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COLLOIDS AND SURFACES B-BIOINTERFACES · 2021 · IF 5.268

Thiram/hydroxypropyl-β-cyclodextrin inclusion complex electrospun nanofibers for a fast dissolving water-based drug delivery system

Shuang Gao,Yanyan Liu,Jingyu Jiang,Xiaoming Li,Fei Ye,Ying Fu,Lixia Zhao

The electrospinning of thiram/hydroxypropyl- β -cyclodextrin inclusion complex nanofiber (thiram/HP β CD-IC-NF) was produced for establishing a quick dissolving water-based drug delivery system. As a dithiocarbamate broad-spectrum fungicide, thiram is insoluble in water. High-concentration HP β CD solutions (180 %, w/v) were applied in thiram/HP β CD systems to implement electrospinning with no extra polymer matrix added. The formation of thiram/HP β CD-IC-NF was identified by Fourier transform infrared spectroscopy, X-ray diffraction as well as nuclear magnetic resonance. Phase solubility study proved HP β CD played a huge role in the improvement in solubility of thiram, and thiram/HP β CD-IC-NF showed an excellent dissolution rate. Scanning electron microscopy was used to examine the configuration of surface of thiram/HP β CD-IC-NF, which exhibited that thiram/HP β CD-IC-NF was uniform and beadless. In addition, thiram/HP β CD-IC-NF exhibited better antifungal activity and thermal stability than pure thiram. In summary, thiram/HP β CD-IC-NF drug delivery system contributed to water solubility, thermal stability and antifungal activity of thiram. It could provide a new idea for the development of new formulations of rapidly dissolving green pesticides, and made efforts to promote the sustainable development of agriculture.

CAS / MDL: 128446-35-5
研究领域: 农业科学 · 药剂学
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FOOD CHEMISTRY · 2020 · IF 6.306

Bimetallic core shelled nanoparticles (Au@AgNPs) for rapid detection of thiram and dicyandiamide contaminants in liquid milk using SERS

Abid Hussain,Da-Wen Sun,Hongbin Pu

Existing methods for contaminants detection in liquid milk are complex, requires chemicals and time-consuming experimental procedure. In this study, SERS based on bimetallic core shelled nanoparticles was employed for simultaneous and fast detection of thiram and dicyandiamide (DCD) in the milk. Spectra ranging from 400 to 1700 cm −1 were selected to examine thiram (0.5, 1, 2, 5 and 10 ppm) and DCD (20, 40, 80,160 and 320 ppm), by employing 28 nm gold cores and silver-shell thickness of 8 nm. A strong peak at 1379 cm −1 was ascribed to thiram with LOD of 0.21 ppm and R 2 of 0.9896, whereas a band at 929 cm −1 was associated with DCD, delivering LOD of 14.88 ppm and R 2 of 0.9956. The proposed method could achieve results within 34 min and this ecofriendly method can be further employed for simultaneous and rapid screening of other accidental contaminants in milk.

研究领域: 分析化学 · 食品科学 · 环境科学
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JOURNAL OF PHYSICS D-APPLIED PHYSICS · 2025 · IF 3.2

SERS substrates of Ag nanoparticles decorated Si nanostage with neck for Thiram detection

Hexing Ren,Yaxin Wang,Jiahong Wen,Fan Zhang,Chengxuan Tang,Xiqiang Zhong,Yongjun Zhang,Yuxia Wang,Renxian Gao,Kun Zhang,Fengyi Zhang,Rufei Cui,Xiaoyu Zhao

Nanosphere lithography enables tunable fabrication of Si nanoarrays (hexagons, stages, cones) on Si (100) by precisely controlling etching time. Specifically, the nanostage arrays, with their high surface area due to neck regions, can absorb more Ag nanoparticles (AgNPs), leading to superior SERS performance through the formation of hotspots. In addition, COMSOL simulations confirm plasmon coupling inter-particle, particle-film, and inter-structure. The linear detection of Thiram (0.05–50 ppm) remains stable within 120 days, meeting practical requirements for pesticide detection and showing potential for food safety applications.

研究领域: 分析化学 · 食品安全 · 纳米技术
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2022 · IF 4.831

Preparation of SERS active filter paper for filtration and detection of pesticides residue from complex sample

Min Hou,Ning Li,Xiaoran Tian,Qian Yu,Juan-P. Hinestroza,Xianming Kong

The selectivity is needed mostly in SERS sensing because analytes of interest are commonly present in a complex mixture containing particles and impurities, which hinder the interactions between the laser and analyte being detected. In this manuscript, we describe our efforts developing a simple and instant. method to prepare a filter paper SERS sensor. Colloidal Ag nanoparticles were immobilized on one side of filter paper via an in-situ growth method. The fabrication process of the sensor could be finished in several minutes, and no special facility needed. The filter paper SERS sensor demonstrated a spectra uniformity with a 7.0 % point-by-point signal deviation. And the filter function of the sensor could effectively filter out interferences from samples in 1 min, that allowing the direct detection of thiram in ketchup by SERS with detection limit of 93 ppb. Furthermore, we used a Quick Easy Cheap Effective Rugged and Safe (QuEChERS) sample preparation method to detect malachite green (MG) in soil with a sensitivity as low as 0.01 ppm without any sample pre-treatment or purification. A SERS filter paper may open a new avenue for rapid testing of food quality during manufacturing as well as fast detection of potential contaminants in a myriad of substrates.

