Separation of Tetracycline Antibiotics by Hydrophilic Interaction Chromatography Using an Amino-Propyl Stationary Phase

In this work the potential of hydrophilic interaction chromatography (HILIC) is explored for the analysis of tetracycline antibiotics. The choice of the polar stationary phase is first discussed and it is demonstrated that aminopropyl stationary phases lead to higher efficiencies and peak symmetry than bare silica ones. The influence of the composition of the mobile phase is studied next : the concentration of the weaker solvent (acetonitrile), the nature and concentration of the more polar solvent (water or methanol), pH, the nature and ionic strength of the buffer. It is shown that high efficiencies are reached only with a citrate buffer that impairs the interactions with the residual silanol groups whatever the mobile phase pH is. We demonstrate that the citrate buffer strongly interacts with the cationic moiety of the aminopropyl stationary phase and thus reduces the accessibility of silanols. The separation of oxytetracycline, tetracycline and chlortetracycline is achieved in a few minutes at pH 3.5 or 5, with no peak tailing as usually observed in reversed phase liquid chromatography with an opposite elution order when compared with reversed phase liquid chromatography.     

Simultaneous Determination of Oxytetra- cycline, Doxycycline, Tetracycline and Chlortetracycline in Tetracycline Antibiotics by High-Performance Liquid Chromatog- raphy with Fluorescence Detection

A simple, rapid and sensitive high-performance liquid chromatographic method with fluorescence detection for the simultaneous determination of oxytetracycline, doxycycline, tetracycline and chlortetracycline was developed, and successfully applied to the analysis of commercial tetracycline antibiotics. The separation was performed on a reverse-phase C₁₈ column with a gradient elution composed of methanol and sodium acetate buffer (containing disodium ethylenediaminetetraacetate and calcium chloride, pH 8.10) as the mobile phase, and fluorescence detection at 532 nm (excitation at 380 nm). The detection limits for oxytetracycline, doxycycline, tetracycline and chlortetracycline were 0.1, 0.5, 0.3 and 0.4 g L^–1, respectively. Data with respect to precision and accuracy were reported and discussed.     

Determination of Tetracycline at a UV‐Irradiated DNA Film Modified Glassy Carbon Electrode

In this study, interaction of tetracycline (TC) and DNA in the Britton? Robinson buffer solution (BR) was studied by cyclic voltammetry. The experimental results reveal that TC can bind strongly to DNA and the association constant and binding number between TC and DNA was obtained. Then DNA was immobilized on a glassy carbon electrode by UV‐irradiation. Through this process, water‐soluble DNA was converted into insoluble materials, and a stable DNA film was formed on the electrode. The electrochemical oxidation behavior of TC was studied at UV‐irradiated DNA film modified glassy carbon electrode (UV‐DNA‐GCE). The response of modified electrode was optimized with respect to pH, accumulation time, ionic strength, drug concentration and other variables. TC at the surface of modified electrode showed a linear dynamic range of 0.30–90.00 µM and a detection limit of 0.27 µM. To demonstrate the applicability of the modified electrode, it was used for the analysis of real samples such as pharmaceutical formulations and milk.     

Quantitative analysis and pharmacokinetics study of tigecycline in human serum using a validated sensitive liquid chromatography with tandem mass spectrometry method

Tigecycline, a novel intravenously administered glycylcycline antibiotic, currently plays a key role in the management of complicated multiorganism infections. However, current liquid chromatography with tandem mass spectrometry methods briefly describe parameters and the only reported internal standard was sometimes difficult to obtain. In our study, an updated liquid chromatography with tandem mass spectrometry method for the quantitative analysis of tigecycline in human serum was developed. Sample preparation involved precipitation with 20% trichloroacetic acid. Chromatographic separation of tigecycline and tetracycline (internal standard) was achieved on a Hypersil GOLD C₁₈ column using gradient elution. The selected reaction monitoring transitions were performed at m/z 586.1→513.2 for tigecycline and m/z 445.1→410.2 for tetracycline. The assay was linear over the concentration range of 5–2000 ng/mL. The intra‐ and interday precisions at three concentration levels (10, 100, and 1600 ng/mL) were <15% and their accuracies were within the range of 95.1–106.1%. The mean recovery ranged from 94.3 to 105.6% and the matrix effect from 92.1 to 97.6%. Tigecycline was stable under all tested conditions. This validated method was successfully applied to a pharmacokinetic study in critically ill patients. The data demonstrated that our method allows quantification of tigecycline in serum in a quick and reliable manner for widespread application.     

