Determination of fluoroquinolones, sulfonamides, and tetracyclines multiresidues simultaneously in porcine tissue by MSPD and HPLC-DAD

An efficient method is provided to detect simultaneously some important veterinary drugs from different classes in highly complex animal tissue matrix. This method using matrix solid-phase dispersion (MSPD) and high performance liquid chromatography (HPLC) with diode array detection (DAD) is developed to effectively determine two fiuoroquinolones (enoxacin and lomefioxacin), two sulfonamides (sulfanilamide and sulfamethoxazole) and one tetracycline (tetracycline) simultaneously in porcine tissues. In the process, MSPD methodology was used to treat samples, washed by n-hexane to remove lipid, eluted the analytes with acetonitrile–dichloromethane (1:1, v/v). Solvent acetonitrile and solvent acetic acid (0.1%) were combined in a gradient. HPLC–DAD analysis of the tissue samples was performed within 15 min at a fiow rate of 1.0 mL/min. The results showed that a recovery at 0.1, 0.5 and 1.0 mg/g fortification levels ranged from 80.6% to 99.2% with satisfactory relative standard deviations (RSDs) (below 6.1%, nfi3) and the limits of quantitation (LOQ) ranged from 7 mg/kg to 34 mg/kg in porcine tissues. Utilization of the method in successfully simultaneous analysis of porcine tissue incurred with veterinary drug multiresidues is described.

Determination of Tetracyclines and Their Epimers in Agricultural Soil Fertilized with Swine Manure by Ultra-High-Performance Liquid Chromatography Tandem Mass Spectrometry

A rapid, sensitive and specific ultra-high-performance liquid chromatography tandem mass spectrometry （UPLC-MS） method was developed for the analysis of tetracycline antibiotics, including tetracycline （TC）, oxytetracycline （OTC）, chlortetracycline （CTC） and their 4-epimers （4-epiTCs） in agricultural soil fertilized with swine manure. Soil samples were extracted and cleaned-up with 10 mL EDTA-McIlvaine buffer solution （pH 4.0）, then cleaned-up and pre-concentrated using the Oasis MAX cartridge and then eluted with 1 mL solution by mixing formic acid, methanol and water at a ratio of 2：15：83 （v/v/v）. The purified samples were separated by an ACQUITY UPLC BEH C18 column using acetonitrile and water containing 0.1% formic acid mobile phase and detected by a single quadrupole MS. The limits of detection for the soil extraction method （LODsoil） ranged from 0.6-2.5 lag kg-~ with recoveries from 23.3-159.2%. Finally, the method was applied to an agricultural field in an area with intensive pig-fattening farming. Tetracyclines were detected in soil from 2.8 to 42.4 μg kg-1 soil. These results demonstrate that soil from swine farms can become severely contaminated with tetracycline antibiotics and their metabolites.

Survey of Tetracyclines, Sulfonamides, Sulfamethazine, and Quinolones in UHT Milk in China Market

This study surveyed 180 samples of ultra high temperature （UHT） milk of four top Chinese dairy brands collected in the 25 cities in China in June 2011, and assessed their contamination with antibiotics, using the ELISA method. The percentages of tetracyclines, sulfonamides, sulfamethazine, and quinolones detected in the samples were 0, 16.7, 40.6, and 100%, respectively. The maximum concentrations of the tetracyclines, sulfonamides, sulfamethazine and quinolones in UHT milk samples were 〈1.5, 26.2, 22.6, and 58.8 μg kg-1, respectively. None of the samples exceeded the maximum residue levels （MRLs） for these four veterinary drugs, according to the regulations set by China, the European Union （EU） and the Codex Alimentarius Commission （CAC）.

Study on Rapid Detection of Tetracyclines,Fluoroquinolones and Sulfonamides in Milk

Aiming at the market demand for rapid detection of tetracyclines,fluoroquinolones and sulfonamides in milk,a golloidal gold immunochromatography test strip for simultaneous detection of tetracyclines,fluoroquinolones and sulfonamides in milk was prepared based on the principle of competitive inhibition immunochromatography. The performance indicators of the test strip were verified. The results showed that the test strip can simultaneously detect 4 tetracyclines,13 fluoroquinolones and 13 sulfonamides,and the detection limits all can meet the national residue limits; the tests strip exhibited false positive rate≤5% and false negative rate = 0; and no cross-reaction with other drugs was commonly found in milk,indicating good specificity. The method is simple,rapid,and has low cost and easy popularization. It provides a means for realizing on-site rapid detection and is of important practical significance to guarantee of safety of milk and dairy products in China.

