Degrading ciprofloxacin(CIP)-polluted water has recently emerged as an urgent environmental issue.This study introduced mechanochemical treatment(MCT)as an innovative and underexplored approach for the degradation of ...Degrading ciprofloxacin(CIP)-polluted water has recently emerged as an urgent environmental issue.This study introduced mechanochemical treatment(MCT)as an innovative and underexplored approach for the degradation of CIP in water.The influence of various additives(CaO,Fe_(2)O_(3),SiO_(2),Al,and Fe)on CIP degradation efficiency was investigated.Additionally,six types of composite additives(Fe-CaO,Fe-Fe_(2)O_(3),Fe-SiO_(2),Fe-Al,Al-SiO_(2),and Al-CaO)were explored,with the composite of 20%Fe and 80%SiO_(2) exhibiting notable performance.The impacts of additive content,pH value,and co-existing ions on CIP degradation efficiency were investigated.Furthermore,the effectiveness of MCT in degrading other medical pollutants(norfloxacin,ofloxacin,and enrofloxacin)was verified.The transformations and changes in the crystal structure,oxidation state,microstructure,and morphology of the Fe-SiO_(2) composite additive were characterized using X-ray diffraction,X-ray photoelectron spectroscopy,and scanning electron microscopy techniques.This study proposed a sigmoid trend kinetic model(the Delogu model)that better elucidates the MCT process.Three plausible degradation pathways were discussed based on intermediate substance identification and pertinent literature.This study not only establishes a pathway for the facile degradation of CIP pollutants through MCT but also contributes to advancements in wastewater treatment methodologies.展开更多
Simultaneous degradation and detoxification during pharmaceutical and personal care product removal are important for water treatment.In this study,sodium niobate nanocubes decorated with graphitic carbon nitride(NbNC...Simultaneous degradation and detoxification during pharmaceutical and personal care product removal are important for water treatment.In this study,sodium niobate nanocubes decorated with graphitic carbon nitride(NbNC/g-C_(3)N_(4))were fabricated to achieve the efficient photocatalytic degradation and detoxification of ciprofloxacin(CIP)under simulated solar light.NaNbO_(3)nanocubes were in-situ transformed from Na_(2)Nb_(2)O_(6)·H_(2)O via thermal dehydration at the interface of g-C_(3)N_(4).The optimized NbNC/g-C_(3)N_(4)-1 was a type-I heterojunction,which showed a high conduction band(CB)level of−1.68 eV,leading to the efficient transfer of photogenerated electrons to O_(2) to produce primary reactive species,•O_(2)^(-).Density functional theory(DFT)calculations of the density of states indicated that C 2p and Nb 3d contributed to the CB,and 0.37 e^(-)transferred from NaNbO_(3)to g-C_(3)N_(4)in NbNC/g-C_(3)N_(4)based on the Mulliken population analysis of the built-in electric field intensity.NbNC/g-C_(3)N_(4)-1 had 3.3-and 2.3-fold of CIP degradation rate constants(k_(1)=0.173 min^(−1))compared with those of pristine g-C_(3)N_(4)and NaNbO_(3),respectively.In addition,N24,N19,and C5 in CIP with a high Fukui index were reactive sites for electrophilic attack by•O_(2)^(-),resulting in the defluorination and ring-opening of the piperazine moiety of the dominant degradation pathways.Intermediate/product identification,integrated with computational toxicity evaluation,further indicated a substantial detoxification effect during CIP degradation in the photocatalysis system.展开更多
The synergistic degradation of contaminants in water by photocatalysis and peroxydisulfate(PDS)activation has been proven to be a promising combined advanced oxidation technology.Consequently,the development of highly...The synergistic degradation of contaminants in water by photocatalysis and peroxydisulfate(PDS)activation has been proven to be a promising combined advanced oxidation technology.Consequently,the development of highly efficient photocatalysts that are activated by visible light and PDS is of immense importance.Herein,different proportions of cobalt-doped Bi_(2)Fe_(4)O_(9)(BFO@Co-x)photocatalysts were effectively synthesized for elimination of ciprofloxacin(CIP).The degradation efficiency of CIP achieved by the BFO@Co/Vis/PDS system attained 84.49%(k=0.0516 min−1)under 40 min light irradiation,outperforming the BFO@Co/Vis and PDS/Vis systems by a factor of 1.45 and 3.6,respectively.Characterization and photoelectric performance assessments revealed that the fabrication of BFO@Co-0.5 was successful,enhancing the photocatalytic degradation efficiency under the synergistic effect of PDS.Moreover,the BFO@Co/Vis/PDS system demonstrated favorable adaptability to various pH,inorganic anions,and humic acid in solution.Additionally,the degradation pathways of CIP and the toxicity of products were evaluated using LC/MS and T.E.S.T software,indicating a reduction in the toxicity of CIP degradation products.This study may provide insights into the application of photocatalyst/Vis/PDS combined systems in the field of water environmental treatment.展开更多
