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FOOD CHEMISTRY · 2025 · IF 9.8

Impact of casein binding on thermal degradation of oxytetracycline: kinetics, products, and their toxicity

Aying Wen,Kexin Chi,Yuhang Du,Shaofeng Yuan,Hang Yu,Yahui Guo,Weirong Yao

This work systematically investigated the effect of casein on the thermal transformation behavior of oxytetracycline (OTC). Fluorescence quenching and isothermal titration calorimetry experiments confirmed that OTC binds spontaneously to casein via non-covalent interactions. The -N(CH 3 ) 2 group in OTC was identified as the primary binding site. Casein-bound OTC was prepared using a combination of dialysis and ultrafiltration. During thermal treatment, the degradation of free OTC followed zero-order kinetics, whereas casein-bound OTC adhered to first-order kinetics. Seven identical thermal transformation products were identified, but the quantities of these products varied significantly depending on the existing form of OTC molecule. The binding of casein weakened the reactivity of the -N(CH 3 ) 2 group while enhancing the reactivity of degradation sites on the adjacent ring, resulting in decreased production of three lower-toxic products and increased production of four higher-toxicity products. Cytotoxicity assays revealed that heating increased the overall toxicity of OTC, particularly in its bound form.

CAS / MDL: 7789-20-0 2058-46-0
研究领域: 食品科学 · 毒理学
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RSC Advances · 2017 ·Vol. 7 ·期 21 ·12827-12834 · IF 3.108

A novel fluorescent sensor based on sulfur and nitrogen co-doped carbon dots with excellent stability for selective detection of doxycycline in raw milk

Jinping Song,Jing Li,Ziying Guo,Wen Liu,Qi Ma,Feng Feng,Chuan Dong

Casein was employed for the first time as a green carbon source to prepare water-soluble sulfur and nitrogen co-doped carbon dots (S,N-CDs). The as-synthesized S,N-CDs were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, UV-Vis absorption spectroscopy, and fluorescence spectroscopy. Results showed that the as-prepared S,N-CDs had excellent stabilities under various external conditions, such as high ionic strength, different pH levels, UV light irradiation, and long storage duration. More importantly, we found that doxycycline (Dox) could result in an effective fluorescence quenching of S,N-CDs via a static quenching process. Thus, a sensitive and selective sensing system for Dox detection was developed. The linear range was 1.0 × 10−7 M to 1.0 × 10−4 M, and the detection limit was 25 nm. Furthermore, the proposed sensing system successfully detected Dox in raw milk samples. This research will demonstrate the feasibility and potential applications of carbon nanomaterials in food and medical monitoring fields.

研究领域: 食品科学 · 分析化学 · 纳米材料科学
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ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH · 2016 ·Vol. 23 ·期 14 ·13822-13831 · IF 2.76

Dissipation kinetics of oxytetracycline, tetracycline, and chlortetracycline residues in soil

Li Yuanzhu,Wang Haijiao,Liu Xiaoxia,Zhao Guangyu,Sun Ying

The dissipation of different residual states of tetracycline antibiotics (TCs) including oxytetracycline (OTC), tetracycline (TC), and chlortetracycline (CTC) laboratory microcosm systems was investigated in this study. The residues were fractionated by stepwise extractions into aqueous state (KCl solution extracts), organic state (MeOH extracts), residual state I (citric acid-sodium citrate buffer and ethyl acetate extracts) and residual state II (acetonitrile-EDTA-McIlvaine buffer extracts) for accurate evaluation of TCs pollution. The antibiotics in the aqueous state were hardly detected, whereas the antibiotics in the organic state dissipated relatively fast (not detectable within 15 days after application) and followed simple first-order kinetics (SFOK) ( R 2 from 0.929 to 0.990). While first-order double-exponential decay model (FODED) ( R 2 from 0.840 to 0.999) and availability-adjusted first-order model (AAFO) ( R 2 from 0.939 to 0.999) had a better fit on the dissipation of both residue state I and II than SFOK. TCs in these states were likely sequestered into a dormant undegradable phase since no degradation product was detected during the entire experiment. In addition, the overall 50 % dissipation values (i.e., stability) of the three TCs were OTC > TC > CTC. The TCs tend to dissipate faster in the high water content and organic matter soil.

