Tetracycline selective electrode based on molecularly imprinted polymer particles

<正>Tetracycline selective electrode using molecularly imprinted polymer particles as quasi-ionophore was constructed the first time, and its performance was carefully characterized.Due to the specific recognition of tetracycline by the particles,the selectivity coefficients for routine interferences were less than 10~(-4).Benefited from the absence of tetracycline in the sensitive membrane and the optimized composition of the inner filling solution,the limit of detection of the electrode was reduced to about 2.5×10~(-8) mol/ L.It exhibited a good electrode slope 57.6 mV/decade near the theoretical Nernstian one,with a wide linear working range from 6.0×10~(-8) to 1.0×10~(-3) mol/L.The fabricated electrode should be used in pH 2-4,response time of which was less than 200 s when the concentration of tetracycline was higher than 1.0×10~(-6) mol/L and no more than 30 min at the concentration of 1.0×10~(-8) mol/L.     

Sonocatalytic degradation of tetracycline hydrochloride with CoFe2O4/g-C3N4 composite

In this work, different mass percent ratios of CoFe₂O₄ coupled g-C₃N₄ (w%-CoFe₂O₄/g-C₃N₄, CFO/CN) nanocomposites were integrated through a hydrothermal process for the sonocatalytic eradication of tetracycline hydrochloride (TCH) from aqueous media. The prepared sonocatalysts were subjected to various techniques to investigate their morphology, crystallinity, ultrasound wave capturing activity and charge conductivity. From the investigated activity of the composite materials, it has been registered that the best sonocatalytic degradation efficiency of 26.71 % in 10 min was delivered when the amount of CoFe₂O₄ was 25% in the nanocomposite. The delivered efficiency was higher than that of bare CoFe₂O₄ and g-C₃N₄. This enriched sonocatalytic efficiency was credited to the accelerated charge transfer and separation of e⁻-h⁺ pair through the S-scheme heterojunctional interface. The trapping experiments confirmed that all the three species i.e. ^•OH, h⁺ and ^•O₂⁻ were involved in the eradication of antibiotics. A strong interaction was shown up between CoFe₂O₄ and g-C₃N₄ in the FTIR study to support charge transfer as confirmed from the photoluminescence and photocurrent analysis of the samples. This work will provide an easy approach for fabricating highly efficient low-cost magnetic sonocatalysts for the eradication of hazardous materials present in our environment.     

Fe3O4@MIL-100(Fe) modified ZnS nanoparticles with enhanced sonocatalytic degradation of tetracycline antibiotic in water

Sonocatalysis has attracted excellent research attention to eradicate hazardous pollutants from the environment effectively. This work synthesised an organic/inorganic hybrid composite catalyst by coupling Fe₃O₄@MIL-100(Fe) (FM) with ZnS nanoparticles using the solvothermal evaporation method. Remarkably, the composite material delivered significantly enhanced sonocatalytic efficiency for removing tetracycline (TC) antibiotics in the presence of H₂O₂ compared to bare ZnS nanoparticles. By adjusting different parameters such as TC concentration, catalyst dosage and H₂O₂ amount, the optimized composite (20 %Fe₃O₄@MIL-100(Fe)/ZnS) removed 78.25% antibiotic in 20 min at the cost of 1 mL of H₂O₂. These much superior activities are attributed to the efficient interface contact, effective charge transfer, accelerated transport capabilities and strong redox potential for the superior acoustic catalytic performance of FM/ZnS composite systems. Based on various characterization, free radical capture experiments and energy band structures, we proposed a mechanism for the sonocatalytic degradation of tetracycline based on S-scheme heterojunctions and Fenton like reactions. This work will provide an important reference for developing ZnS-based nanomaterials to study sonodegradation of pollutants.     