In this work,a novel electrochemical sensor based on covalent organic framework@carbon black@molecularly imprinted polydopamine(COF@CB@MPDA)was developed for selective recognition and determination of ciprofloxacin(CF...In this work,a novel electrochemical sensor based on covalent organic framework@carbon black@molecularly imprinted polydopamine(COF@CB@MPDA)was developed for selective recognition and determination of ciprofloxacin(CF).COF@CB@MPDA possessed good water dispersibility and was synthesized by the selfpolymerization of dopamine under alkaline conditions in the presence of the COF,CB and CF.The high surface area COF enhanced the adsorption of CF,whilst CB gave the composites high electrical conductivity to improve the sensitivity of the proposed COF@CB@MPDA/glassy carbon electrode(GCE)sensor.The specific recognition of CF by COF@CB@MPDA involved hydrogen bonding and van der Waals interactions.Under optimized conditions,the sensor showed a good linear relationship with CF concentration over the range of 5.0×10^(–7)and 1.0×10^(–4)mol/L,with a limit of detection(LOD)of 9.53×10^(–8)mol/L.Further,the developed sensor exhibited high selectivity,repeatability and stability for CF detection in milk and milk powders.The method used to fabricate the COF@CB@MPDA/GCE sensor could be easily adapted for the selective recognition and detection of other antibacterial agents and organic pollutants in the environment.展开更多
Efficient removal of antibiotics is of great significance for the sustainability of aquatic ecosystems.In this work,a new polyoxometalate-based metal-organic hybrid material[Ag_(3)L_(0.5)(HSiW_(12)O_(4)0)]·2C_(2)...Efficient removal of antibiotics is of great significance for the sustainability of aquatic ecosystems.In this work,a new polyoxometalate-based metal-organic hybrid material[Ag_(3)L_(0.5)(HSiW_(12)O_(4)0)]·2C_(2)H_(5)OH·2CH_(3)CN(Ag-L-SiW_(12))was prepared by using Keggin-type polyoxometalate anion and thiacalix[4]arene-based ligand(L)via solvothermal method.Subsequently,a composite heterojunction Ag-L-SiW_(12)@BiVO_(4)photoanode was fabricated by loading Ag-L-SiW_(12)on the surface of BiVO_(4).The photoelectrocatalytic degradation performance of ciprofloxacin(CIP)was explored under the simulated solar radiation.Remarkably,the CIP degradation efficiency reached 93%within 240 min using the optimal Ag-LSiW_(12)@BiVO_(4)photoanode,which is approximately 2 and 23 times those of pristine BiVO_(4)and Ag-L-SiW_(12),respectively.Furthermore,density functional theory(DFT)calculations were conducted to elucidate the role of Ag-L-SiW_(12)during the photoelectrocatalytic process.This work offers an example of the efficient composite photoelectrocatalysts for the treatment of antibiotic wastewater.展开更多
The indiscriminate use and disposal of ciprofloxacin(CIP)have led to its detection in water globally,which pose a huge risk to public health and water environment.Herein,(Zn-Al)LDHs modified 3D reduced graphene oxide ...The indiscriminate use and disposal of ciprofloxacin(CIP)have led to its detection in water globally,which pose a huge risk to public health and water environment.Herein,(Zn-Al)LDHs modified 3D reduced graphene oxide nanocomposite((Zn-Al)LDHs/3D-rGO)was synthesized through a feasible onepot hydrothermal method for CIP removal.The highly distributed(Zn-Al)LDHs flakes on the surface of 3D-rGO endow the resulted(Zn-Al)LDHs/3D-rGO with an excellent adsorption performance for CIP.The adsorption results showed that the adsorption process could be well interpreted by Temkin isothermal model and the pseudo second-order kinetics model.The maximal adsorption capacity of 20.01 mg·g^(-1)for CIP could be achieved under the optimal conditions optimized by response surface methodology(RSM).The inhibitory effect of co-existing ions on CIP adsorption were also discussed.The probable adsorption mechanism might be ascribed toπ-πinteractions,hydrogen bonding,electrostatic,and surface complexation.Regeneration tests showed that the obtained 3D porous material also possessed pronounced recyclability.The obtained(Zn-Al)LDHs/3D-rGO holds a great potential for removal of CIP from actual wastewater.展开更多
Addressing the contamination of antibiotics has attracted ever-increasing and imperative attention due to their widespread existence,easy-to-cause drug-resistant bacteria infection,coupled with their intrinsic toxicit...Addressing the contamination of antibiotics has attracted ever-increasing and imperative attention due to their widespread existence,easy-to-cause drug-resistant bacteria infection,coupled with their intrinsic toxicity and hazard to environments and human health.Herein,a novel CC/CoNi-LDH-10%Ce anode material was directly constructed through a simple and rapid electrodeposition strategy,serving as an efficacious electrocatalyst for removing ciprofloxacin(CIP)from aqueous solution.Such novel CC/CoNi-LDH-10%Ce anode delivered a higher charge transfer,relatively abundant oxygen vacancies,and a higher electrochemical active area.The as-fabricated CC/CoNi-LDH-10%Ce electrode achieved a substantially boosted CIP removal efficiency of 52.5%relative to that of pure CC at about 23.9%.Notably,doping an appropriate amount of Ce^(3+)can endow the pristine CC/CoNi-LDH with richer oxygen vacancies and excellent electrocatalytic performance.Additionally,the electrocatalytic oxidation of CIP was attributed to both direct oxidation on the electrode surface and indirect oxidation induced by the generated active species(superoxide radicals and hydroxyl radicals).This study provides a simple,universal and flexible tactic for other researchers in designing and manufacturing avenues of electrodes.展开更多