研究领域: 环境科学 · 微生物学 · 药理学
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JOURNAL OF HAZARDOUS MATERIALS · 2018 · IF 6.434

Simultaneous removal of tetracycline and oxytetracycline antibiotics from wastewater using a ZIF-8 metal organic-framework

Na Li,Long Zhou,Xiaoying Jin,Gary Owens,Zuliang Chen

In this paper, a Zeolite Imidazole Framework-8 (ZIF-8), was investigated for the removal of a mixture of two common antibiotics, tetracycline (TC) and oxytetracycline hydrochloride (OTC). Batch experiments showed that 90.7% of TC and 82.5% of OTC were simultaneously removed using ZIF-8. The maximum adsorption capacities for TC and OTC were 303.0 and 312.5 mg g −1 , respectively. For both antibiotics’ adsorption followed pseudo-second-order kinetics and best fit the Langmuir adsorption model with R 2 of 0.963 and 0.981, for TC and OTC at 303 K, respectively. The relatively large specific surface area of ZIF-8 (1158.2 m 2  g -1 ) combined with scanning electron microscopy (SEM) and transmission electron microscopy (TEM) indicated that both antibiotics were adsorbed on to the surface of ZIF-8. X-ray powder diffraction (XRD) and Fourier Transform Infrared (FTIR) spectroscopy both indicated the presence of benzene ring structures, associated with both pollutants, on ZIF-8 after reaction; which confirmed adsorption was occurring. XPS also showed the presence of C O double bonds on the surface of ZIF-8 indicating the presence of antibiotics. The adsorption mechanism most likely involved π-π interactions between the conjugated groups in TC/OTC and the imidazole rings of ZIF-8.

CAS / MDL: 693-98-1 2058-46-0
研究领域: 环境科学 · 材料科学 · 生物学
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WATER RESEARCH · 2023 · IF 12.8

Biosurfactant-affected mobility of oxytetracycline and its variations with surface chemical heterogeneity in saturated porous media

Yinhan Jin,Jiuyan Chen,Qiang Zhang,Usman Farooq,Taotao Lu,Bin Wang,Zhichong Qi,Weifeng Chen

Herein, the influences of rhamnolipid (a typical biosurfactant) on oxytetracycline (OTC) transport in the porous media and their variations with the surface heterogeneities of the media (uncoated sand, goethite (Goe)-, and humic acid (HA)-coated sands) were explored. Compared to uncoated sand, goethite and HA coatings suppressed OTC mobility by increasing deposition sites. Interestingly, rhamnolipid-affected OTC transport strongly depended on the chemical heterogeneities of aquifers and biosurfactant concentrations. Concretely, adding rhamnolipid (1–3 mg/L) inhibited OTC mobility through sand columns because of the bridging effect of biosurfactant between sand and OTC. Unexpectedly, rhamnolipid of 10 mg/L did not further improve the inhibition of OTC transport owing to the fact that the deposition capacity of rhamnolipid reached its maximum. OTC mobility in Goe-coated sand columns was inhibited by 1 mg/L rhamnolipid. However, the inhibitory effect decreased with the increasing rhamnolipid concentration (3 mg/L) and exhibited a promoted effect at 10 mg/L rhamnolipid. This surprising observation was that the increased rhamnolipid molecules gradually occupied the favorable deposition sites (i.e., the positively charged sites). In comparison, rhamnolipid facilitated OTC transport in the HA-coated sand column. The promotion effects positively correlated with rhamnolipid concentrations because of the high electrostatic repulsion and deposition site competition induced by the deposited rhamnolipid. Another interesting phenomenon was that rhamnolipid's enhanced or inhibitory effects on OTC transport declined with the increasing solution pH because of the decreased rhamnolipid deposition on porous media surfaces. These findings benefit our understanding of the environmental behaviors of antibiotics in complex soil-water systems containing biosurfactants.