Indirect Flow Injection Chemiluminescence Method for the Determination of Tetracyclines Using Cu(Ⅱ) as a Probe Ion

This paper reported an indirect flow injection chemiluminescence （FI-CL） method for the determination of the drugs tetracycline （TC）, chlortetracycline （CTC） and oxytetracycline（OTC） using Cu（ Ⅱ ） as a probe ion. The CL reaction was induced on-line and after injection of the sample the negative peaks appeared as a result of complexation. The method was applied to the determination of TCs in pharmaceuticals and human urine with recoveries in the range95-105%.

Green remediation of tetracyclines in soil-water systems

The presence of tetracyclines in soil and surface water is an emerging concern. The present study was undertaken to investigate remediation of tetracylines (tetracycline (TC), oxytetracycline (OTC) and chlortetracycline (CTC)) from aqueous solution using vetiver grass, water lettuce, and sunflower and root exudates of water lettuce, sunflower and from soil by tomato, Indian mustard and carrot plant. The data of this study denote that vetiver grass, water lettuce, sunflower remedy tetracyclines from water. The remediation % after 63 days of treatment was 87-61 for TC;88-68 for OTC and 87-68 for CTC. The remediation of tetracyclines at lower concentration of antibiotics in presence of root exudates of water lettuce and sunflower was more than 99% and remediation was faster than water lettuce or sunflower. The remediation of tetracyclines from aqueous solution may be due to oxidation of-OH group(s) of tetracycline through a process that is thought to involve reactive oxygen intermediates and/or role of peroxidase enzyme. The plant crops viz., tomato, Indian mustard and carrot can remedy 41%-72% of amended tetracyclines. The maximum bioaccumulation of TC and CTC was in Indian mustard and OTC was maximally bioaccumulated in tomato.

Fate of tetracyclines in swine manure of three selected swine farms in China

Veterinary antibiotics can enter the environment due to the common practice of land application of manure from treated animals.The environmental fate of tetracyclines in swine manure after composting and field application remains largely unknown.This study analyzed the concentrations of tetracyclines in manure,manure-based compost and compost amended soil in selected swine farms from Beijing,Jiaxing and Putian,China to determine the dilution effects of antibiotics when released into the soil environment.The results demonstrate that residues of antibiotics were detected in all samples and chlortetracycline as well as its degradation products should be regarded critically concerning their potential ecotoxicity.Application of manure-based compost to soil could reduce the possible risk posed by antibiotic contamination,but the trigger value of 100 μg/kg was still exceeded in soil samples （776.1 μg/kg dw） from Putian City after application of compost.Field studies such as the present one can help to improve the routine administration of antibiotic-containing composted manure.

Fabrication of magnetic multi-template molecularly imprinted polymer composite for the selective and efficient removal of tetracyclines from water

Antibiotic contamination of the water environment has attracted much attention from researchers because of their potential hazards to humans and ecosystems.In this study,a multi-template molecularly imprinted polymer(MIP)modified mesoporous silica coated magnetic graphene oxide(MGO@MS@MIP)was prepared by the surface imprinting method via a sol-gel process and was used for the selective,efficient and simultaneous removal of tetracyclines(TCs),including doxycycline(DC),tetracycline(TC),chlorotetracycline(CTC)and oxytetracycline(OTC)from water.The synthesized MIP composite was characterized by Fourier transform infrared spectroscopy,transmission electron microscope and thermogravimetric analysis.The adsorption properties of MGO@MS@MIP for these TCs were characterized through adsorption kinetics,isotherms and selectivity tests.The MIP composite revealed larger adsorption quantities,excellent selectivity and rapid kinetics for these four tetracyclines.The adsorption process was spontaneous and endothermic and followed the Freundlich isotherm model and the pseudo-second-order kinetic model.The MGO@MS@MIP could specifically recognize DC,TC,CTC and OTC in the presence of some chemical analogs.In addition,the sorption capacity of the MIP composite did not decrease significantly after repeated application for at least five cycles.Thus,the prepared magnetic MIP composite has great potential to contribute to the effective separation and removal of tetracyclines from water.