Piezoelectric effect,plasma effect and semiconductor heterostructure are important strategies for enhanced photocatalytic performance.Herein,we developed a novel heterostructure piezoelectric photocatalyst,Ag/Ag_(2)S/...Piezoelectric effect,plasma effect and semiconductor heterostructure are important strategies for enhanced photocatalytic performance.Herein,we developed a novel heterostructure piezoelectric photocatalyst,Ag/Ag_(2)S/BiFeO_(3)(AAS/BFO),for photocatalytic degradation of ciprofloxacin from water.Experimental results verified the enhancement of combining heterostructure piezoelectric polarization effect,which promotes efficient migration and separation of photogenerated carriers due to the localized surface plasmon resonance effect of Ag nanoparticles.Additionally,the introduction of Ag_(2)S constructs a new heterostructure,that enhances the electron transport rate and improves the separation efficiency on electron-hole pairs.Under ultrasonic stimulation and visible light irradiation,the degradation efficiencies of 15%-AAS/BFO towards ciprofloxacin,methyl orange and methylene blue are significantly enhanced compared to pure BFO fibers.The demonstrated AAS/BFO material based on the synergistic piezoelectric effect and plasmon heterostructure shows potential in efficient organic pollutants water treatment and transforming mechanical energy into chemical energy.展开更多
Piezo-photocatalysis is an emerging photocatalytic technology in which the piezoelectric electric field drives photogenerated carriers to separate,thereby improving the photocatalytic activity of the catalyst.Herein,s...Piezo-photocatalysis is an emerging photocatalytic technology in which the piezoelectric electric field drives photogenerated carriers to separate,thereby improving the photocatalytic activity of the catalyst.Herein,solid phase and one-step molten salt processes were used to prepare SrBi_(2)Nb_(2)O_(9)(SBN)powders with granular and sheet morphologies,respectively.The influence of micromorphology on the piezo-photocatalytic performances of SBN was determined by degrading ciprofloxacin hydrochloride(CIP).SBN nanosheets demonstrate remarkable piezo-photocatalytic performance,achieving an 89.13%CIP degradation rate in 60 min and an apparent rate constant of 34.73×10^(-3) min^(-1).This performance is approximately 2.65 times higher than that of granular SBN and outperformed many recently reported piezo-photocatalysts under similar experimental conditions.Free radical trapping techniques,electron spin resonance spectroscopy and liquid chromatography-mass spectrometry are utilized to study the potential paths and mechanisms of CIP degradation.Piezoresponse force microscopy and finite element simulation show that the piezo-response of SBN nanosheets is significantly higher than that of granular SBN.SBN nanosheets achieve high degradation efficiency due to their optimized conduction band positions and enhanced piezoelectric effect,facilitated by the two-dimensional nanosheet structures.In this work,the piezoelectric internal electric field of piezoelectric catalysts can be increased by tuning the catalyst morphology,which points to a possible direction for the production of high-performance piezoelectric catalysts.展开更多
The photo-assisted Fenton-like method is an effective and sustainable way to remove organic pollutants from water.Herein,a series of three-dimensional composites containing MIL-88A(Fe)-derived α-Fe_(2)O_(3)and graphe...The photo-assisted Fenton-like method is an effective and sustainable way to remove organic pollutants from water.Herein,a series of three-dimensional composites containing MIL-88A(Fe)-derived α-Fe_(2)O_(3)and graphene aerogel(GA-Fe-X)were designed and used as catalysts to degrade ciprofloxacin(CIP)by peroxymonosulfate(PMS)activated photo-Fenton-like technology.The as-prepared GA-Fe-1 displayed remarkable enhancement with a CIP degradation rate constant(0.017 min^(-1))higher than that of graphene aerogel(0.0031 min^(-1))and MIL-88A(Fe)(0.0039 min^(-1)).Experimental results demonstrated that the combination of MIL-88A(Fe)-derived α-Fe_(2)O_(3)and graphene aerogel forming GA-Fe-X enhanced the separation efficiency of electron-hole pairs,activating PMS to produce SO_(4)^(·-),^(·)OH and ^(1)O_(2) for enhanced CIP degradation through radical and non-radical pathways.The factors affecting CIP degradation during the photoFenton-like process were thoroughly investigated.The possible CIP degradation pathways and ecotoxicity of the intermediates were also analyzed.This work enhances our understanding of the photo-Fenton-like effect in three-dimensional graphene aerogel composites.展开更多
Aim Ciprofloxacin polylactic acid microspheres (CFX-PLA-MS) were preparedusing solvent evaporation method from a solid-in-oil-in-water emulsion system. Methods Orthogonalexperiment was used to optimize the method of C...Aim Ciprofloxacin polylactic acid microspheres (CFX-PLA-MS) were preparedusing solvent evaporation method from a solid-in-oil-in-water emulsion system. Methods Orthogonalexperiment was used to optimize the method of CFX-PLA-MS preparation. Microspheres werecharacterized in terms of morphology, size, encapsulation efficiency, drug loading and in vitro drugrelease. Results The physical state of CFX-PLA-MS was determined by scanning electron microscopy(SEM) and differential scanning calorimetry (DSC) . Microspheres formed were spherical with smoothsurfaces. Drug was enveloped in microspheres without mixing physically with PLA. The averageparticle size was 280.80 ± 0.15 μm, with over 90% of microspheres falling in the range of 250 -390 μm. The encapsulation efficiency was 65.8% ± 0.58% and the drug loading was 34.1% ± 0.51% .In vitro release study revealed a profile of sustained release of Ciprofloxacin from CFX-PLA-MS. Theaccumulated release percentage and half-life (T_(1/2) of Ciprofloxacin microspheres were 84.0% in53.2 h, and 31.9 h, respectively. Higuchi equation was Q= -0.0043 + 0.003 9 t^(1/2), r = 0.9941.Conclusion Ciprofloxacin microspheres have been successfully prepared and sustained release of CFXfrom microspheres is achieved.展开更多
