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FOOD CHEMISTRY · 2022 · IF 9.231

Cu2+ assisted carnation-like fluorescent metal–organic framework for triple-mode detection of glyphosate in food samples

Jianping Guan,Qing He,Qi Liu,Xiaoqing Chen

Herein, by employing a novel synthesized ligand H 2 L, a flower-like luminescent metal–organic framework IRMOF-3-L was constructed for developing a triple-mode sensor for glyphosate (Glyp) detection. The ligand H 2 L was designed to contain three functional parts, which endowed the resulted IRMOF-3-L with peroxidase-like activity and unique fluorescence property, as well as specific combining capacity for Cu 2+ to quench its fluorescence. The quenched fluorescence of IRMOF-3-L/Cu 2+ could be recovered by Glyp to realize fluorescence detection of Glyp. Besides, the peroxidase activity of IRMOF-3-L/Cu 2+ could also be inhibited by Glyp, and result in the decrease of catalysate oxTMB, concurrently reducing the changes of colorimetric and SERS signal. Therefore, the fluorescent/colorimetric/SERS triple-mode based detection of Glyp was favorably realized, and the detection limits were calculated as low as 0.738, 2.26 and 0.186 nM, respectively. Furthermore, a portable test strips-smartphone sensing platform was constructed for point of care testing of Glyp in food samples.

研究领域: 分析化学 · 食品安全
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ECOTOXICOLOGY AND ENVIRONMENTAL SAFETY · 2023 · IF 6.8

Dose-dependent inhibitory effects of glyphosate on invasive Pomacea canaliculata reproductive and developmental growth under oxidative deposition

Dongxia Liang,Yinshi Li,Shuoyu Li,Dele Meng,Fengchun Li,Siying Huang,Maojian Gong,Junhao Qin,Huashou Li

Glyphosate (GLY) is the most widely used herbicide worldwide, and its effects on animals and plants have attracted increasing attention. In this study, we explored the following: (1) the effects of multigenerational chronic exposure to GLY and H 2 O 2, alone or in combination, on the egg hatching rate and individual morphology of Pomacea canaliculata ; and (2) the effects of short-term chronic exposure to GLY and H 2 O 2 , alone or in combination, on the reproductive system of P. canaliculata . The results showed that H 2 O 2 and GLY exposure had distinct inhibitory effects on the hatching rate and individual growth indices with a substantial dose effect, and the F1 generation had the lowest resistance. In addition, with the prolongation of exposure time, the ovarian tissue was damaged, and the fecundity decreased; however, the snails could still lay eggs. In conclusion, these results suggest that P. canaliculata can tolerate low concentrations of pollution and in addition to drug dosage, the control should focus on two time points, the juvenile and early stage of spawning.

CAS / MDL: 7722-84-1
研究领域: 环境毒理学 · 水生生物学 · 生态毒理学
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CHEMICAL ENGINEERING JOURNAL · 2022 · IF 16.744

Core-shell structured cobalt–nickel bimetallic sulfide with dual redox cycles to activate peroxymonosulfate for glyphosate removal

Jie Li,Zhuobiao Ni,Qiongzhi Gao,Xixian Yang,Yueping Fang,Rongliang Qiu,Mingshan Zhu,Shengsen Zhang

Glyphosate is a widely used herbicide in agriculture. Its residues pose a great threat to ecological balance and human health. The potential impact of glyphosate and its by-products on the soil and water environment is of great concern. Here, a core–shell structured cobalt–nickel bimetallic sulfide NiCo 2 S 4 /Co 9 S 8 /NiS (NCS) is synthesized by a simple two-step hydrothermal method, and used as a novel peroxymonosulfate (PMS) activator for degradation of glyphosate. The effects of various reaction conditions on the degradation of glyphosate in the NCS-PMS system are investigated. The NCS is used to activate PMS by the dual redox cycle of Co 2+ /Co 3+ and Ni 2+ /Ni 3+ under its core–shell structure to efficiently degrade glyphosate. The optimized NCS achieved 82.2 % removal of 10 -4 mol⋅L -1 glyphosate in 35 min with an initial pH = 3.9. The removal performance is 25.7 and 1.5 times higher than that of monometallic sulfides Ni 3 S 2 /NiS and Co 3 S 4 prepared by the same process of NCS, respectively. The radical quenching experiments reveal that NCS interacted with PMS to generate SO 4 •− and •OH radicals, O 2 •− as well as 1 O 2 together to achieve efficient degradation of glyphosate. The main intermediates of glyphosate degradation by NCS-activated PMS are identified by liquid chromatography-quadrupole time-of-flight mass spectrometry, and possible degradation pathways of glyphosate are proposed and the relative toxicity of degraded products is evaluated. This work provides a novel insight to produce high-performance multiphase catalysts for glyphosate degradation as well as practical applications.