Determination of Tetracyclines in Honey Using Liquid Chromatography with Ultraviolet Absorbance Detection and Residue Confirmation by Mass Spectrometry

A determination method has been optimized and validated for the simultaneous analysis of tetracycline （TC）, oxytetracycline （OTC）, chlortetracycline （CTC） and doxycycline （DC） in honey. Tetracyclines （TCs） were removed from honey samples by chelation with metal ions bound to small Chelating Sepharose Fast Flow columns and eluted with Na2EDTA-Mcllvaine pH 4.0 buffers. Extracts were further cleaned up by Oasis HLB solid-phase extraction （SPE）, while other solid-phase extraction cartridges were compared. Chromatographic separation was achieved using a polar end-capped C 18 column with an isocratic mobile phase consisting of oxalic acid, acetonitrile and methanol. LC with ultraviolet absorbance at 355 nm resulted in the quantitation of all four tetracycline residues from honey samples fortified at 15, 50, and 100 ng/g, with liner ranges for tetracyclines of 0.05 to 2 μg/mL. Mean recoveries for tetracyclines were greater than 50% with R.S.D. values less than 10% （n= 18）. Detection limits of 5, 5, 10, 10 ng/g for oxytetracycline, tetracycline, chlortetracycline and doxycycline, respectively and quantitation limits of 15 ng/g for all the four tetracyclines were determined. Direct confirmation of the four residues in honey （2-50 ng/g） was realized by liquid chromatography-tandem mass spectrometry （LC/MS/MS）. The linear ranges of tetracyclines determined by LC/MS/MS were between 5 to 300 ng/mL, with the linear correlation coefficient r〉 0.995. The limits of detection of 1 to 2 ng/g were obtained for the analysis of the TCs in honey.

Achieving high-efficient photocatalytic persulfate-activated degradation of tetracycline via carbon dots modified MIL-101(Fe)octahedrons

The synergistic reaction of photocatalysis and advanced oxidation is a valid strategy for the degradation of harmful antibiotic wastewater.Herein,carbon dots(CDs)modified MIL-101(Fe)octahedrons to form CDs/MIL-101(Fe)composite photocatalyst was synthesized for visible light-driven photocatalytic/persulfate(PS)-activated tetracycline(TC)degradation.The electron spin resonance(ESR)spectra,scavenging experiment and electrochemical analysis were carried out to reveal that the high visible light-driven photocatalytic degradation activity of TC over CDs/MIL-101(Fe)photocatalysts is not only ascribed to the production of free active radicals in the CDs/MIL-101(Fe)/PS system(·OH,·SO_(4-),^(1)O_(2),h^(+)and·O_(2)^(-))but also attributed to the consumption of electrons caused by the PS,which can suppress the recombination of photo-generated carriers as well as strong light scattering and electron trapping effects of CDs.Finally,the possible degradation pathways were proposed by analyzing intermediates via liquid chromatography-mass spectrometry technique.This research presents a rational design conception to construct a CDs/PS-based photocatalysis/advanced oxidation technology with high-efficient degradation activity for the remediation of organic antibiotic pollutant wastewater and for the improvement of carrier transport kinetics of photocatalysts.

Carbon-doped CuFe_(2)O_(4) with C-O-M channels for enhanced Fenton-like degradation of tetracycline hydrochloride: From construction to mechanism

Carbon-doped copper ferrite(C–CuFe_(2)O_(4))was synthesized by a simple two-step hydrothermal method,which showed enhanced tetracycline hydrochloride(TCH)removal efficiency as compared to the pure CuFe_(2)O_(4) in Fenton-like reaction.A removal efficiency of 94%was achieved with 0.2 g L^(-1) catalyst and 20 mmol L^(-1) H_(2)O_(2) within 90 min.We demonstrated that 5%C–CuFe_(2)O_(4) catalyst in the presence of H_(2)O_(2) was significantly efficient for TCH degradation under the near-neutral pH(5–9)without buffer.Multiple techniques,including SEM,TEM,XRD,FTIR,Raman,XPS M€ossbauer and so on,were conducted to investigate the structures,morphologies and electronic properties of as-prepared samples.The introduction of carbon can effectively accelerate electron transfer by cooperating with Cu and Fe to activate H_(2)O_(2) to generate·OH and·O_(2)^(-).Particularly,theoretical calculations display that the p,p,d orbital hybridization of C,O,Cu and Fe can form C–O–Cu and C–O–Fe bonds,and the electrons on carbon can transfer to metal Cu and Fe along the C–O–Fe and C–O–Cu channels,thus forming electron-rich reactive centers around Fe and Cu.This work provides lightful reference for the modification of spinel ferrites in Fenton-like application.