This paper describes an effective method for determining ciprofloxacin lactate. An excess of sodium tetraphenylboron was added to precipitate ciprofloxacin lactate in HAc-NaAc buffer solution (pH=4.0). After filtering...This paper describes an effective method for determining ciprofloxacin lactate. An excess of sodium tetraphenylboron was added to precipitate ciprofloxacin lactate in HAc-NaAc buffer solution (pH=4.0). After filtering off the precipitate, the excessive sodium tetraphenylboron in the filtrate was titrated with cetyltrimethylammonium bromide standard solution, with bromophenol blue as indicator. The method is simple and rapid, it has been applied to the determination of ciprofloxacin lactate raw material with satisfactory results. The recovery was between 99.66% and 100.2%, the relative error was less than ±0.40%. Experiments showed that the method gave the same results as the approach using nonaqueous titration (ChP).展开更多
Modified 1-ethyl-3-(3-dimethylaminopropy) carbodiimide(EDC) method was employed to synthesize the artificial antigen of enrofloxacin(ENR),and New Zealand rabbits were used to produce anti-ENR polyclonal antibody(pAb)....Modified 1-ethyl-3-(3-dimethylaminopropy) carbodiimide(EDC) method was employed to synthesize the artificial antigen of enrofloxacin(ENR),and New Zealand rabbits were used to produce anti-ENR polyclonal antibody(pAb).Based on the checkerboard titration,an indirect competitive enzyme-linked immunosorbent assay(ELISA) standard curve was established.This assay was sensitive and had a linear range from 0.6 to 148.0 μg/kg(R2=0.9567),with the half maximal inhibitory concentration(IC50) and limit of detection(LOD) values of 9.4 μg/kg and 0.2 μg/kg,respectively.Of all the competitive analogues,the produced pAb exhibited a high cross-reactivity to ciprofloxacin(CIP)(87%),the main metabolite of ENR in tissues.After optimization,the matrix effects can be ignored using a 10-fold dilution in beef and 20-fold dilution in pork.The overall recoveries and coefficients of variation(CVs) were in the ranges of 86%-109% and 6.8%-13.1%,respectively.It can be concluded that the established ELISA method is suitable for simultaneous detection of ENR and CIP in animal tissues.展开更多
A chemically prepared carbon was synthesized from date palm leaflets via sulphuric acid carbonization at 160℃. Adsorption of ciprofloxacin （CIP） from aqueous solution was investigated in terms of time, pH, concentr...A chemically prepared carbon was synthesized from date palm leaflets via sulphuric acid carbonization at 160℃. Adsorption of ciprofloxacin （CIP） from aqueous solution was investigated in terms of time, pH, concentration, temperature and adsorbent status （wet and dry）. The equilibrium time was found to be 48 hr. The adsorption rate was enhanced by raising the temperature for both adsorbents, with adsorption data fitting a pseudo second-order model well. The activation energy, Ea, was found to be 17 kJ/mol, indicating a diffusion-controlled, physical adsorption process. The maximum adsorption was found at initial pH 6. The wet adsorbent showed faster removal with higher uptake than the dry adsorbent, with increased performance as temperature increased （25--45℃）. The equilibrium data were found to fit the Langmuir model better than the Freundlich model. The thermodynamic parameters showed that the adsorption process is spontaneous and endothermic. The adsorption mechanism is mainly related to cation exchange and hydrogen bonding.展开更多
In this study, used tea leaves （UTLs） were pyrolyzed to obtain used tea-leaf biochar （UTC）, and then the UTC was used as an adsorbent to remove ciprofioxacin （CIP） from aqueous solutions. Batch experiments were ...In this study, used tea leaves （UTLs） were pyrolyzed to obtain used tea-leaf biochar （UTC）, and then the UTC was used as an adsorbent to remove ciprofioxacin （CIP） from aqueous solutions. Batch experiments were conducted to investigate the CIP adsorption performance and mechanism. The results showed that the CIP-adsorbing ability first increased and then declined as the UTC pyrolysis temperature increased. The UTC obtained at 450℃ presented excellent CIP-absorbing ability at pH 6 and 40℃. The maximum monolayer adsorption capacity was 238.10 mg/g based on the Langrnuir isotherm model. The pseudo-second-order kinetic equation agreed well with the CIP adsorption process, which was controlled by both external boundary layer diffusion and intra-particle diffusion. The characterization analysis revealed that the - OH groups, G=C bonds of aromatic rings, C- H groups in aromatic tings and phenolic C - O bonds play vital roles in the CIP adsorption process, and that the N - C, N - O, O- C-O and C- OH groups of UTC were consumed in large quantities. π-π interactions, hydrogen bonding and electrostatic attraction are inferred as the main adsorption mechanisms. The present work provides not only a feasible and promising approach for UTLs utilization but also a potential adsorbent material for removing high concentrations of CIP from aqueous solutions.展开更多