研究领域: 环境科学 · 农业科学
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SCIENCE OF THE TOTAL ENVIRONMENT · 2023 · IF 9.8

Effects of glyphosate exposure on gut–liver axis: Metabolomic and mechanistic analysis in grass carp (Ctenopharyngodon idellus)

Biao Yan,Yumiao Sun,Kaiyu Fu,Yindan Zhang,Lei Lei,Jun Men,Yongyong Guo,Shengmin Wu,Jian Han,Bingsheng Zhou

Glyphosate, one of the most widely used herbicide worldwide, is potentially harmful to non-target aquatic organisms. However, the environmental health risks regarding impacts on metabolism homeostasis and underlying mechanisms remain unclear. Here we investigated bioaccumulation, metabolism disorders and mechanisms in grass carp after exposure to glyphosate. Higher accumulation of glyphosate and its major metabolite, aminomethylphosphonic acid, in the gut was detected. Intestinal inflammation, barrier damage and hepatic steatosis were caused by glyphosate exposure. Lipid metabolism disorder was confirmed by the decreased triglyceride, increased total cholesterol and lipoproteins in serum and decreased visceral fat. Metabolomics analysis found that glyphosate exposure significantly inhibited bile acids biosynthesis in liver with decreased total bile acids content, which was further supported by significant downregulations of cyp27a1 , cyp8b1 and fxr . Moreover, the dysbiosis of gut microbiota contributed to the inflammation in liver and gut by increasing lipopolysaccharide, as well as to the declined bile acids circulation by reducing secondary bile acids. These results indicated that exposure to environmental levels of glyphosate generated higher bioaccumulation in gut, where evoked enterohepatic injury, intestinal microbiota dysbiosis and disturbed homeostasis of bile acids metabolism; then the functional dysregulation of the gut-liver axis possibly resulted in ultimate lipid metabolism disorder. These findings highlight the metabolism health risks of glyphosate exposure to fish in aquatic environment.

CAS / MDL: 28920-43-6
研究领域: 环境科学 · 毒理学 · 水生生物学 · 代谢学
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MICROCHEMICAL JOURNAL · 2025 · IF 5.1

Ratiometric fluorescent probe based on amino-functionalized MOF for on-site glyphosate detection via smartphone-integrated hydrogel platform

Hao Su,Si-qi Yang,Qiu-ling Zhang,Wei-peng Qiu,Lin Luo,Ya-li Zhao,Zhen-lin Xu,Hong Wang,Peng Wen

Considering the hazards of glyphosate and the limitations of current detection methods, a method for rapid detection of glyphosate is designated. Herein, a novel sensing platform based on the immobilization of ratiometric fluorescent probe NH 2 -MIL-101(Fe)@[Ru(bpy) 3 ] 2+ (briefly as MOF@Ru) into agarose hydrogel was fabricated for the rapid and selective detection of glyphosate. Firstly, MOF@Ru with an octahedral morphology was synthesized, and the chemical structure composition was further characterized by X-ray diffraction (XRD), fourier transform infrared spectrometer (FTIR) and X-ray photoelectron spectroscopy (XPS). After that, the ratiometric fluorescence probe was assembled, and the optimized conditions were investigated. Under the optimal detection conditions, the ratiometric fluorescent probe enabled rapid detection (within <2 s), demonstrating a linear response within the concentration range of 0–100 μM (R 2  = 0.9934), and the detection limit was determined to be 0.63 μM. In the spiked recovery experiments with food samples, the recovery rates ranged from 98.90 % to 112.52 %, with a relative standard deviation of less than 6.86 %. Moreover, the fabricated ratiometric fluorescent probe was immobilized into agarose hydrogel, forming a portable test kit, which was compatible with smartphone RGB analysis. The R/B ratio exhibited a concentration-dependent behavior (R 2  = 0.9980), enabling the on-site detection with a detection limit of 0.78 μM, suggesting the potential for the rapid and on-site detection of glyphosate.