纳米Ag/TiO_(2)纳米管阵列基底构建及表面增强拉曼散射光谱检测与降解盐酸四环素北大核心CSCD

将阳极氧化与光还原法结合,在TiO_(2)纳米管阵列(TiO_(2)NTAs)表面修饰Ag纳米粒子,获得一种均匀有序、稳定性高且可循环的TiO_(2)NTAs/Ag活性基底。采用X射线粉末衍射(XRD)、X射线光电子能谱(XPS)、紫外可见漫反射光谱(UV-Vis DRS)、表面增强拉曼散射光谱(SERS)和扫描电子显微镜(SEM)等手段对TiO_(2)NTAs/Ag的组成和结构进行了表征。进一步研究了该TiO_(2)-NTAs/Ag阵列对盐酸四环素(TC-HCl)的SERS响应,结果表明,该复合基底对TC-HCl具有较高的检测灵敏度,在水中检测限可达1×10^(−14) mol/L,而TiO_(2)-NTAs与Ag之间的协同效应对其检测性能的提高起着关键作用。此外,TiO_(2)NTAs/Ag基底在光照下对TC-HCl展示了优异的降解活性,且至少可循环使用8次。表明该TiO_(2)NTAs/Ag基底在环境中有机污染物的SERS检测和降解领域具有潜在的应用前景。     

Photocatalytic removal of tetracycline by a Z-scheme heterojunction of bismuth oxyiodide/exfoliated g-C3N4: performance,mechanism, and degradation pathway

Antibiotics, once being released into the environment, become recalcitrant organic pollutants, which pose a potential risk to ecological balance and human health. In this study, a Z-scheme heterojunction of bismuth oxyiodide (BiOI)/exfoliated g-C₃N₄ (BiOI/ECN hereafter) was synthesized by the combination of thermal exfoliation of g-C₃N₄ and chemical precipitation of BiOI for efficient photocatalytic degradation of tetracycline in aqueous solutions under visible light irradiation. The optimized BiOI/ECN delivered an outstanding degradation rate at circa 0.0705 min^?1, which was 10 times higher than that of the bulk g-C₃N₄. The photocatalytic degradation efficiency of tetracycline remained almost unchanged in a pH range of 3–11, and the BiOI/ECN displayed an excellent photostability upon recycled usage. The photocatalytic mechanism of tetracycline was ascribed to the main reactive oxidation species of photogenerated holes and superoxide radicals. In addition, the possible degradation pathways of tetracycline were investigated by HPLC-MS to identify intermediates. The toxicity of photocatalytic-generated intermediates of tetracycline was found significantly alleviated according to the calculation of quantitative structure–activity relationship prediction. This work not only provides an attractive photocatalyst for the removal of tetracycline but also opens a new avenue for rational design of Z-scheme heterojunction composites for tetracycline degradation.     

Synthesis of Z-scheme g-C3N4 nanosheets/Ag3PO4 photocatalysts with enhanced visible-light photocatalytic performance for the degradation of tetracycline and dye

Graphene-like C3N4/Ag3PO4 photocatalysts are synthesized by calcination and solutions precipitating method.The obtained g-C3N4/Ag3PO4 composites display excellent photocatalytic activity for the degradation of methylene orange(MO),rhodamine B(RhB)and tetracycline(TC)under visible light irradiation.The solutions containing RhB(10 mg/L)and MO(10 mg/L)can be efficiently degraded within15 min and 30 min.Especially,nearly 80%of TC(50 mg/L)is degraded within 20 min.which are much better than those of pure g-C3N4 nanosheets and Ag3PO4,implying that strong interaction and reasonable energy band alignment in the contact interface can effectively transfer the carries.Furthermore,the g-C3N4/Ag3PO4 composites exhibit the improved stability,and only a slight decrease is observed after three recycling runs.Moreover,the impact of inorganic ions and PH values on the degradation performance is rather small.The Z-scheme photocatalytic mechanism of the g-C3N4/Ag3PO4 composites based on the active species trapping experimental is proposed.This work demonstrates the promising applications of the g-C3N4/Ag3PO4 composites in environmental issues.     

