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SCIENCE OF THE TOTAL ENVIRONMENT · 2019 · IF 5.589

Chlorination of enoxacin (ENO) in the drinking water distribution system: Degradation, byproducts, and toxicity

Tuqiao Zhang,Guilin He,Feilong Dong,Qingzhou Zhang,Yuan Huang

Chlorine is widely used as a drinking water disinfectant to ensure water security. However, the transformation mechanisms of its degradation of emerging pollutants within the water distribution system (WDS) is insufficiently understood. Thus, the kinetics, degradation byproducts, and toxicity of the chlorination of enoxacin (ENO, a type of emerging pollutant) were explored in a pilot-scale WDS for the first time. It was found that the chlorination rate of ENO was higher in deionized water (DW) than in the pilot-scale WDS, and the degradation followed second-order kinetics in DW. The degradation efficiency was found to be sensitive to pH, and was highest at a pH of 7.4. The chlorination rate of ENO increased with increasing temperature in both DW and WDS. For different pipe materials, the relative performance of ENO chlorination efficiency followed the order of steel pipe > ductile iron pipe > polyethylene (PE) pipe. Seven intermediates were identified during ENO chlorination, and the primary oxidation reaction involved the cleavage of the piperazine group. Finally, it was found that the potential for chlorine toxicity in treated drinking water in the presence of ENO is higher than it is without this pollutant.

研究领域: 环境科学 · 毒理学 · 水质工程
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Journal of Bionic Engineering · 2022 ·Vol. 19 ·期 2 ·483-496 · IF 2.995

Effect of Antibacterial Enoxacin on the Properties of Injectable Nano-hydroxyapatite/Polyurethane Cement for Bone Repairing

Zhang Jinzheng,Lei Xiaoyu,Tang Jiajing,Chen Jie,Zhao Qing,Fang Wei,Zhang Yinglong,Li Yubao,Zuo Yi

Biomaterial-associated infection (BAI) is a kind of serious post-operative complication in orthopaedic surgery. Antibiotic-loaded bone cement shines a light on BAI prevention for convenient manipulation and complex filling. To this aim, we designed an antibacterial bone cement based on Nano-hydroxyapatite/Polyurethane (PUHA) loading with antibiotic Enoxacin (EN). The distinct shear-thinning behavior of the prepolymers was observed, indicating a good injectability. The PUHA bone cement possessed a suitable curing speed, and the addition of EN might slightly expedite the curing process and enhance the mechanical properties. The EN release profile indicated that the EN-loaded bone cement could reach the minimum inhibitory concentration in 2 h, and sustainedly released EN for almost 8 days, exhibiting an antibacterial delivery potential. Antibacterial test further confirmed the antibacterial ability of EN-loaded bone cement is in a dose-dependent manner. However, the osteogenic performance of drug-loaded bone cement with high dosage is not as good as antibacterial activity. When the EN concentration of antibacterial cement was lower than 32 μg⋅mL −1 , the proliferation and osteogenic differentiation of rat mesenchymal stem cells could be significantly promoted. Overall, this study verified the potential of the EN-loaded PUHA bone cement in anti-infection and osteogenesis for bone repairing.

研究领域: 生物材料学 · 骨科医学 · 药剂学
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JOURNAL OF CHROMATOGRAPHY A · 2024 · IF 3.8

Synthesis of reusable hierarchical Pore PVDF-MIL-101(Cr) foam for Solid phase extraction of fluoroquinolones from water and its adsorption behavior for anionic and cationic dyes