CAS / MDL: 6153-64-6
研究领域: 环境科学 · 土壤学
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JOURNAL OF ENVIRONMENTAL MANAGEMENT · 2024 · IF 8

The role of magnesium ion in the interactions between humic acid and tetracycline in solution

Shinan Wang,Yue Yuan,Erping Bi

Coexisting tetracycline (TC), dissolved organic matter (DOM), and metal cations in aqueous environments might form complexes and consequently affect the environmental fate of TC. In this study, the interactions among coexisting humic acid (HA), TC, and Mg(II) in solutions were investigated by equilibrium dialysis batch experiments and nuclear magnetic resonance hydrogen spectroscopy ( 1 H NMR) characterization. In the binary systems, the dimethylamine (4Me 2 NH + ) functional group on the A-ring of TC bound to the oxygen-containing functional groups of HA via hydrogen bond. The solution pH affected the agglomeration morphology and dissociation of the oxygen-containing functional groups of HA as well as protonation and spatial conformation of TC, which in turn affected the HA-TC interactions. The complexation sites and ratio of Mg(II) on TC affect the binding mode in the ternary system. When the TC-Mg(II) complexation ratio is 1:1, the B, C, and D rings of TC preferentially complex with Mg(II), resulting in the change of TC from an extended to a twisted conformation. At this time, Mg(II) had a weaker inhibitory effect on binding affinity between HA and TC. When the complexation ratio was 1:2, the second Mg(II) complexation deactivated the 4Me 2 NH  +  on the A ring and further stabilized TC twisted conformation, resulting in a stronger inhibitory effect on the binding of TC to HA. Under acidic conditions, the solution pH mainly caused the difficulty in forming TC-Mg(II) complexes. The inhibitory effect of Mg(II) on the binding between HA and TC is weaker than that under alkaline conditions.

CAS / MDL: 64-75-5
研究领域: 环境科学 · 化学
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MOLECULES · 2024 ·Vol. 29 ·期 3 ·659 · IF 4.2

The Degradation of Aqueous Oxytetracycline by an O3/CaO2 System in the Presence of HCO3−: Performance, Mechanism, Degradation Pathways, and Toxicity Evaluation

Zedian Li,Liangrui Xiang,Shijia Pan,Dahai Zhu,Shen Li,He Guo

This research constructed a novel O3/CaO2/HCO3−system to degrade antibiotic oxytetracycline (OTC) in water. The results indicated that CaO2andHCO3−addition could promote OTC degradation in an O3system. There is an optimal dosage of CaO2(0.05 g/L) andHCO3−(2.25 mmol/L) that promotes OTC degradation. After 30 min of treatment, approximately 91.5% of the OTC molecules were eliminated in the O3/CaO2/HCO3−system. A higher O3concentration, alkaline condition, and lower OTC concentration were conducive to OTC decomposition. Active substances including ·OH,1O2,·O2−, and ·HCO3−play certain roles in OTC degradation. The production of ·OH followed the order: O3/CaO2/HCO3−> O3/CaO2> O3. Compared to the sole O3system, TOC and COD were easier to remove in the O3/CaO2/HCO3−system. Based on DFT and LC-MS, active species dominant in the degradation pathways of OTC were proposed. Then, an evaluation of the toxic changes in intermediates during OTC degradation was carried out. The feasibility of O3/CaO2/HCO3−for the treatment of other substances, such as bisphenol A, tetracycline, and actual wastewater, was investigated. Finally, the energy efficiency of the O3/CaO2/HCO3−system was calculated and compared with other mainstream processes of OTC degradation. The O3/CaO2/HCO3−system may be considered as an efficient and economical approach for antibiotic destruction.