研究领域: 环境监测 · 分析化学 · 材料科学 · 食品安全 · 传感器与生物传感器
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ECOTOXICOLOGY AND ENVIRONMENTAL SAFETY · 2025 · IF 6.1

Impact of chronic exposure to field-level glyphosate on the gut microbiota of Apis cerana and Apis mellifera

Changsheng Ma,Sihao Chen,Xiaoyu Shi,Lianyang Bai,Hongmei Li-Byarlay,Zuren Li

Glyphosate (GLY) stands as one of the most extensively used pesticides globally. Although several studies have investigated the effects of sublethal doses of GLY on the gut microbiota of bees, limited information is available on how residual concentrations of GLY in bee food affect Apis cerana (Asian honey bees) and Apis mellifera (European honey bees) at different time points. To explore these effects, we employed 16S rRNA Illumina sequencing technology to evaluate the consequences of chronic GLY exposure (0.7 mg/kg, GLY residual in beebread) on the gut microbiome of A. cerana and A. mellifera on days 3 and 12 of the exposure period. Even though our findings revealed no significant difference in the microbiota abundance between control bees and GLY-treated bees on the 3rd day, GLY-treated bees exhibited 55.56 % abundance of the genus Snodgrassella (a core gut bacterium) and 4.54 % of the genus Commensalibacter (a non-core gut bacterium) compared to control bees in A. cerana and A. mellifera , respectively. In addition, our results showed that a noticeable trend indicated that the gut of A. mellifera was more susceptible to GLY than that of A. cerana . Considering the vital role of gut microbiota in the health of honey bee colonies, our results suggest that 0.7 mg/kg of GLY are likely to have adverse effects on the health of honey bees.

CAS / MDL: 1071-83-6
研究领域: 环境毒理学 · 微生物生态学 · 养蜂学 · 农药科学 · 昆虫微生物学
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Food Chemistry-X · 2025 · IF 8.2

Enhancing glyphosate detection in rice by SERS: controlled aggregation of silver nanoparticles and carbon disulfide-mediated signal amplification

Hui Ma,Anqi Wen,Tianmin Wang,Qianhong Li,Zihan Li,Weijie Lan,Kang Tu,Xiaoman Ji,Leiqing Pan

A highly sensitive and rapid surface-enhanced Raman spectroscopy (SERS) method was developed for glyphosate (GPH) detection in rice by combining carbon disulfide (CS 2 )-mediated derivatization with an optimized silver nanoparticle (AgNP) aggregation strategy. GPH was converted into a SERS-active thiazole derivative through pH-controlled reactions. An adsorption-first strategy (analyte pre-adsorption before aggregation) enhanced signals by 64.78 % at 1 min and maintained 11.83 % higher intensity after 6 min versus conventional aggregation-first methods, due to optimized hotspot positioning. The method achieved a detection limit of 0.13 μmol/L (signal-to-noise ratio = 3), below European Union regulatory limits, with excellent reproducibility (RSD = 8.39 %), high selectivity against amino acid interferents, and high time efficient (22 min total analysis). Moreover, spike-recovery tests in rice yielded 80.82 % − 129.62 % recovery, providing a robust platform for detection of trace GPH in complex food matrices. Consequently, this work establishes a time-efficient and cost-effective alternative to conventional chromatography, which facilitates rapid on-site monitoring.

CAS / MDL: 1071-83-6 6461-04-7
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SEPARATION AND PURIFICATION TECHNOLOGY · 2026 · IF 9.1

Tuning the electronic structure of Fe2O3 via sulfur doping to boost peroxymonosulfate activation for high-efficiency glyphosate degradation

Yijun Mo,Liwen Fan,Chao Wang,Xiaoli Sun,Ziyi Guo,Shengran Yu,Wei Wang,Shi-Wen Lv,Yanqing Cong