Tianci Lv,Fubin Liu,Mengqian Xiao,Ying Liu,Litao Wang,Guihua Gao

In this study, a novel hierarchical pore MIL-101(Cr) foam (HPF-MIL-101) was designed and prepared using the sacrificial template method with NaCl as the sacrificial template. This method involved grinding, heating, and washing the NaCl template to produce HPF-MIL-101, with PVDF as the binder and MIL-101(Cr) as the adsorbent. This preparation process is both straightforward and cost-effective, avoiding the use or generation of any organic reagents, thereby offering an environmentally sustainable approach for producing metal-organic framework (MOF) composites. The prepared HPF-MIL-101 exhibited excellent adsorption capabilities for both anionic dye (methyl orange, MO) and cationic dye (methylene blue, MB). The adsorption process followed a pseudo-second-order kinetic model and Friedrich isotherm model, indicating a multilayer adsorption. This is further supported by the Weber-Morris intraparticle diffusion model, which divided the adsorption process into three stages. Furthermore, the adsorption process was consistent with the Freundlich isotherm model, with a correlation coefficient ( r ) greater than 0.96. HPF-MIL-101 can also be used as an adsorbent for solid phase extraction (SPE). Therefore, an SPE method combined with high-performance liquid chromatography (HPLC) was developed using HPF-MIL-101 as the adsorbent to analyze five fluoroquinolones (FQs) in water samples. This analytical method showed good linearity in the range of 30–2000 ng·mL −1 , with excellent linear correlation coefficient ( r = 0.9991–0.9999), reasonable extraction recoveries ranging from 80.39 to 112.7 % (RSD ≤ 7.9 %), and low limits of detection (8–30 ng·mL −1 ). Overall, the results indicated that HPF-MIL-101 not only had a simple, environment-friendly, and pollution-free preparation process but also can be reused for enrichment and detection of trace FQs in water. Thus, HPF-MIL-101 exhibits immense application potential in environmental pollutant removal and also provides a valuable reference for the preparation and application of other MOF composites.

研究领域: 环境科学 · 分析化学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Electrochemical assisted single atom copper modified novel nitrogen doped porous carbon mediated catalytic activity based on D-band center modification: Rapid degradation of enoxacin

Yuanchuan Ren,Yan Hu,Nanqi Ren,Xiaojuan Su,Fenghui Wu,Dandan Chen,Xuejun Zhu,Qiang Niu,Yan Guo

Persulfate (PMS) is an excellent free radical initiator with selective degradation of organic pollutants. This article presents the preparation of a high-performance Cu-SA@NCA(Single atom copper modified nitrogen doped aerogel carbon) electrocatalyst with adjustable interfacial separation enhancement effect for the first time. Under the optimal process parameters, the removal rates of ENO, COD, and TOC obtained after 5 min of reaction were 100 %, 73.41 % and 55.15 %, respectively. The average energy consumption was saved by 59.63∼123.25 kWh/kg ENO. After 6 cycles of degrading ENO wastewater, the removal rate of ENO only decreased by 8.55 %. It was demonstrated through characterization such as high-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM), X-ray absorption near edge structure (XANES), and Fourier Transform Extended X-ray Absorption Fine Spectroscopy (FT-EXAFS) that the single atom copper loaded on the Cu-SA@NCA surface is tightly bound to N in NCA through Cu-N 4 bond bridges, promoting the formation of double electron centers on the catalyst surface. The particle electrode catalyst significantly enhances the PMS activation process over a wide pH range and can accelerate the degradation of enoxacin (ENO). As the reaction center for PMS adsorption and activation, Cu-N 4 has a lower charge transfer resistance and can attract PMS to the catalyst surface, resulting in a higher current response in the PMS system. Organic pollutants release electrons through the carbon matrix of carbon based catalysts and transfer them to Cu-SA@NCA-PMS, promoting PMS activation and the formation of high valence copper ions, enhancing the degradation of pollutants. Density functional theory (DFT) further indicate that the regulatory effect of N on the electron distribution of Cu d orbitals is beneficial for the stretching and cleavage of Cu active centers by PMS, accelerating the process of SO 4 − · and ·OH generation rate, which is consistent with the results of XANES. In addition, during the degradation process of salt containing organic pollutants in PMS, Cu-SA@NCA exhibits strong resistance to inorganic ions, natural organic matter, and pH value. This work developed a new catalyst that selectively produces SO 4 − · and ·OH with 97.46 % selectivity, achieving high selectivity and efficiency in degrading pollutants.