研究领域: 环境科学 · 化学工程 · 毒理学
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Water · 2021 ·Vol. 13 ·期 24 ·3497 · IF 3.103

The Effect of Exogenous Oxytetracycline on High-Temperature Anaerobic Digestion of Elements in Swine Wastewater

Zhongda Hu,Zijing Fan,Qixuan Song,Rabia Khatoon,Mei Zhang,Ning Wang,Xingzhang Luo

Tetracycline antibiotics (TCs) are a common type of antibiotic found in swine wastewater. Oxytetracycline (OTC) is a significant type of TC. This study mainly examined the influence of OTC on high-temperature anaerobic digestion by adding OTC to collections of swine wastewater at different times during the digestion process. The results showed that high-temperature anaerobic digestion was suitable for the removal of TCs, with an 87% OTC removal efficiency achieved by day 20. Additionally, OTC added from external sources was found to inhibit the chlortetracycline degradation process and affect the first-order degradation kinetic model of TCs. Complexation reactions were the main ways in which OTC affected the heavy metal content of the water. The exogenous addition of OTC was found to inhibit the activity of some digester microbial strains, reduce the proportion of dominant strains, such asMBA03, and kill certain specific strains. This performance alteration was most obvious when OTC was added in the middle of the reaction.Keywords:swine wastewater;high-temperature anaerobic digestion;tetracycline antibiotics;oxytetracycline

研究领域: 环境工程 · 微生物学
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CHEMOSPHERE · 2022 · IF 8.943

Surfactants-mediated the enhanced mobility of tetracycline in saturated porous media and its variation with aqueous chemistry

Fei Wang,Jiuyan Chen,Yalei Xu,Usman Farooq,Taotao Lu,Weifeng Chen,Xinhai Wang,Zhichong Qi

Knowledge of the mobility of tetracycline (TC) antibiotics in porous media is critical to understand their potential environmental influences. The transport characteristics of TC in sand columns with three different surfactants, including Tween 80, sodium dodecylbenzene sulfonate (SDBS), and didodecyldimethylammonium bromide (DDAB) under various conditions were investigated in this study. Results demonstrated that all surfactants enhanced TC transport under neutral conditions (10 mM NaCl at pH 7.0). The observation was attributed mostly to deposition site competition, higher electrostatic repulsion between TC molecules and sand grains, steric hindrance, and the increase of TC hydrophilicity. Furthermore, the order of the transport-enhancement effects was generally observed as follows: DDAB > SDBS > Tween 80. The trend was controlled by the variation in the physicochemical properties of surfactants. It was noticed that the presence of Cu 2+ (a model divalent cation) in the background solution, the cation-bridging contributed to the promotion effects of DDAB or Tween 80 on TC mobility. Interestingly, SDBS considerably suppressed TC transport due to the precipitation of SDBS–Cu 2+ complexes onto sand surfaces. Moreover, the enhancement order of surfactants at pH 5.0 was similar to that pH 7.0. However, DDAB could inhibit TC transport in sand columns at pH 9.0, which were mainly caused by the decrease of electrostatic repulsion and the hydrophobicity induced by the binding cationic surfactant. Findings from this work provide novel insight into involvement of surfactants in antibiotic transport behaviors in the subsurface environment.

研究领域: 环境科学 · 土壤学
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CHEMOSPHERE · 2023 · IF 8.8

Unveiling the traits of dry and wet pre-magnetized zero-valent iron-activated peroxymonosulfate: Degradation of oxytetracycline

Yang Wu,Jia-wen Bai,Jing-ying Zhu,Zhi-hao Li,Yi-fan Shao,Qing-qing Xiao

It has been previously reported that pre-magnetization could enhance the efficacy of zero-valent iron (ZVI) in removing contaminants. However, little is known about the effects and persistence of different magnetization methods on pre-magnetized ZVI (Pre-ZVI) when used in advanced oxidation processes (AOPs). Gaining a comprehensive understanding of the durability of various pre-magnetization methods in enhancing the removal efficiency of different pollutants will significantly impact the widespread utilization of Pre-ZVI in practical engineering. Herein, we investigated the efficiency of dry and wet Pre-ZVI-activated peroxymonosulfate (PMS) in eliminating oxytetracycline (OTC) and evaluated the durability of Pre-ZVI. Additionally, we examined several factors that influence the degradation process's efficiency. Our results found that the reaction constant k values corresponding to the dry Pre-ZVI/PMS system at the pH values of 3, 7, and 9 varied from approximately 0.0384, 0.0331, and 0.0349 (day 1) to roughly 0.0297, 0.0278, and 0.0314 (day 30), respectively. Meanwhile, the wet Pre-ZVI/PMS system exhibited k values ranging from approximately 0.0392, 0.0349, and 0.0374 (day 1) to roughly 0.0380, 0.0291, and 0.0322 (day 30), respectively. Moreover, we proposed four OTC degradation pathways using LC-MS/MS and density functional theory calculations. The toxicity of the degradation products was assessed using the ecological structure activity relationship and the toxicity estimation software tool . Overall, this study provides insights into the application of Pre-ZVI/PMS that can be selectively used to eliminate tetracycline antibiotics from water.