Sorption behavior of tetracyclines on suspended organic matters originating from swine wastewater

Tetracyclines（TCs） discharged from livestock wastewater have aroused public concerns due to their pharmacological threats to ecosystems and human health. As an important medium in the wastewater, suspended organic matters（SOMs） play vital roles in antibiotics transport and degradation. However, limited information has been reported in the relevant literature. This study investigated TCs sorption behavior on SOM, withdrawn from swine wastewater. High TCs sorption capacities were detected, with the maximum values ranging from 0.337 to 0.679 mg/g. Increasing p H and temperature led to the decline of sorption capacity. Results from three-dimensional excitation–emission matrix fluorescence spectroscopy and Fourier transform infrared spectrometry revealed that amide and carboxyl groups were the main functional groups for TCs adsorption. The interactions between SOM and TCs were clarified as predominated by hydrogen-bonding and cation-exchange in acid conditions, and electrostatic repulsion in neutral or alkaline conditions. Adsorption kinetics modeling was conducted, and a satisfactory fitting was achieved with the Freundlich equation. These results indicated that the adsorption process was a rather complex process, involving a combination of cation-exchange and hydrogen-bonding. The results will provide a better understanding of the capability of SOM for TCs transport and abatement in the wastewater treatment process.

Facile one-pot synthesis of a BiOBr/Bi_(2)WO_(6) heterojunction with enhanced visible-light photocatalytic activity for tetracycline degradation

Photocatalytic removal of tetracycline(TC)from the wastewater is of great value in the chemical and environmental engineering field.Here,we introduced a facile one-step method for the synthesis of BiOBr/Bi2WO6 heterojunctions by using cheap CTAB as the Br source.We showed the possibility of our method to fine-tune the content of BiOBr in the produced BiOBr/Bi2WO6 by simply changing the dosage of cetyltrimethylammonium bromide(CTAB),providing a platform for the delicate tuning of the visiblelight absorbance ability of the composites.With a suitable heterojunction structure of BiOBr/Bi2WO6-0.2,it exhibited an ultrarapid photocatalytic activity towards TC(20 mg
L^(-1)),with a competitive removal efficiency of 88.1%within 60 min and an ultrahigh removal rate of 0.0349 min^(-1).It could also be robustly recycled for at least 5 cycles with slight removal efficiency loss.We demonstrated that this exciting photocatalytic performance was due to the highly decreased recombination of photoinduced electrons and holes on our composites by constructing this heterojunction structure,and the resulting
OH and
O^(-)_(2)contributed to the effective degradation of TC to CO_(2).

Synthesis of porous carbon nanomaterials and their application in tetracycline removal from aqueous solutions

The low-cost and efficient elimination of tetracycline from wastewater and to decrease the concentration in soils,sediments,rivers,underground water,or lakes are crucial to human health.Herein,threedimensional porous carbon nanomaterials were synthesized using glucose and NH_(4)Cl by sugarblowing process at 900℃ and then oxidized under air atmosphere for surface functional group modification.The prepared 3D porous carbon nanomaterials were applied for the removal of tetracycline from aqueous solutions.The sorption isotherms were well simulated by the Langmuir model,with the calculated sorption capacity of 2378 mg·g^(-1) for C-450 at pH=6.5,which was the highest value of today's reported materials.The porous carbon nanomaterials showed high stability at acidic conditions and selectivity in high salt concentrations.The good recycle ability and high removal efficiency of tetracycline from natural groundwater indicated the potential application of the porous carbon nanomaterials in natural environmental antibiotic pollution cleanup.The outstanding sorption properties were attributed to the structures,surface areas and functional groups,strong interactions such as H-bonding,π-π interaction,electrostatic attraction,etc.This paper highlighted the synthesis of porous carbon nanomaterials with high specific surfaces,high sorption capacities,stability,and reusability in organic chemicals'pollution treatment.

