (G), Bowman’s capsule (BC), Bowman’s space (BS), distal convoluted tubule (DCT), and proximal convoluted tubule (PCT) were observed in all female rat groups. There was atrophy in the glomerulus (G) size and Bowman’s space (BS) dilatation in male rats of <span class="html-italic">p</span>FNT-10 and <span class="html-italic">p</span>FNT-20 groups.</p>
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17 pages, 5330 KiB  
Article
Simultaneous Hydrolysis and Detection of Organophosphate by Benzimidazole Containing Ligand-Based Zinc(II) Complexes
by Gaber A. M. Mersal, Hamdy S. El-Sheshtawy, Mohammed A. Amin, Nasser Y. Mostafa, Amine Mezni, Sarah Alharthi, Rabah Boukherroub and Mohamed M. Ibrahim
Crystals 2021, 11(6), 714; https://doi.org/10.3390/cryst11060714 - 21 Jun 2021
Cited by 6 | Viewed by 2325
Abstract
The agricultural use of organophosphorus pesticides is a widespread practice with significant advantages in crop health and product yield. An undesirable consequence is the contamination of soil and groundwater by these neurotoxins resulting from over application and run-off. Here, we design and synthesize [...] Read more.
The agricultural use of organophosphorus pesticides is a widespread practice with significant advantages in crop health and product yield. An undesirable consequence is the contamination of soil and groundwater by these neurotoxins resulting from over application and run-off. Here, we design and synthesize the mononuclear zinc(II) complexes, namely, [Zn(AMB)2Cl](ClO4) 1 and [Zn(AMB)2(OH)](ClO4) 2 (AMB = 2-aminomethylbenzimidazole), as artificial catalysts inspired by phosphotriesterase (PTE) for the hydrolysis of organophosphorus compounds (OPs) and simultaneously detect the organophosphate pesticides such as fenitrothion and parathion. Spectral and DFT (B3LYP/Lanl2DZ) calculations revealed that complexes 1 and 2 have a square-pyramidal environment around zinc(II) centers with coordination chromophores of ZnN4Cl and ZnN4O, respectively. Both 1 and 2 were used as a modifier in the construction of a biomimetic sensor for the determination of toxic OPs, fenitrothion and parathion, in phosphate buffer by square wave voltammetry. The hydrolysis of OPs using 1 or 2 generates p-nitrophenol, which is subsequently oxidized at the surface of the modified carbon past electrode. The catalytic activity of 2 was higher than 1, which is attributed to the higher electronegativity of the former. The oxidation peak potentials of p-nitrophenol were obtained at +0.97 V (vs. Ag/AgCl) using cyclic voltammetry (CV) and +0.88 V (vs. Ag/AgCl) using square wave voltammetry. Several parameters were investigated to evaluate the performance of the biomimetic sensor obtained after the incorporation of zinc(II) complex 1 and 2 on a carbon paste electrode (CPE). The calibration curve showed a linear response ranging between 1.0 μM (0.29 ppm) and 5.5 μM (1.6 ppm) for fenitrothion and 1.0 μM (0.28 ppm) and 0.1 μM (0.028 ppm) for parathion with a limit of detection (LOD) of 0.08 μM (0.022 ppm) and 0.51 μM (0.149 ppm) for fenitrothion and parathion, respectively. The obtained results clearly demonstrated that the CPE modified by 1 and 2 has a remarkable electrocatalytic activity towards the hydrolysis of OPs under optimal conditions. Full article
(This article belongs to the Special Issue Research about Vital Organic Chelates and Metal Ion Complexes)
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Figure 1

Figure 1
<p>(<b>a</b>) ORTEP structure of complex <b>1</b>, (<b>b</b>) numbered DFT optimized structure of complex <b>2</b> and (<b>c</b>) 2D packing model of complex <b>1</b> along the a-axis showing the hydrogen bond network.</p>