The introduction of sulfur endows Fe 2 O 3 with superior catalytic activity. • Sulfur doping regulates Fe spin state to accelerate interfacial electron transfer. • The formation of Fe S bonds triggers abundant oxygen vacancies. • The S-Fe 2 O 3 /PMS system achieves efficient glyphosate degradation dominated by 1 O 2 . Glyphosate residues in aquatic ecosystems pose serious threats to ecological safety and public health owing to their strong biological recalcitrance and intrinsic toxic properties. Herein, sulfur-doped Fe 2 O 3 (designated S-Fe 2 O 3 ) is synthesized via a facile sulfur annealing strategy to tune the electronic configuration of Fe sites and enhance its catalytic activity toward peroxymonosulfate (PMS) activation. Comprehensive characterizations confirm the successful formation of Fe S bonds, abundant oxygen vacancies, and an increased fraction of surface Fe 2+ after sulfur modification. More importantly, sulfur incorporation regulates the spin state of Fe active sites and lowers the work function of Fe 2 O 3 , which accelerates interfacial charge transfer. In addition, the generated Fe S bonds shift the Fe d-band center upward, further elevating the PMS activation capability of S-Fe 2 O 3 . Benefiting from the optimized electronic structure, the S-Fe 2 O 3 /PMS system realizes 94.6% glyphosate elimination within 14 min, with its reaction rate constant 7.8 times larger than that of bare Fe 2 O 3 . Meanwhile, S-Fe 2 O 3 exhibits excellent pH adaptability and prominent anti-interference performance against coexisting inorganic anions. Radical trapping and EPR tests further validate that 1 O 2 serves as the major contributor for glyphosate degradation, while both SO 4 •– and •OH also contribute to pollutant removal. Collectively, this work offers a facile modification route for iron-based catalysts and provides a promising strategy for remediating glyphosate-contaminated wastewater. Download: Download high-res image (252KB) Download: Download full-size image

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Journal of Environmental Chemical Engineering · 2026 ·Vol. 14 ·期 3 ·122410 · IF 7.5

Chloride-modulated CuFe₂O₄ /Illite for enhanced H₂O₂ activation for glyphosate degradation: Unraveling the active species transformation

Jun Wan,Zhaozhe Zhan,Xinchi Wang,Tingyang Li,Yan Wu,Zhiyong Yan

The effective degradation of persistent and potentially toxic glyphosate in water remains a challenge. Herein, we report an engineering strategy of chloride-modulated synthesis to fabricate illite-modified CuFe₂O₄ composite (CuFe₂O₄/Illite) as robust heterogeneous Fenton-like catalysts. The optimized catalyst exhibited outstanding glyphosate removal efficiency (98.6% in 60 min), wide pH adaptability (pH 3–11), and excellent stability (87.85% efficiency after four cycles). Chloride ions were found to slightly promote degradation, whereas common anions like HCO₃ - , NO₃ - , and SO₄² - showed mild inhibition. Quenching experiments and electron paramagnetic resonance (EPR) analysis identified •OH and O₂• - as the primary reactive oxygen species, with a minor contribution from ¹O₂ contribution. X-ray photoelectron spectroscopy (XPS) results revealed that the facilitated Cu²⁺/Cu⁺ and Fe³ ⁺/Fe²⁺ redox cycles served as an efficient electron-transfer highway, dramatically enhancing the heterolytic cleavage of H 2 O 2 and the sustained generation of reactive species. Based on liquid chromatography-mass spectrometry (LC-MS) analysis, a degradation pathway involving C-P bond cleavage and side-chain oxidation was proposed, leading to the mineralization of toxic intermediate Aminomethylphosphonic acid (AMPA) into CO₂, NH₄⁺, and PO₄³ - . This work provides a promising catalyst and elucidates the underlying mechanism for glyphosate wastewater remediation.

CAS / MDL: 106-51-4
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MICROCHEMICAL JOURNAL · 2026 · IF 5.2

Self-powered photoelectrochemical platform with Cs3BiBr6/AgInS2 photoanode and CuBi2O4 photocathode for ultrasensitive glyphosate analysis in food samples

Rui Xu,Qin Wei,Dan Li

A self-powered PEC sensor was developed for sensitivity glyphosate detection. • Cs 3 BiBr 6 -AgInS 2 was used as photoanode to provide photo electrons transmission. • CuBi 2 O 4 used as photocathode for providing electric energy for target detection. • The proposed glyphosate sensor showed a wide linear range of 1 × 10 −10 - 5 × 10 −4  mol/L. A self-powered photoelectrochemical (PEC) sensor was developed for the ultrasensitive and rapid detection of glyphosate, a widely used herbicide and potential contaminant in fruits and vegetables. The sensor integrates a Cs 3 BiBr 6 /AgInS 2 composite photoanode with a CuBi 2 O 4 -based photocathode. As a lead-free halide perovskite, Cs 3 BiBr 6 exhibits broad light absorption and prolonged carrier lifetime, while AgInS 2 modification markedly enhances the photoelectric conversion efficiency and optical stability of the photoanode. Meanwhile, CuBi 2 O 4 possesses excellent biocompatibility and abundant active sites, enabling efficient aptamer immobilization for the selective recognition of glyphosate. Under optimized conditions, the photocurrent response decreased linearly with increasing glyphosate concentrations over the range of 1.0 × 10 −10 –5.0 × 10 −4  mol/L, with a low limit of detection (LOD) of 4.6 × 10 −11  mol/L. In addition, the proposed PEC sensor demonstrated excellent stability, reproducibility, and accuracy in the analysis of real food samples, including soybean and corn, highlighting its considerable potential as a reliable analytical platform for on-site monitoring of pesticide residues in agricultural products. Download: Download high-res image (144KB) Download: Download full-size image