A convenient competitive enzyme-linked immunosorbent assay(ELISA) for ciprofloxacin(CPFX) was developed by using rabbit monoclonal antibodies(RabMAbs) against a hapten-protein conjugate of CPFX-bovine serum albumin(BS...A convenient competitive enzyme-linked immunosorbent assay(ELISA) for ciprofloxacin(CPFX) was developed by using rabbit monoclonal antibodies(RabMAbs) against a hapten-protein conjugate of CPFX-bovine serum albumin(BSA).The indirect competitive ELISA of CPFX had a concentration at 50% inhibition(IC50) of 1.47 ng/ml and a limit of detection(LOD) of 0.095 ng/ml.The mAb exhibited some cross-reactivity,however,not so high with enrofloxacin(28.8%),ofloxacin(13.1%),norfloxacin(11.0%),fleroxacin(22.6%),and pefloxacin(20.4%).And it showed almost no cross-reactivity with other antibiotics or sulfonamides evaluated in this study.The competitive ELISA kit developed here could be used as a screening tool to detect and control illegal addition of CPFX in food products.This kit had been applied to milk detection and the recovery rates from samples spiked by CPFX were in a range of 63.02%-84.60%,with coefficients of variation of less than 12.2%.展开更多
Turbot Scophthalmus maximus, an important aquaculture species in China, currently suffers from epizootic diseases because of high density aquaculture. Enrofloxacin has been used to treat various systemic bacterial fis...Turbot Scophthalmus maximus, an important aquaculture species in China, currently suffers from epizootic diseases because of high density aquaculture. Enrofloxacin has been used to treat various systemic bacterial fish infections. However, studies concerning the pharmacokinetics of enrofloxacin in turbot are limited. In this study, the pharmacokinetics of enrofloxacin and its metabolite ciprofloxacin, were investigated in the turbot following intravenous and oral administration at 10 mg enrofloxacin/kg body weight, at 16℃ and 10℃ water temperatures. The concentrations of enrofloxacin and ciprofloxacin in the main tissues （plasma, muscle, liver and kidney） were detected by HPLC. The results show that the plasma concentration-time data for enrofloxacin were best described as a two-compartment open model after intravenous and oral administration. Three pharmacokinetic equations were established between the concentrations and temperatures. The kinetic profile of enrofloxacin was temperature dependent. The absorption half-life of enrofloxacin was 1.99 h and 2.17 h after oral administration, whereas the elimination half-life of the drug was 98.63 h and 136.59 h at 16℃ and 10℃, respectively. The peak concentration of enrofloxacin in plasma and tissues was higher at 16℃ than that at 10℃, and the peak plasma concentration time in the liver was the shortest at both temperatures among those of other tissues. The plasma ℃/MIC ratio varied between 11.08 and 5 540.00 at 16℃; and between 7.92 and 3 960.00 at 10℃. The AUC/MIC ratio was 467.82-280 690.00 at 16℃, and 359.48-215 690.00 at 10℃. These ratios indicate that it is possible to obtain therapeutic efficacy. Very low levels of ciprofloxacin were detected. The AUC ratios of ciprofloxacin and enrofloxacin in plasma suggest that plasma ciprofloxacin might play a minor role in enrofloxacin treatment for turbot.展开更多
基金supported by the National Key Research and Development Program of China(Grants No.2021YFC2902701,2021YFC2902100,2019YFC1805600,2018YFC1801800)the Fundamental Research Funds for the Central Universities(Grant No.2022QN1051)+1 种基金the Shandong Provincial Major Science and Technology Innovation Project(Grant No.2021CXGC011206)the Key Project of the National Natural Science Foundation of China(Grant No.52130402).
文摘Degrading ciprofloxacin(CIP)-polluted water has recently emerged as an urgent environmental issue.This study introduced mechanochemical treatment(MCT)as an innovative and underexplored approach for the degradation of CIP in water.The influence of various additives(CaO,Fe_(2)O_(3),SiO_(2),Al,and Fe)on CIP degradation efficiency was investigated.Additionally,six types of composite additives(Fe-CaO,Fe-Fe_(2)O_(3),Fe-SiO_(2),Fe-Al,Al-SiO_(2),and Al-CaO)were explored,with the composite of 20%Fe and 80%SiO_(2) exhibiting notable performance.The impacts of additive content,pH value,and co-existing ions on CIP degradation efficiency were investigated.Furthermore,the effectiveness of MCT in degrading other medical pollutants(norfloxacin,ofloxacin,and enrofloxacin)was verified.The transformations and changes in the crystal structure,oxidation state,microstructure,and morphology of the Fe-SiO_(2) composite additive were characterized using X-ray diffraction,X-ray photoelectron spectroscopy,and scanning electron microscopy techniques.This study proposed a sigmoid trend kinetic model(the Delogu model)that better elucidates the MCT process.Three plausible degradation pathways were discussed based on intermediate substance identification and pertinent literature.This study not only establishes a pathway for the facile degradation of CIP pollutants through MCT but also contributes to advancements in wastewater treatment methodologies.