CAS / MDL: 1074-36-8 569-64-2
研究领域: 分析化学 · 食品安全检测
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NEW JOURNAL OF CHEMISTRY · 2016 ·Vol. 41 ·期 4 ·1582-1590 · IF 3.277

Fabrication of Fe3O4@SiO2@Ag magnetic–plasmonic nanospindles as highly efficient SERS active substrates for label-free detection of pesticides

Qinye He,Aiwu Zhao,Lei Li,Henghui Sun,Dapeng Wang,Hongyan Guo,Mei Sun,Ping Chen

Fe3O4@SiO2@Ag magnetic–plasmonic nanospindles with efficient SERS performance and magnetic responsiveness have been successfully fabricated. Uniform and monodispersed Fe3O4@SiO2 nanospindles were prepared by a robust strategy through annealing the obtained β-FeOOH@SiO2 nanospindles in hydrogen atmospheres at 350 °C; the SiO2 shell could be regarded as an interlayer to maintain the morphology and offer a solid support for the further growth of Ag nanoparticles. Ag nanoparticles were introduced via in situ reduction of AgNO3, and the coverage rate of Ag nanoparticles anchored on Fe3O4@SiO2 was adjusted through regulating the AgNO3 concentration. Fe3O4@SiO2@Ag magnetic–plasmonic nanospindles can serve as highly efficient SERS active substrates with controllable magnetic aggregation due to steady enrichment of mass molecules in close proximity to abundant hot spots. Moreover, these nanospindles are used for label-free detection of thiram, and the detection limit is as low as 1 × 10−7 M (about 0.024 ppm), which is lower than the maximal residue limit of 7 ppm in fruits prescribed by the U.S. Environmental Protection Agency. Therefore, such magnetic–plasmonic nanospindles in the magnetic aggregation state may be potentially applied in rapid trace detection of residual pesticides or other specific analytes.

CAS / MDL: 1193-02-8 137-26-8
研究领域: 材料科学 · 分析化学
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2024 · IF 7.7

Quaternized chitosan-based organic-inorganic nanohybrid nanoparticles loaded with prothioconazole for efficient management of fungal diseases with minimal environmental impact

Junfan Niu,Chao Wang,Ke Qiao,Min Liao,Ying Liu,Yi Ding,Huanhuan Yao,Huili Zhang,Haiqun Cao

Poor foliar deposition and retention of pesticides results in serious pesticide residues and environmental pollution. Organic-inorganic hybridized nanoparticles (OIHN), combining the advantages of organic and inorganic materials, can be used as carriers to load pesticides for efficient and safe application. Herein, a novel multifunctional OIHN composed of mesoporous silica nanoparticles (MSNs) and cationic chitosan quaternary ammonium salt (HACC) was constructed and used as a delivery system for prothioconazole (PTC). The resultant PTC@MSNs-HACC exhibited a remarkable loading capacity of 39.07 wt% and demonstrated enhanced PTC release (31.47 %) under alkaline conditions. The UV-shielding properties of MSNs efficiently shielded PTC from photodegradation, increasing its photostability by over threefold. The strong positive charge of HACC conferred excellent adhesion of PTC@MSNs-HACC to fungal cell membranes, leading to high deposition on wheat leaves with improved rain-wash resistance (increased by 30 %). Consequently, PTC@MSNs-HACC (EC 50 : 12.48 mg/L) exhibited superior wheat scab control compared to PTC emulsifiable concentrate (EC 50 : 28.49 mg/L). Additionally, PTC@MSNs-HACC displayed excellent uptake and transport in plants, ensuring plant safety and reducing toxicity to zebrafish by >1-fold. The potential application of the developed PTC@MSNs-HACC in agricultural production holds significant promise and is anticipated to find widespread use in the future.

研究领域: 农业科学 · 植物保护 · 材料科学
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MICROCHIMICA ACTA · 2019 ·Vol. 186 ·期 7 ·1-9 · IF 5.479

A 3D spongy flexible nanosheet array for on-site recyclable swabbing extraction and subsequent SERS analysis of thiram

Wang Ying,Yu Xiaofei,Chang Yuhong,Gao Cuiling,Chen Jing,Zhang Xiaoli,Zhan Jinhua

A sponge inspired three dimensional flexible aluminum foil based ZnO nanosheet array substrate is described for use in real-world surface enhanced Raman spectroscopic detection. Gold and silver nanoparticles were employed to form numerous hot spots on uniformly grown ZnO nanosheets on the substrate. This flexible spongy substrate can extract analytes (such as the fungicide thiram) from various complex sample surfaces by physical swabbing. Specifically, this substrate was applied to detect thiram on the surface of fruits and vegetables. Non-destructive recycling detection with a relative standard deviation of 6.1% was accomplished by monitoring the characteristic Raman peak at 1382 cm −1 . This modified substrate has a low detection limit (0.2 ng cm −2 of thiram for apple and tomato), outstanding uniformity (relative standard deviation = 8.9%) and thermal stability (relative standard deviation = 0.9%). Schematic representation of using a aluminum foil modified with ZnO nanosheets as a flexible and recyclable substrate for SERS analysis of pollutants. The substrate can be cleaned after use by UV irradiation.