电化学还原氧化石墨烯用于四环素电催化检测

四环素(TTC)因其广泛的抗菌性和低生产成本等特点而成为应用最广泛的兽医药物. TTC的大量使用不可避免地导致其进入地表水、地下水和污水处理厂.迄今,已有许多方法用于TTC检测,包括免疫测定法、微生物检测法和化学-物理法等.然而,这些方法费用高,耗时长或需要复杂的样品预处理过程,不适合现场测量或常规分析.电化学分析法具有操作简单、成本低廉、选择性和灵敏度较高、易实现在线检测等特点,在检测领域具有重要优势.石墨烯在电化学传感器领域表现出优越的应用性能,但有关石墨烯材料应用于电分析和电催化方面的报道仍然有限.石墨烯的前驱体氧化石墨烯(GO)片层底面上具有各种类型的含氧官能团和层状边缘,导致其绝缘并具有很多缺陷,使GO包含了sp2和sp3杂化碳原子,为GO提供了独特的具有化学功能的异构电子结构.通过对GO进行还原,可以生成新的sp2域或者改变含氧官能团的数量和类型,从而为GO提供更多的特殊性质.研究表明,电化学还原是一种绿色快速的还原方法,可以控制GO的还原程度和还原过程.本文利用电化学还原法来调整GO表面的官能团和缺陷度,利用在–0.8 V还原电位下得到的电化学还原氧化石墨烯(ERGO-0.8V)修饰玻碳电极(GC)为工作电极(GC/ERGO-0.8V),采用循环伏安法对溶解在pH=3的缓冲溶液中的TTC进行电化学检测,发现ERGO-0.8V对TTC具有电催化性能.利用红外光谱(FT-IR)、X射线光电子能谱(XPS)和拉曼光谱对ERGO-0.8V, ERGO-1.2V, GO及化学还原得到的石墨烯(CRGO)表面官能团和缺陷程度进行了表征,考察了TTC在ERGO-0.8V/GC上的电化学行为,对其电催化还原机理进行了推测.结果表明,与GO, ERGO-1.2V及CRGO修饰电极相比, GC/ERGO-0.8V修饰电极的催化还原峰在0–0.5 V,对TTC表现出独特的电催化性能, GC/ERGO-0.8V电极对浓度为0.1–120 mg/L的TTC溶液具有良好的检测性能,在不同浓度范围内其氧化峰峰电流与峰电位的线性关系不同. FT-IR和XPS结果显示,在–0.8 V还原电位下得到的ERGO-0.8V,其官能团类型和数量发生变化,但仍存在大量官能团,主要是羧基、羟基和环氧基.同时,拉曼表征显示ERGO-0.8V的缺陷密度增大,同时新生成的sp2域减小而使得ERGO的sp2域减小.对比GO等其他材料的表征结果推测,官能团变化是影响ERGO独特电催化性质的主要因素,除此之外还有材料的缺陷度和sp2域.推测GC/ERGO-0.8V修饰电极对TTC可能的催化机理为： TTC在GC/ERGO电极上的还原与氢醌和醌之间的转换有关;而对于ERGO,则可能对应于羧基和羟基之间的转化.然而,同样具有羧基和羟基的ERGO-1.2V则对TTC没有产生电催化作用.其原因可能是在–0.8到–1.2 V还原电位下,形成的羧基位于石墨烯片层内部,而片层内的电子传递较慢.     

Development and validation of polymerized high internal phase emulsion monoliths coupled with HPLC and fluorescence detection for the determination of trace tetracycline antibiotics in environmental water samples

A polymerized high internal phase emulsion monolith was used as a novel sorbent for solid‐phase extraction coupled with high‐performance liquid chromatography and fluorescence detection for the determination of oxytetracycline, tetracycline, doxycycline, and chlorotetracycline in environmental water samples. The polymerized high internal phase emulsion monolithic column was prepared by the in situ polymerization of the continuous phase of a high internal phase emulsion containing glycidyl methacrylate, styrene, and divinylbenzene in pipette tips, and then functionalized with iminodiacetic acid. The resulting monolith exhibited highly interconnected porosity and large surface areas, making it an excellent candidate as an solid‐phase extraction sorbent for the enrichment of trace tetracycline antibiotics. Several factors affecting the extraction performance of polymerized high internal phase emulsion monoliths, including the pH of sample solution, the eluting solvents, the sample loading flow rate and volume, were investigated, respectively. Under the optimized conditions, the mean recoveries of oxytetracycline, tetracycline, doxycycline, and chlorotetracycline spiked in pond and farm wastewater samples ranged from 78.1 to 119.3% with relative standard deviation less than 15%. The detection limits (S/N = 3) of the proposed method were in the range of 51–137 pg/mL. This study demonstrated that the monolithic polymerized high internal phase emulsion would be promising solid‐phase extraction sorbents in the extraction and proconcentration of trace analytes from complex samples.     

Bismuth Film Electrode for Analysis of Tetracycline in Flow Injection System

A bismuth film was prepared on glassy carbon electrode (GCE) and used in a flow injection amperometric system to analyze tetracycline. Bismuth film electrode (BiFE) preparation and flow injection amperometric parameters were optimized. System performances of BiFE were compared to GCE. BiFE was validated with three different lots of real sample, 250 mg tetracycline capsules, the results showed good agreement, i.e., between 240 and 260 mg per capsule. Good relative recoveries were also obtained in the range of 86–106%.     