Colloidal Gold Immunochromatographic Assay for Rapid On-Site Detection of Tetracycline in Seawater

Recently increasing concerns from the scientists and public have been paid for seawater pollution due to tetracycline(TC)overuse in maricultural area.However,there are few methods or instruments that can be used for specific and rapid detection of this antibiotic in seawater.In this study,the colloidal gold immunochromatographic assay(CG-ICA)was used to achieve this goal.A commercialized monoclonal antibody against TC(anti-TC mAb)was selected because of its higher sensitivity(half-maximal inhibitory concentration of 2.38μgL^(-1)).The prepared CG particles(average diameter of 20 nm)were used to label anti-TC mAb at pH 8.0.The conjugate pad was formed by spraying the CG-labeled anti-TC mAb on a glass fibre membrane followed by proper dryness.The test pad was made by immobilizing artificial antigen and anti-mouse mAb in the test line and the control line,respectively,in a nitrocellulose membrane.The test strip,assembled with sample pad,conjugate pad,test pad and absorbent pad,could be used to detect TC during seawater sample flowing through these components in turn.The results could be observed by the naked eye in 10min.The visible limit of detection(vLOD)was 20μgL^(-1) for TC in seawater.The CG-ICA test results were in good agreement with those of liquid chromatography-tandem mass spectrometry(LC-MS/MS).The assay also showed that,oxytetracycline(OTC)and chlortetracycline(CTC),as the structural analogues of TC,did not interfere with TC determination.Furthermore,the TC concentration given by test strip could not be affected by the fluctuation of temperature(10℃–30℃),pH(7–9)and salinity(0–40)of seawater.Therefore,CG-ICA is a suitable tool for rapid,on-site,and semi-quantitative detection of TC in seawater.

Efficacy and safety of modified tetracycline dosing in a quadruple therapy for Helicobacter pylori:A retrospective single center study

BACKGROUND Although highly effective as a component of Helicobacter pylori(H.pylori)treatment regimen,tetracycline is associated with a high incidence of medicationrelated adverse events.Modified dosing of tetracycline as part of quadruple therapy may improve safety while providing comparable eradication rates.AIM To evaluate the efficacy and safety of modified dosing of tetracycline in patients receiving tetracycline and furazolidone-containing quadruple therapy in patients with H.pylori infection.METHODS Consecutive patients(10/2020-12/2021)who received tetracycline and furazolidone quadruple therapy for H.pylori infection at Sir Run Run Shaw Hospital were identified.All patients received tetracycline,furazolidone,proton pump inhibitor,and bismuth for 14 d as primary or rescue therapy.Modified tetracycline dose group received tetracycline 500 mg twice daily while standard group received 750 mg twice daily or 500 mg three times daily.RESULTS Three hundred and ninety-four patients[mean age=46.3±13.9,male=137(34.8%),and 309(78.4%)primary therapy]completed tetracycline and furazolidone quadruple therapy for H.pylori infection including those who received modified tetracycline dose in 157 and standard doses in 118(750 mg twice daily)and 119(500 mg three times daily).Eradication rates in the modified tetracycline dose group were 92.40%and in the standard groups,eradication rates were 93.20%for 750 mg twice daily group and 92.43%for 500 mg three times daily group,respectively,without statistical difference(P=0.959).The incidence of adverse events was lower in the modified tetracycline dose(15.3%vs 32.3%and 29.4%;P=0.002)compared to the standard dose group.CONCLUSION In a real-world experience,modified tetracycline dosing as part of tetracycline and furazolidone quadruple therapy for 14 d demonstrated high efficacy,comparable to standard tetracycline dose regimens,with a favorable safety profile.