基金the National Key Research and Development Program of China(Nos.2021YFA1202500 and 2022YFF1303004)Shenzhen Science and Technology Program(No.JCYJ20220531093205013)+6 种基金the National Natural Science Foundation of China(NSFC)(Nos.52100069,52270053 and 52200084)the Beijing Natural Science Foundation(No.8232035),the Beijing Nova Program(No.20220484215)the Beijing National Laboratory for Molecular Sciences(No.BNLMS2023011)Emerging Engineering Interdisciplinary-Young Scholars Project(Peking University),the Fundamental Research Funds for the Central Universities are greatly acknowledgedsupported by the High-Performance Computing Platform of Peking Universitythe National Key Scientific and Technological Infrastructure project“Earth System Numerical Simulation Facility”(EarthLab)are also acknowledgedsupported by the program of“Research on Advanced Treatment Technology of New Pollutants in Domestic Sewage of Residential District”.
文摘Simultaneous degradation and detoxification during pharmaceutical and personal care product removal are important for water treatment.In this study,sodium niobate nanocubes decorated with graphitic carbon nitride(NbNC/g-C_(3)N_(4))were fabricated to achieve the efficient photocatalytic degradation and detoxification of ciprofloxacin(CIP)under simulated solar light.NaNbO_(3)nanocubes were in-situ transformed from Na_(2)Nb_(2)O_(6)·H_(2)O via thermal dehydration at the interface of g-C_(3)N_(4).The optimized NbNC/g-C_(3)N_(4)-1 was a type-I heterojunction,which showed a high conduction band(CB)level of−1.68 eV,leading to the efficient transfer of photogenerated electrons to O_(2) to produce primary reactive species,•O_(2)^(-).Density functional theory(DFT)calculations of the density of states indicated that C 2p and Nb 3d contributed to the CB,and 0.37 e^(-)transferred from NaNbO_(3)to g-C_(3)N_(4)in NbNC/g-C_(3)N_(4)based on the Mulliken population analysis of the built-in electric field intensity.NbNC/g-C_(3)N_(4)-1 had 3.3-and 2.3-fold of CIP degradation rate constants(k_(1)=0.173 min^(−1))compared with those of pristine g-C_(3)N_(4)and NaNbO_(3),respectively.In addition,N24,N19,and C5 in CIP with a high Fukui index were reactive sites for electrophilic attack by•O_(2)^(-),resulting in the defluorination and ring-opening of the piperazine moiety of the dominant degradation pathways.Intermediate/product identification,integrated with computational toxicity evaluation,further indicated a substantial detoxification effect during CIP degradation in the photocatalysis system.
基金The National Key Research and Development Program of China(2020YFD1100501).
文摘The synergistic degradation of contaminants in water by photocatalysis and peroxydisulfate(PDS)activation has been proven to be a promising combined advanced oxidation technology.Consequently,the development of highly efficient photocatalysts that are activated by visible light and PDS is of immense importance.Herein,different proportions of cobalt-doped Bi_(2)Fe_(4)O_(9)(BFO@Co-x)photocatalysts were effectively synthesized for elimination of ciprofloxacin(CIP).The degradation efficiency of CIP achieved by the BFO@Co/Vis/PDS system attained 84.49%(k=0.0516 min−1)under 40 min light irradiation,outperforming the BFO@Co/Vis and PDS/Vis systems by a factor of 1.45 and 3.6,respectively.Characterization and photoelectric performance assessments revealed that the fabrication of BFO@Co-0.5 was successful,enhancing the photocatalytic degradation efficiency under the synergistic effect of PDS.Moreover,the BFO@Co/Vis/PDS system demonstrated favorable adaptability to various pH,inorganic anions,and humic acid in solution.Additionally,the degradation pathways of CIP and the toxicity of products were evaluated using LC/MS and T.E.S.T software,indicating a reduction in the toxicity of CIP degradation products.This study may provide insights into the application of photocatalyst/Vis/PDS combined systems in the field of water environmental treatment.
基金supported by the Project of Key R&D Program of Shandong Province(2023CXGC010712).Geoffrey I.N.
文摘In this work,a novel electrochemical sensor based on covalent organic framework@carbon black@molecularly imprinted polydopamine(COF@CB@MPDA)was developed for selective recognition and determination of ciprofloxacin(CF).COF@CB@MPDA possessed good water dispersibility and was synthesized by the selfpolymerization of dopamine under alkaline conditions in the presence of the COF,CB and CF.The high surface area COF enhanced the adsorption of CF,whilst CB gave the composites high electrical conductivity to improve the sensitivity of the proposed COF@CB@MPDA/glassy carbon electrode(GCE)sensor.The specific recognition of CF by COF@CB@MPDA involved hydrogen bonding and van der Waals interactions.Under optimized conditions,the sensor showed a good linear relationship with CF concentration over the range of 5.0×10^(–7)and 1.0×10^(–4)mol/L,with a limit of detection(LOD)of 9.53×10^(–8)mol/L.Further,the developed sensor exhibited high selectivity,repeatability and stability for CF detection in milk and milk powders.The method used to fabricate the COF@CB@MPDA/GCE sensor could be easily adapted for the selective recognition and detection of other antibacterial agents and organic pollutants in the environment.
基金supported by the National Natural Science Foundation of China(Grant No.21471029).