CAS / MDL: 1193-02-8 5970-45-6
研究领域: 分析化学 · 环境科学
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ACS Nano · 2025 · IF 16

Cellulase- and pH-Stimulating Selenium Nanopesticide Enhances Antifungal Efficacy to Anthracnose: Action Mechanism and Environmental Safety

Jingyuan Wang,Xiaoyan Li,Panpan Chen,Rong Li,Jingwei Hu,Xiangwei Wu,Yi Wang,Hui Li

Nanopesticides (NPs) provide a sustainable approach to reducing the use of chemical pesticides and mitigating their environmental risks in agriculture. In the present study, a pH and cellulase dual-stimulating system with the loaded pesticide penthiopyrad (PEN) was developed by incorporating hydroxypropyl cellulose (HPC) on the surfaces of mesoporous nanoselenium (MSe). In the measurement of antifungal efficacy of PEN against Colletorichum orbiculare Arx, compared to the neutral environment, i.e., pH = 7 without cellulase, the cumulative release of PEN from HPC@PEN@MSe NPs increased 5.7 and 4.8 times of the amount released at pH 3 and 5, respectively; at pH 7, the presence of cellulase solution substantially enhanced PEN release by 6.1 times more than that without cellulase. The HPC@PEN@MSe NPs demonstrated 3.2-fold of antifungal efficacy greater than the commercial 20% PEN suspension concentrate (20% PEN SC). This dual-stimulating NPs can induce oxidative stress responses and cell structural damage in pathogens, demonstrating a broad spectrum of antifungal activity. Mechanistic investigations illustrated that HPC@PEN@MSe NPs specifically promote the accumulation of reactive oxygen species, including hydroxyl radicals (•OH), superoxide radicals (•O2–), and singlet oxygen (1O2) in pathogenic cells by regulating gene expressions relevant to oxidative phosphorylation and lipid metabolism pathways, ultimately leading to eradication of pathogens. In vivo, HPC@PEN@MSe NPs sprayed could be transported in plants and specifically activated at the infected leafy, stem, and root tissues of cucumber plants, with the maximum PEN concentration at 0.93 mg/kg detected in the infected leaves at 12 h. The PEN residual concentration still had 0.09 mg/kg after 14 days, which suggests long-lasting activity. Moreover, the results of detached cucumber leaves and pot experiments indicated that HPC@PEN@MSe NPs significantly increased antioxidant enzyme levels, enhanced resistance to anthracnose, and manifested no apparent effects on plant growth. This eco-friendly plant protection strategy developed in this study exhibits apparent potential in practical applications while maintaining ecological sustainability and providing a potential path to address plant health management in modern agriculture.

研究领域: 农业科学 · 纳米技术 · 植物病理学 · 环境科学 · 材料科学 · 生物化学 · 微生物学 · 生物技术
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Analytical Methods · 2023 ·Vol. 15 ·期 37 ·4851-4861 · IF 3.1

Sensitive determination of thiram in apple samples using a ZIF-67 modified Si/Au@Ag composite as a SERS substrate

Rui Yang,Baowen Zhang,Ya Wang,Yi Zheng,Qian Zhang,Xiupei Yang

Substrate materials with high sensitivity and storage stability are crucial for the practical analytical application of surface-enhanced Raman scattering (SERS) techniques. In this work, a SERS-active substrate (Si/Au@Ag/ZIF-67) was fabricated with a metal–organic framework (ZIF-67) on a plasmonic surface (Si/Au@Ag) via self-assembly. The as-prepared material combined the properties of the abundant hotspots of the Au@Ag nanoparticles and the excellent adsorption performance of ZIF-67 for organic molecules. The synergy leads to high sensitivity of the composite substrate with a low detection limit for 4-aminothiophenol (a typical Raman reporter molecule) down to 2.0 × 10−9 M and the analytical enhancement factor (AEF) of the SERS substrate is 3.4 × 106. Moreover, the substrates exhibited good repeatability, high reproducibility, and reliable stability due to the MOF coating. The SERS signal was stable after 60 days of storage at room temperature. Ultimately, the optimal Si/Au@Ag/ZIF-67 was applied as a SERS sensor to analyze thiram, and the results showed a linear concentration range from 10−7 to 10−5 M with good linearity (R2 = 0.9934). The recoveries of thiram in spiked apple juice were in the range of 95.7–102.3%, with relative standard deviations less than 4.3%. These results predict that the proposed SERS substrates may hold great potential for the detection of environmental and food pollution in practical applications.

研究领域: 分析化学 · 环境科学 · 食品科学
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