研究领域: 环境科学 · 电化学 · 催化材料
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Analytical Methods · 2024 ·Vol. 16 ·期 22 ·3551-3561 · IF 2.7

Deep eutectic solvent-assisted synthesis of La–Ce hybrid nanorods for the colorimetric determination of tetracycline in foods

Kaigang An,Xin Li,Jia Chen,Shuang Zhang,Jing Xiao,Qing Wang,Hongdeng Qiu

Tetracycline (TC) as a broad-spectrum antibiotic, is widely used in the prevention and treatment of various bacterial diseases. However, its abuse in the livestock industry may lead to interference in human microecology, thereby causing various side effects. In this study, deep eutectic solvents (DESs) were synthesized using L-(–)-threonine (L-(–)-Thr) and cerium nitrate hexahydrate (Ce(NO3)3·6H2O), and later lanthanum nitrate hexahydrate (La(NO3)3·6H2O) was doped to synthesize La–Ce hybrid nanorods. These nanorods can be used for the determination of TC with high sensitivity and selectivity by the colorimetric method. This approach has a linear response to TC between 0.05 μM and 10 μM, with a detection limit of 0.016 μM. In this system, good dispersion provides the substance with a distinct peroxidase activity, which is used to create a colorimetric sensor for detecting TC. Mechanism studies show that the superoxide radical generated by the La–Ce nanomembrane plays a key role in peroxidase catalysis. Finally, the practicality of the method was verified by the determination of TC in food products (milk, pork and honey), which demonstrated that a good recovery rate can be obtained (91.4–102%).

研究领域: 分析化学 · 食品安全 · 纳米材料科学
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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Engineering Brønsted acid sites for enhanced nonradical pathways in antibiotic contaminant degradation

Xiuzhen Wei,Zelong Chen,Liangliang Xu,Yue Li,Xuekang Zhang,Xianghao Zhang,Qinghua Zhou,Meilan Pan

Peroxymonosulfate (PMS)-mediated advanced oxidation processes (AOPs) via nonradical pathways offer high selectivity and efficiency for pollutant degradation. However, achieving precise control over these pathways through catalyst design remains a significant challenge. This study focuses on Mn x Cu 0.4 Ni-layered double hydroxides (Mn x Cu 0.4 Ni-LDH) as catalysts optimized for enhancing PMS activation through a singlet oxygen ( 1 O 2 )-mediated pathway. Structural analysis reveals that Mn x Cu 0.4 Ni-LDH, featuring a Cu-Ov-Mn(IV) configuration, create Brønsted acid sites essential for catalysis. Compared to Cu 0.4 Ni-LDH, Mn x Cu 0.4 Ni-LDH demonstrates higher stability and efficiency in PMS activation, producing significant 1 O 2 (11.22 μM) and achieving superior degradation rates (0.29 min −1 for levofloxacin). Density functional theory (DFT) simulations suggest that Brønsted acid sites, synergistic Cu atoms and Mn atoms interactions, and oxygen vacancies (Ov) collectively enhance PMS activation by stabilizing active sites and facilitating electron transfer. These advancements improve catalyst performance, highlighting a promising strategy for pollutant-specific nonradical oxidation.

研究领域: 环境科学 · 催化化学
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JOURNAL OF FOOD COMPOSITION AND ANALYSIS · 2024 · IF 4

Fabrication of magnetic functionalized layered double hydroxide nanomaterials for detecting trace fluoroquinolones residues in meat integrated with HPLC-MS/MS

Wenrui Li,Yike Dang,Ruihong Wang,Weizhong Jin,Xiangli Chen,Yafei Zhai,Zhuoqun Su,Guoliang Li

Fluoroquinolones (FQs) are widely used to treat various animal diseases. The high residue of veterinary drugs in animal-origin food are new pollutants that seriously threaten human health. In this work, Fe 3 O 4 @LDH/ZIF was prepared by the in situ growth of zeolitic imidazolium skeletons (ZIFs) on Fe 3 O 4 @Zn/Al-layered double hydroxides (Fe 3 O 4 @Zn/Al-LDH), which was used as the adsorbent of FQs for magnetic solid phase extraction (MSPE). The prepared materials were characterized by using FT-IR, XRD, TEM, SEM, VSM, zeta, and nitrogen adsorption-desorption analyses. Under the optimized conditions, the limit of detections (LODs) of proposed methods for FQs is determined as low as 0.1–0.6 μg·kg −1 with good linearity (R 2 ≥0.9972). Furthermore, the MSPE approach has been effectively utilized to extract of FQs from a range of meat varieties including fish, pork, chicken, bullfrog, and beef. The recoveries from the spiked samples ranged from 86.5 % to 107 %, with relative standard deviations (RSD) below 8.8 %. These results demonstrated that the prepared nanoparticles hold unique advantages for trace FQs analysis in foodstuffs. This study provides a magnetic adsorbent for food sample pretreatment, which can rapidly enrich compounds similar in structure to fluoroquinolones.