文摘Efficient removal of antibiotics is of great significance for the sustainability of aquatic ecosystems.In this work,a new polyoxometalate-based metal-organic hybrid material[Ag_(3)L_(0.5)(HSiW_(12)O_(4)0)]·2C_(2)H_(5)OH·2CH_(3)CN(Ag-L-SiW_(12))was prepared by using Keggin-type polyoxometalate anion and thiacalix[4]arene-based ligand(L)via solvothermal method.Subsequently,a composite heterojunction Ag-L-SiW_(12)@BiVO_(4)photoanode was fabricated by loading Ag-L-SiW_(12)on the surface of BiVO_(4).The photoelectrocatalytic degradation performance of ciprofloxacin(CIP)was explored under the simulated solar radiation.Remarkably,the CIP degradation efficiency reached 93%within 240 min using the optimal Ag-LSiW_(12)@BiVO_(4)photoanode,which is approximately 2 and 23 times those of pristine BiVO_(4)and Ag-L-SiW_(12),respectively.Furthermore,density functional theory(DFT)calculations were conducted to elucidate the role of Ag-L-SiW_(12)during the photoelectrocatalytic process.This work offers an example of the efficient composite photoelectrocatalysts for the treatment of antibiotic wastewater.
基金support from Basic research project of Education Department of Liaoning Province(LJKZ0256)Special Fund for Basic Scientific Research of Liaoning Province(LJKZSYLUGX027).
文摘The indiscriminate use and disposal of ciprofloxacin(CIP)have led to its detection in water globally,which pose a huge risk to public health and water environment.Herein,(Zn-Al)LDHs modified 3D reduced graphene oxide nanocomposite((Zn-Al)LDHs/3D-rGO)was synthesized through a feasible onepot hydrothermal method for CIP removal.The highly distributed(Zn-Al)LDHs flakes on the surface of 3D-rGO endow the resulted(Zn-Al)LDHs/3D-rGO with an excellent adsorption performance for CIP.The adsorption results showed that the adsorption process could be well interpreted by Temkin isothermal model and the pseudo second-order kinetics model.The maximal adsorption capacity of 20.01 mg·g^(-1)for CIP could be achieved under the optimal conditions optimized by response surface methodology(RSM).The inhibitory effect of co-existing ions on CIP adsorption were also discussed.The probable adsorption mechanism might be ascribed toπ-πinteractions,hydrogen bonding,electrostatic,and surface complexation.Regeneration tests showed that the obtained 3D porous material also possessed pronounced recyclability.The obtained(Zn-Al)LDHs/3D-rGO holds a great potential for removal of CIP from actual wastewater.
基金the funds granted by the Ningxia Natural Science Foundation(2023AAC05003,2024AAC03048,2024AAC03051)the National Natural Science Foundation of China(22108130,22368039)+1 种基金the Ningxia Key Research&Development Program(2023BDE03001)the Ningxia Overseas Returnee Innovation and Entrepreneurship Project for the financial support。
文摘Addressing the contamination of antibiotics has attracted ever-increasing and imperative attention due to their widespread existence,easy-to-cause drug-resistant bacteria infection,coupled with their intrinsic toxicity and hazard to environments and human health.Herein,a novel CC/CoNi-LDH-10%Ce anode material was directly constructed through a simple and rapid electrodeposition strategy,serving as an efficacious electrocatalyst for removing ciprofloxacin(CIP)from aqueous solution.Such novel CC/CoNi-LDH-10%Ce anode delivered a higher charge transfer,relatively abundant oxygen vacancies,and a higher electrochemical active area.The as-fabricated CC/CoNi-LDH-10%Ce electrode achieved a substantially boosted CIP removal efficiency of 52.5%relative to that of pure CC at about 23.9%.Notably,doping an appropriate amount of Ce^(3+)can endow the pristine CC/CoNi-LDH with richer oxygen vacancies and excellent electrocatalytic performance.Additionally,the electrocatalytic oxidation of CIP was attributed to both direct oxidation on the electrode surface and indirect oxidation induced by the generated active species(superoxide radicals and hydroxyl radicals).This study provides a simple,universal and flexible tactic for other researchers in designing and manufacturing avenues of electrodes.
基金supported by the National Natural Science Foundation of China(Nos.52372090 and 52073177)the National Natural Science Foundation of Guangdong,China(No.2023A1515010947)Shenzhen Basic Research Program(No.JCYJ20220531102207017).
文摘Piezoelectric effect,plasma effect and semiconductor heterostructure are important strategies for enhanced photocatalytic performance.Herein,we developed a novel heterostructure piezoelectric photocatalyst,Ag/Ag_(2)S/BiFeO_(3)(AAS/BFO),for photocatalytic degradation of ciprofloxacin from water.Experimental results verified the enhancement of combining heterostructure piezoelectric polarization effect,which promotes efficient migration and separation of photogenerated carriers due to the localized surface plasmon resonance effect of Ag nanoparticles.Additionally,the introduction of Ag_(2)S constructs a new heterostructure,that enhances the electron transport rate and improves the separation efficiency on electron-hole pairs.Under ultrasonic stimulation and visible light irradiation,the degradation efficiencies of 15%-AAS/BFO towards ciprofloxacin,methyl orange and methylene blue are significantly enhanced compared to pure BFO fibers.The demonstrated AAS/BFO material based on the synergistic piezoelectric effect and plasmon heterostructure shows potential in efficient organic pollutants water treatment and transforming mechanical energy into chemical energy.
基金funded by the National Natural Science Foundation of China(22272057)Natural Science Foundation of Guangdong Province(2019A1515012129)Science and Technology Planning Project of Guangzhou City(202002030420).