CAS / MDL: 7439-89-6
研究领域: 环境科学 · 化学工程
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SEPARATION AND PURIFICATION TECHNOLOGY · 2021 · IF 7.312

Multiple production of highly active particles for oxytetracycline degradation in a large volume strong ionization dielectric barrier discharge system: Performance and degradation pathways

Rongjie Yi,He Guo,Huijuan Wang,Daolin Du,Qi Zhang,Chengwu Yi

In this study, the degradation of oxytetracycline (OTC) in aqueous solution by humid O 2 strong ionization dielectric barrier discharge (DBD) with a 2.2 t/h large volume was investigated. Based on the electron spin resonance (ESR) results and the detection of O 3 and H 2 O 2 concentrations, the existence of high concentrations of hydroxyl radicals ( OH) (0.85 mmol/L), O 3 (14.2 mg/L), and H 2 O 2 (63.3 mg/L) produced via humid O 2 strong ionization discharge DBD was verified. In addition, the effects of the reaction conditions, including the input voltage (2.1–3.8 kV), the initial pH value (3.1–10.3), the OH inhibitors, the inorganic ions, and the natural organic matter (NOM), on the OTC degradation efficiency were measured, and the optimal parameters were determined based on the results of single factor experiments. The results showed that the OTC removal efficiency and the kinetic constant can be increased by enhancing the input voltage, and about 93.7% of the OTC was removed at 3.8 kV and in a neutral pH (6.9) solution. The presence of OH inhibitors, inorganic ions and NOM in the solution can reduce the OTC removal efficiency and the kinetic constant. Moreover, compared to dry O 2 strong ionization dielectric DBD, the active particle yield ( OH, O 3 , H 2 O 2 ), the kinetic constant, and the TOC removal by humid O 2 strong ionization discharge DBD were better. Subsequently, five main by-products were identified and four different transformation pathways, including hydroxylation (+16 Da), deamidation (−46 Da), demethylation (−14 Da), and dehydration (−18 Da), were observed. In addition, the acute toxicity of the intermediates was reduced, but the mutagenicity of the biotoxicity was positive.

研究领域: 环境科学 · 化学工程
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Green Processing and Synthesis · 2023 ·Vol. 12 ·期 1 · IF 4.3

Preparation of Zr-MOFs for the adsorption of doxycycline hydrochloride from wastewater

Qinhui Ren,Yufu Ma,Fuhua Wei,Lan Qin,Hongliang Chen,Zhao Liang,Siyuan Wang

Zr-metal-organic frameworks (Zr-MOFs) were prepared by a solvothermal method and characterized by X-ray diffraction, scanning electron microscopy, and thermogravimetry. Zr-MOFs were used to remove doxycycline hydrochloride (DOC) from wastewater. According to the experimental results, the maximum adsorption capacity of DOC by Zr-MOFs within 5 h was 148.7 mg·g −1 . From the pseudo-second-order kinetics model, all R 2 values were greater than 0.99, which proved that the adsorption of DOC by Zr-MOFs was consistent with practice. According to the Freundlich isotherm model, the adsorption of DOC by Zr-MOFs proceeded via multilayer adsorption. The aforementioned results show that Zr-MOFs have good application prospects for removing DOC from wastewater.

研究领域: 环境科学 · 材料科学
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