研究领域: 食品科学 · 分析化学 · 纳米材料科学
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Foods · 2025 ·Vol. 14 ·期 3 ·538 · IF 5.1

Self-Enhanced Near-Infrared Copper Nanoscale Electrochemiluminescence Probe for the Sensitive Detection of Ciprofloxacin in Foods

Jie Wu,Yuanjie Qin,Xiaoxin Mei,Lin Cai,Wen Hao,Guozhen Fang

Ciprofloxacin (CIP), a widely used broad-spectrum antibiotic, poses a serious threat to human health and environmental safety due to its residues. The complementary monomers molecularly imprinted electrochemiluminescence sensor (MIECLS) based on a polyvinylpyrrolidone-functionalized copper nanowires (CuNWs@PVP) luminescent probe was constructed for the ultra-sensitive detection of CIP. CuNWs with low cost and high conductivity exhibited near-infrared electrochemiluminescence (NIR ECL) properties, yet their self-aggregation and oxidation led to a weakened emission phenomenon. PVP with solvent affinity and large skeleton was in situ attached to CuNWs surface to avoid CuNWs sedimentation and aggregation, and self-enhanced ECL signals were achieved. The bifunctional monomers molecularly imprinted polymer (MIP) possessed complementary active centers that increased their affinity with CIP, enhancing the accurate and sensitive detection of the target substances. The linear range of CIP using MIECLS was 5.00 × 10 −9 –5.00 × 10 −5 mol L −1 with a low limit of detection (LOD) of 2.59 × 10 −9 mol L −1 , while the recovery rates of CIP in the spiking recovery experiment were 84.39% to 92.48%. The combination of bifunctional monomer MIP and NIR copper-based nano-luminescent probe provides a new method for the detection of CIP in food.

研究领域: 分析化学 · 食品安全 · 生物传感技术
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TALANTA · 2025 · IF 6.1

Ratiometric fluorescent sensor CQDx@Co/Mn-MOF for rapid and sensitive detection of quinolone antibiotics

Yin-Xia Sun,Xue Bai,Ai-Ping Luo,Yu Sun,Zhe-Peng Deng,Wan-Hong Sun,Wen-Yu Han

Quinolone antibiotics pose a threat to health and the environment due to their difficulty in decomposition and misuse. A novel fluorescence composite material CQD x @Co/Mn-MOF has been developed, which uses cobalt (Co) and manganese (Mn) as metal centers and 1,3,5-triazobenzene as organic ligands. Meaningfully, CQD x @Co/Mn-MOF can be designed as a ratiometric fluorescence sensor for detecting quinolone antibiotics, especially norfloxacin (NFX). In a series of CQD x @Co/Mn-MOF, CQD 6μL @Co/Mn-MOF sensor exhibits good linearity within the NFX concentration range of 1–4 × 10 −5  M, with a detection limit of 0.70 μM. Compared with Co/Mn-MOF, introducing CQDs significantly reduces the detection limit from 3.50 μM to 0.70 μM and increases the detection sensitivity by five times. The CQD 6μL @Co/Mn-MOF sensor exhibits fast response time (2 s), high selectivity and sensitivity to NFX, making it an ideal ratiometric fluorescent sensor for the detection of these antibiotics. Based on its excellent detection performance, the sensor was further applied to the quantitative determination of NFX in chicken, beef and honey samples and satisfactory results were obtained with recoveries ranging from 97.51 % to 108.60 %. In addition, based on CQD 6μL @Co/Mn-MOF test strips, convenient and real-time detection of quinolone antibiotics has been achieved. In conclusion, the CQD 6μL @Co/Mn-MOF ratiometric fluorescent sensor provides a reliable, sensitive and efficient analytical method for the detection and evaluation of trace NFX in food, which is of great significance for ensuring food safety and public health.