UV spectrophotometric flow-injection assay of tetracycline antibiotics retained on Sephadex QAE A-25 in drug formulations

A flow injection analysis system with solid phase spectrophotometric transduction has been developed for the assay of tetracycline (TC), doxycicline (DTC), oxycicline (OTC) and chlortetracycline (CTC). The packing material of the flow-through cell consists of Sephadex QAE A-25 resin on which tetracyclines are temporarily retained. The carrier itself acts as the desorbing solution. The measurements of the intrinsic absorbance of tetracyclines (1000 μl of sample volume) were made at 380 nm (TC, DTC and OTC) and 387 nm (CTC). The detection limits were found to be 0.069 (TC and OTC), 0.081 (DTC) and 0.121 (CTC) μg ml⁻¹ and the linear dynamic range extended between 0.5 and 12 (TC, DTC and OTC) and 1–20 μg ml⁻¹ (CTC). The relative standard deviations (n=10) ranged between 0.7 and 1.2%. A study of the potentially interfering species was carried out. Using the proposed method, tetracyclines were satisfactorily determined without any interference from excipients in pharmaceutical preparations.     

三元磁性氮化碳复合光催化剂的制备和表征及其在可见光下去除四环素的应用

g-C3N4作为一种新型有机半导体材料,由于其良好的化学稳定性和可直接利用可见光等优点已经引起了人们的广泛关注,近年来已逐渐将其应用于光催化氧化环境污染物等方面.同时在实际应用中因其光能利用率低、难回收、电子-空穴易复合等缺点也受到了限制.研究发现将四氧化三铁与氮化碳相结合,可以有效提高复合催化剂的光催化活性,而且可回收再利用很大程度上降低成本.采用光催化氧化技术处理实际环境污染物废水时,将光催化剂投入到废水中后,环境及水体的温度往往会对催化剂的催化活性产生一定的影响,导致无法实现最佳的光催化处理效果.制备一种催化活性不受外界温度影响的智能光催化材料是当今面临的一项挑战.我们研究制备了一种具有温度响应的磁性复合光催化剂PNIPAM/Fe3O4/g-C3N4,其可根据外界温度的不同而表现出不同的光催化活性.温敏型聚合物PNIPAM是一类结构、性能和形态随温度变化而做出响应的功能材料,将光催化材料与温敏型PNIPAM智能高分子材料相结合,实现了智能催化的效果.PNIPAM温敏聚合物在水溶液中存在一个低临界溶解温度,其可以作为开关,通过改变温度实现对光催化过程的控制,达到过程智能化的效果.随着温度的改变,温敏聚合物的溶解状态在临界点附近会发生变化.不同温度对催化速率影响很大,当温度升高到临界值以上,催化反应速率降低很多;当温度降低到临界值以下,催化活性随之升高.这样不仅随时控制反应的进行,还可以通过改变温度控制反应速率.同时,温敏聚合层又相当于一个保护层,可以增强其抗腐蚀能力,提高对内部光催化材料的保护,进而提高其稳定性.众所周知四环素等抗生素类药物生产废水,属于高浓度有机废水,具有一定的毒性,一般较难处理.我们将制备的PNIPAM/Fe3O4/g-C3N4复合光催化材料用于四环素废水的处理取得了很好的效果.XRD,FT-IR、Raman等表征手段充分证明了我们所制备的三元复合材料PNIPAM/Fe3O4/g-C3N4的组成及各个组分的存在.并对PNIPAM/Fe3O4/g-C3N4复合光催化剂在不同温度(20和45°C)条件下处理四环素废水进行了系统的研究,从20和45℃的吸附曲线结果可以看出,低温时PNIPAM/Fe3O4/g-C3N4的吸附性较强,高温时吸附较差.同时PNIPAM/Fe3O4/g-C3N4低温时具有较高的催化活性,高温时催化活性较低.经过分析可知这种对温度响应的特殊性能与PNIPAM的亲水及疏水性密切相关.另外,通过对PNIPAM/Fe3O4/g-C3N4复合材料的VSM测试及5次循环实验测试可以看出,PNIPAM/Fe3O4/g-C3N4复合材料由于Fe3O4的引入而表现出较好的磁性,且在外加磁铁的作用下很容易实现分离回收.另外,PNIPAM/Fe3O4/g-C3N4在经过5次重复利用后其催化活性几乎没有减退,说明催化剂具有很好的稳定性.另一方面,说明我们的复合光催化剂在工业废水等污染治理方面有一定的潜在应用价值.