Preparation of Ag3PO4/CoWO4 S-scheme heterojunction and study on sonocatalytic degradation of tetracycline

In this study, 0.6Ag₃PO₄/CoWO₄ composites were synthesized by hydrothermal method. The prepared materials were systematically characterized by techniques of scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffractometer (XRD), X-ray photoelectron spectroscopy (XPS), N₂ adsorption/desorption, and UV–vis diffuse reflectance spectrum (DRS). Furthermore, the sonocatalytic degradation performance of 0.6Ag₃PO₄/CoWO₄ composites towards tetracycline (TC) was investigated under ultrasonic radiation. The results showed that, combined with potassium persulfate (K₂S₂O₈), the 0.6Ag₃PO₄/CoWO₄ composites achieved a high sonocatalytic degradation efficiency of 97.89 % within 10 min, which was much better than bare Ag₃PO₄ or CoWO₄. By measuring the electrochemical properties, it was proposed that the degradation mechanism of 0.6Ag₃PO₄/CoWO₄ is the formation of S-scheme heterojunction, which increases the separation efficiency of electron-hole pairs (e^--h⁺) and generates more electrons and holes, thereby enhancing the degradation activity. The scavenger experiments confirmed that hole (h⁺) was the primary active substance in degrading TC, and free radicals (OH) and superoxide anion radical (O₂^–) were auxiliary active substances. The results indicated that 0.6Ag₃PO₄/CoWO₄ nanocomposites could be used as an efficient and reliable sonocatalyst for wastewater treatment.     

Biotin-avidin mediated competitive enzyme-linked immunosorbent assay to detect residues of tetracyclines in milk

Tetracycline (TC) antibiotics are widely used for prevention and control of disease because they inhibit the growth of bacteria. However, the presence of TC antibiotics residues in food causes harmful effects on consumer's health such as allergic reactions, liver damage and gastrointestinal disturbance, so that many countries have set MRLs (maximum residue levels). Therefore, it is necessary to detect tetracycline residues, to develop suitable analytical techniques to be used as routine screens and field detection.A new approach to the biotin-avidin mediated competitive ELISA is developed to determine tetracycline residues in milk. After optimization, the LOD and LOQ were 1.0 × 10^− 10 M (0.048 μg/L) and 1.0 × 10^− 9 M, respectively, and the working range from 3.16 × 10^− 10 M to 3.16 × 10^− 7 M toward TC in milk. No cross-reactivity was observed with the structurally similar compounds; chlortetracycline (13.7%), oxytetracycline (10%) and doxytetracycline (< 1%). Additionally percent recoveries of TC spiked in milk were quite satisfactory (∼ 90%). Comparing our results obtained in this work with others, it shows with the capability to detect TC ranging in MRLs (100 μg/L in milk) sufficiently with highly sensitivity in milk, and with simple pre-treatment. In addition, this method can apply to developing useful ELISA test kit for determination of TCs in milk.     

Synthesis of molecular imprinted polymer modified TiO2 nanotube array electrode and their photoelectrocatalytic activity

A tetracycline hydrochloride (TC) molecularly imprinted polymer (MIP) modified TiO₂ nanotube array electrode was prepared via surface molecular imprinting. Its surface was structured with surface voids and the nanotubes were open at top end with an average diameter of approximately 50 nm. The MIP-modified TiO₂ nanotube array with anatase phase was identified by XRD and a distinguishable red shift in the absorption spectrum was observed. The MIP-modified electrode also exhibited a high adsorption capacity for TC due to its high surface area providing imprinted sites. Photocurrent was generated on the MIP-modified photoanode using the simulated solar spectrum and increased with the increase of positive bias potential. Under simulated solar light irradiation, the MIP-modified TiO₂ nanotube array electrode exhibited enhanced photoelectrocatalytic (PEC) activity with the apparent first-order rate constant being 1.2-fold of that with TiO₂ nanotube array electrode. The effect of the thickness of the MIP layer on the PEC activity was also evaluated.     

Synchronous fluorescence and UV-vis spectroscopic studies of interactions between the tetracycline antibiotic, aluminium ions and DNA with the aid of the Methylene Blue dye probe

Synchronous fluorescence spectroscopy (SFS) was applied for the investigation of interactions of the antibiotic, tetracycline (TC), with DNA in the presence of aluminium ions (Al³⁺). The study was facilitated by the use of the Methylene Blue (MB) dye probe, and the interpretation of the spectral data with the aid of the chemometrics method, parallel factor analysis (PARAFAC). Three-way synchronous fluorescence analysis extracted the important optimum constant wavelength differences, Δλ, and showed that for the TC-Al³⁺-DNA, TC-Al³⁺ and MB dye systems, the associated Δλ values were different (Δλ = 80, 75 and 30 nm, respectively). Subsequent PARAFAC analysis demonstrated the extraction of the equilibrium concentration profiles for the TC-Al³⁺, TC-Al³⁺-DNA and MB probe systems. This information is unobtainable by conventional means of data interpretation. The results indicated that the MB dye interacted with the TC-Al³⁺-DNA surface complex, presumably via a reaction intermediate, TC-Al³⁺-DNA-MB, leading to the displacement of the TC-Al³⁺ by the incoming MB dye probe.