研究领域: 分析化学 · 食品安全 · 环境科学
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Analytical Methods · 2024 · IF 2.7

Quantum dot-based biomimetic fluorescence immunoassays for enrofloxacin detection in animal-derived foods

Gaoshuang Hu,Ziyang Liu,Yiqin Zhang,Tao Zhao,Zhuqing Xing,Shan Gao,Jianxiong Hao

Long-term consumption of foods with excessive enrofloxacin (ENRO) residues may cause the accumulation of ENRO in the human body, thus damaging human health. In this study, quantum dot-based biomimetic fluorescence immunoassays were used for enrofloxacin detection in food of animal origin. Under the most suitable conditions, the detection limit (IC15) of the method in standard solution was 0.13 ± 0.02 ng L−1 and the sensitivity (IC50) was 0.13 ± 0.18 μg L−1. The recoveries for ENRO from four fortified food samples, including chicken, eggs, shrimp, and milk, ranged from 85.74% to 114.19% and the coefficients of variation were 0.01–18.09%. The established method shows good agreement with the results obtained using commercial ELISA kits, with a correlation coefficient of 0.997. The proposed method shows the advantages of high sensitivity, specificity and wide detection range. It can be used as an alternative method for the rapid and sensitive detection of ENRO in food of animal origin.

研究领域: 食品科学 · 分析化学 · 生物技术 · 兽医学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Tuning the heterostructure improves the catalytic activity of recyclable nanozymes for efficient absorption and degradation of norfloxacin-contaminated water

Yanning Zheng,Dankui Liao,Bimei Xie,Jinlei Sun,Jianhua Sun,Zhangfa Tong,Guangzhi Zhou

Effective removal of antibiotic residues from water is crucial for maintaining balance and cleanliness in the ecological environment. To achieve this, we conducted a study on the development of a highly efficient catalyst from the in-situ growth of Fe 3 O 4 nanoparticles on nitrogen-doped hollow porous carbon spheres (Fe 3 O 4 @N-HollCS). We controlled the in-situ growth time to optimize its performance. Material characterization and theoretical calculations revealed that the improved catalytic performance of Fe 3 O 4 @N-HollCS is due to electron transfer from the graphitic-N in N-HollCS to the catalytic interface of Fe 3 O 4 nanoparticles. Fe 3 O 4 @N-HollCS, with an ordered mesoporous structure and high specific surface area, had remarkable adsorption capacity for NOR antibiotics, with an enrichment efficiency exceeding 60% within 10 min. Moreover, the Fe 3 O 4 @N-HollCS degraded more than 90% of fluoroquinolone antibiotics, especially norfloxacin (NOR), which was eliminated within 60 min. The Fe 3 O 4 @N-HollCS also exhibited stable catalytic recycling ability within 10 magnetic separations. Fukui function predicted the sensitive sites of NOR, and we proposed potential degradation pathways. Ecological structure activity relationship model evaluation showed that the intermediate produced by Fe 3 O 4 @N-HollCS degradation of NOR has low levels of ecotoxicity. Overall, Fe 3 O 4 @N-HollCS catalysts have great potential for antibiotic wastewater treatment.

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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2026 · IF 9.6

Hybrid Ag/Au nanocavity arrays for ultrasensitive SERS discrimination of molecular isomers via machine learning

Zhiming Chen,Jiabin Chen,Haoming Bao,Kaitao Liu,Pan Zeng,Fan Yang,Wei Cao,Dongqi Yang,An Cao,Tao Zhang,Yue Li

Surface-enhanced Raman scattering (SERS) has been one of the efficient strategies for trace molecular analysis, but the traditional substrates with sharp tips cannot effectively detecting the molecular isomers. Here, we develop a facile way to fabricate large-area, reproducible Ag/Au nanocavity arrays by the combination of microsphere-templated soft lithography and self-assembly. Compared to the flat and convex substrate, the Ag/Au units arranged on the concave surface exhibit a high-density of hotspots via spatial light confinement and multi-reflection-enhanced electromagnetic coupling, which enables highly sensitive detection of probe molecules down to10 −12 M. Moreover, by integrating machine learning algorithms, the test set shows a coefficient of determination (R 2 ) of 0.9896, achieving advanced training performance for classifying four structurally analogous quinolone antibiotics (ciprofloxacin, enrofloxacin, danofloxacin, and enoxacin) with a quantitative prediction of 10 −10  M. This work demonstrates a robust pathway for the controllable fabrication of high-performance SERS substrates for the development of intelligent, quantitative, and on-site sensing platforms in complex practical scenarios. Download: Download high-res image (179KB) Download: Download full-size image

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