CAS / MDL: 1071-83-6 68-11-1
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ANALYTICA CHIMICA ACTA · 2026 · IF 6.1

Plant-wearable fluorescent hydrogel patch based on PDA-PEI copolymer dots for on-site visual detection of glyphosate

Shuqi Wang,Shuzhen Zheng,Hongzhi Lu,Changsheng Wang,Shoufang Xu

Background Glyphosate (GLY) residues are difficult to remove from agricultural products and pose potential risks to food safety, making their sensitive detection highly desirable. In this study, a Cu 2+ -mediated ratiometric fluorescence sensing platform was constructed for the sensitive detection of GLY by physically mixing polydopamine-polyethyleneimine copolymer dots (PDA-PEI CPDs) with terephthalic acid (PTA) based on a competitive coordination strategy. Results Cu 2+ coordinated with the amino groups on the surface of CPDs and the carboxyl groups of PTA to form a CPDs-PTA-Cu 2+ complex. This process quenched the green fluorescence of CPDs at 530 nm while generating a new blue emission at 450 nm. Upon the addition of GLY, competitive coordination between GLY and Cu 2+ disrupted the complex, resulting in fluorescence recovery at 530 nm and fluorescence quenching at 450 nm, thereby producing a ratiometric fluorescence response. The sensor shows linear ranges of 0-80 μg/mL for GLY (LOD = 5.73 ng/mL). To meet the requirements of on-site applications, a CPDs-Cu 2+ @sodium alginate hydrogel was further prepared. Under 365 nm excitation, the hydrogel responded to GLY through single-emission fluorescence recovery at 530 nm. The hydrogel enabled smartphone-assisted RGB quantitative analysis and in situ semi-quantitative screening of GLY on vegetable surfaces using a wearable hydrogel patch. Significance By integrating solution-phase ratiometric fluorescence quantification with hydrogel-based visual readout, a simple and portable sensing platform was established for accurate GLY determination and visual screening of surface residues.

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JOURNAL OF HAZARDOUS MATERIALS · 2026 · IF 10.6

Harnessing pollutant complexation for self-accelerated remediation: Glyphosate oxidation and toxicity mitigation in a Fe(II)/O2 system

Fen Liu,Wei Xiang,Chen Wang,Yongchun Zhao,Tao Zhou,Mingjie Huang,Xiaohui Wu

High-concentration glyphosate (Gly) wastewater presents a formidable remediation challenge due to its recalcitrance and the inherent risk of generating toxic intermediates like aminomethylphosphonic acid (AMPA). Herein, we report a facile “waste-treats-waste” strategy utilizing a self-accelerated Fe(II)/O 2 system that operates efficiently under neutral pH, effectively circumventing the acidic constraints of traditional Fenton processes. This system achieved a 57% Gly removal efficiency (initial concentration 0.5 g/L) within 60 min, with a kinetic rate constant ( k obs = 0.029 min −1 ) significantly outperforming conventional oxidation technologies. Mechanistic investigations reveal that Gly acts as a suicide ligand, forming an inner-sphere Fe(II)-Gly complex that lowers the Gibbs free energy barrier, thereby rendering O 2 activation thermodynamically favorable. The degradation proceeds via a dual-pathway mechanism, synergizing hydroxyl radical (•OH) attack (∼40%) with a dominant intramolecular ligand-to-metal charge transfer (LMCT) process (∼60%). Crucially, density functional theory (DFT) calculations elucidate that Fe(III) coordination induces a regioselective weakening of the C–N bond adjacent to the phosphonate group. This steric and electronic modulation steers the reaction pathway toward the preferential formation of benign glycine, successfully suppressing the generation of highly toxic AMPA. Bioassays using Tetrahymena thermophila confirmed that this glycine-selective pathway optimization significantly mitigates the acute toxicity of the effluent, validating the system as a sustainable and eco-safe solution for herbicide wastewater treatment.

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