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<p>FTIR spectra of zinc(II) model complexes [Zn(AMB)<sub>2</sub>Cl](ClO<sub>4</sub>) <b>1</b> and [Zn(AMB)<sub>2</sub>(OH)](ClO<sub>4</sub>) <b>2</b>.</p>
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<p>Raman spectra of the ligand AMB∙2HCl and its zinc(II) model complexes [Zn(AMB)<sub>2</sub>Cl](ClO<sub>4</sub>) <b>1</b> and [Zn(AMB)<sub>2</sub>(OH)](ClO<sub>4</sub>) <b>2</b>.</p>
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<p><sup>1</sup>H NMR titration of zinc(II) complex <b>1</b> (2.0 × 10<sup>−3</sup> M) as a function of pD in CD<sub>3</sub>OD:D<sub>2</sub>O (3:1, <span class="html-italic">I</span> = 0.1 M NaNO<sub>3</sub>, 25 ± 0.1 °C).</p>
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<p>Cyclic voltammetric response for: (a) bare carbon paste electrode, (b) carbon paste electrode modified with AMB ligand, (c) carbon paste electrode modified with complex <b>1</b> and (d) carbon paste electrode modified with complex <b>2</b>. These used 5.0 mM K<sub>3</sub>[Fe(CN)<sub>6</sub>]/K<sub>4</sub>[Fe(CN)<sub>6</sub>], a potential scan rate of 50 mV s<sup>−1</sup> and a potential range from +1.5 to −1.5 V (vs. Ag/AgCl).</p>
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<p>Equivalent circuit (<b>A</b>) and Nyquist plots (<b>B</b>) of bare CPE (a), CPE modified by AMB (b), CPE modified by Zn complex 1 (c) and CPE modified by Zn complex 2 (d) in a solution containing 1 mM [Fe(CN)<sub>6</sub>]<sup>3−/4−</sup> and 5 M KCl.</p>
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<p>Cyclic voltammograms of 1.0 mM of <span class="html-italic">p</span>-nitrophenol at a CPE modified with Zn(II) complex <b>2</b> at different pH values: (<b>a</b>) 7, (<b>b</b>) 8, (<b>c</b>) 9 and (<b>d</b>) 10; scan rate = 50 mV/s.</p>
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<p>Electrochemical behavior of 1 × 10<sup>−3</sup> M (<b>a</b>) parathion and (<b>b</b>) fenitrothion in a phosphate buffer (pH = 8.0) using cyclic voltammetry.</p>
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<p>The repetitive cyclic voltammograms for 1 × 10<sup>−3</sup> M fenitrothion in phosphate buffer (pH 8) in presence of CTAB (1 × 10<sup>−3</sup> M).</p>
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<p>Effect of scan rate (from 10 to 100 mV/s) on the cyclic voltammograms for 1 × 10<sup>−3</sup> M fenitrothion in phosphate borate buffer pH 8 in presence of CTAB with 50 mV/s scan rate.</p>
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<p>Effect of different concentration in the square wave voltammetric voltammograms on the peak current signal for fenitrothion (<b>a</b>), calibration plot for fenitrothion (<b>b</b>) and calibration plot for parathion (<b>c</b>) in a phosphate buffer (pH = 8.0) using cyclic voltammetry.</p>
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<p>Effect of different concentration in the square wave voltammetric voltammograms on the peak current signal for fenitrothion (<b>a</b>), calibration plot for fenitrothion (<b>b</b>) and calibration plot for parathion (<b>c</b>) in a phosphate buffer (pH = 8.0) using cyclic voltammetry.</p>
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<p>(<b>a</b>) Calculated (DFT) HOMO orbital of the complex <b>2</b>, (<b>b</b>) calculated (DFT) LUMO orbital of the substrate (Parathion) and (<b>c</b>) the calculated (DFT) <b>2</b>. OPs complex stabilized by hydrogen bond.</p>
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<p>Proposed mechanism for the hydrolysis of parathion with complex <b>2</b>.</p>
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