Preliminary Study on the Treatment Efficiency of Pasteurized Lime Thermal Alkaline Hydrolysis for Excess Activated Sludge and Reduction of Tetracycline Resistance Genes

Thermal alkaline hydrolysis is a common pretreatment method for the utilization of excess activated sludge(EAS).Owing to strict environment laws and need for better energy utilization,new methods were developed in this study to improve the efficiency of pretreatment method.Direct thermal hydrolysis(TH),pasteurized thermal hydrolysis(PTH),and alkaline pasteurized thermal hydrolysis(PTH+CaO and PTH+NaOH)methods were used to treat EAS.Each method was compared and analyzed in terms of dissolution in ammonium nitrogen(NH_(4)^(+)-N)and soluble COD(SCOD)in EAS.Furthermore,the removal of tetracycline resistance genes(TRGs)and class 1 transposon gene intI1 from EAS was investigated.The NH_(4)^(+)-N and SCOD concentrations in EAS treated by PTH were 1.24 and 2.58 times higher than those of TH.However,the removal efficiency of total TRGs and intI1 between the groups was comparable.The SCOD concentration of the PTH+NaOH group was 4.37 times higher than that of the PTH group,and the removal efficiency of total TRGs was increased by 9.52%compared with that by PTH.The NH_(4)^(+)-N and SCOD concentrations of the PTH+CaO group could reach 85.04%and 92.14%of the PTH+NaOH group,but the removal efficiency of total TRGs by PTH+CaO was 19.78%lower than that by PTH+NaOH.Thus,to reduce the financial cost in actual operation,lime(CaO)can be used instead of a strong alkali(NaOH),and pasteurized steam at 70℃ instead of conventional high-temperature heating to treat EAS.This study provides a reference for the development of alkaline hydrolysis under moderate temperatures along with the removal of TRGs in EAS.

牛肉中5种四环素类兽药残留的UPLC-MS/MS检测

A method for simultaneous analysis of five tetracyclines(tetracycline,oxytetracycline,chlortetracycline,doxycycline and minocycline) in bovine muscle was developed by UPLC-MS/MS.The sample was extracted with Mcllvaine buffer-EDTA(pH 4.0) and cleaned up by solid-phase extraction on Oasis HLB cartridges.Analytes were separated by UPLC,and detected by mass spectrum with MRM mode.The calibration curves showed good linear relations in the concentration range of 1-100 μg·L-1(r>0.994) for five tetracyclines.The average recoveries at the spiked concentration levels of 1,20,50 and 100 μg·kg-1 were range of 68%-105% and the RSD were less than 34.1%.The LOD of the method was 0.05 μg·kg-1 for five tetracyclines.

HPLC-ESI MS/MS对动物组织中痕量四环素类抗生素的同时测定

A method for simultaneous determination of oxytetracycline,tetracycline,chlortetracycline in animal tissue was successfully established by HPLC-ESI MS/MS.The tetracycline antibiotics in animal tissue were extracted by liquid-solid extraction and cleaned up by SPE.The mass spectrometer was operated in the positive-ion mode using selected reaction monitoring(SRM).The results showed that three tetracycline antibiotics were well separated under the optimal conditions.The detection limits of oxytetracycline,tetracycline and chlortetracycline were 0.16 ng/g,0.1 ng/g and 0.1 ng/g,respectively.The spiked recoveries were range of 84%-94% and the relative standard deviations were 2.4%-2.9%.

Environmental Assessment of Tetracycline’s Residues Detected in Pig Slurry and Poultry Manure

The widespread use of antimicrobials in animal husbandry has led to an increase in concentrations of antibiotics in animal faeces. Furthermore, the spreading of this waste as fertilizer on agricultural land indirectly introduces antimicrobial residues into the environment. This study examined samples of pig slurry and poultry manure for three tetracyclines—oxytetracycline (OTC), chlortetracycline (CTC) and doxycycline (DOC) and conducted an environmental evaluation of soils. The samples were taken from manure heaps on eight broiler chicken farms and from slurry ponds on eight pig farms. The tetracycline analysis was conducted using high-performance liquid chromatography combined with tandem mass spectrometry (HPLC/MS). The risk assessment was carried out on the basis of the estimated PECsoil value and the ecotoxicological information available for terrestrial organisms. TC concentrations were between >0.01 and 1.38 mg/kg. OCT was detected in 37% of the poultry manure and in 20% of the pig slurry samples. DOC was present in 50% of pig slurry samples with an average concentration of 1.2 mg/kg, while CTC was only found in one slurry sample at a concentration of 0.56 mg/kg. Compared with published values for these two farm animals from other countries, the TC concentrations obtained in this study were low. The environmental importance of the data generated was also discussed.