文摘Piezo-photocatalysis is an emerging photocatalytic technology in which the piezoelectric electric field drives photogenerated carriers to separate,thereby improving the photocatalytic activity of the catalyst.Herein,solid phase and one-step molten salt processes were used to prepare SrBi_(2)Nb_(2)O_(9)(SBN)powders with granular and sheet morphologies,respectively.The influence of micromorphology on the piezo-photocatalytic performances of SBN was determined by degrading ciprofloxacin hydrochloride(CIP).SBN nanosheets demonstrate remarkable piezo-photocatalytic performance,achieving an 89.13%CIP degradation rate in 60 min and an apparent rate constant of 34.73×10^(-3) min^(-1).This performance is approximately 2.65 times higher than that of granular SBN and outperformed many recently reported piezo-photocatalysts under similar experimental conditions.Free radical trapping techniques,electron spin resonance spectroscopy and liquid chromatography-mass spectrometry are utilized to study the potential paths and mechanisms of CIP degradation.Piezoresponse force microscopy and finite element simulation show that the piezo-response of SBN nanosheets is significantly higher than that of granular SBN.SBN nanosheets achieve high degradation efficiency due to their optimized conduction band positions and enhanced piezoelectric effect,facilitated by the two-dimensional nanosheet structures.In this work,the piezoelectric internal electric field of piezoelectric catalysts can be increased by tuning the catalyst morphology,which points to a possible direction for the production of high-performance piezoelectric catalysts.
基金National Natural Science Foundation of China(Nos.12075152,42177405,12075147)for the financial support。
文摘The photo-assisted Fenton-like method is an effective and sustainable way to remove organic pollutants from water.Herein,a series of three-dimensional composites containing MIL-88A(Fe)-derived α-Fe_(2)O_(3)and graphene aerogel(GA-Fe-X)were designed and used as catalysts to degrade ciprofloxacin(CIP)by peroxymonosulfate(PMS)activated photo-Fenton-like technology.The as-prepared GA-Fe-1 displayed remarkable enhancement with a CIP degradation rate constant(0.017 min^(-1))higher than that of graphene aerogel(0.0031 min^(-1))and MIL-88A(Fe)(0.0039 min^(-1)).Experimental results demonstrated that the combination of MIL-88A(Fe)-derived α-Fe_(2)O_(3)and graphene aerogel forming GA-Fe-X enhanced the separation efficiency of electron-hole pairs,activating PMS to produce SO_(4)^(·-),^(·)OH and ^(1)O_(2) for enhanced CIP degradation through radical and non-radical pathways.The factors affecting CIP degradation during the photoFenton-like process were thoroughly investigated.The possible CIP degradation pathways and ecotoxicity of the intermediates were also analyzed.This work enhances our understanding of the photo-Fenton-like effect in three-dimensional graphene aerogel composites.
基金National Natural Science Foundation of Guangdong Province (020885,980504).
文摘Aim Ciprofloxacin polylactic acid microspheres (CFX-PLA-MS) were preparedusing solvent evaporation method from a solid-in-oil-in-water emulsion system. Methods Orthogonalexperiment was used to optimize the method of CFX-PLA-MS preparation. Microspheres werecharacterized in terms of morphology, size, encapsulation efficiency, drug loading and in vitro drugrelease. Results The physical state of CFX-PLA-MS was determined by scanning electron microscopy(SEM) and differential scanning calorimetry (DSC) . Microspheres formed were spherical with smoothsurfaces. Drug was enveloped in microspheres without mixing physically with PLA. The averageparticle size was 280.80 ± 0.15 μm, with over 90% of microspheres falling in the range of 250 -390 μm. The encapsulation efficiency was 65.8% ± 0.58% and the drug loading was 34.1% ± 0.51% .In vitro release study revealed a profile of sustained release of Ciprofloxacin from CFX-PLA-MS. Theaccumulated release percentage and half-life (T_(1/2) of Ciprofloxacin microspheres were 84.0% in53.2 h, and 31.9 h, respectively. Higuchi equation was Q= -0.0043 + 0.003 9 t^(1/2), r = 0.9941.Conclusion Ciprofloxacin microspheres have been successfully prepared and sustained release of CFXfrom microspheres is achieved.
文摘This paper describes an effective method for determining ciprofloxacin lactate. An excess of sodium tetraphenylboron was added to precipitate ciprofloxacin lactate in HAc-NaAc buffer solution (pH=4.0). After filtering off the precipitate, the excessive sodium tetraphenylboron in the filtrate was titrated with cetyltrimethylammonium bromide standard solution, with bromophenol blue as indicator. The method is simple and rapid, it has been applied to the determination of ciprofloxacin lactate raw material with satisfactory results. The recovery was between 99.66% and 100.2%, the relative error was less than ±0.40%. Experiments showed that the method gave the same results as the approach using nonaqueous titration (ChP).
基金supported by the Henan Innovation Project for University Prominent Research Talents (No. 2010HASTIT026)the Key Scientific & Technological Project of Education Department in Henan Province of China (No. 2011A230003)
文摘Modified 1-ethyl-3-(3-dimethylaminopropy) carbodiimide(EDC) method was employed to synthesize the artificial antigen of enrofloxacin(ENR),and New Zealand rabbits were used to produce anti-ENR polyclonal antibody(pAb).Based on the checkerboard titration,an indirect competitive enzyme-linked immunosorbent assay(ELISA) standard curve was established.This assay was sensitive and had a linear range from 0.6 to 148.0 μg/kg(R2=0.9567),with the half maximal inhibitory concentration(IC50) and limit of detection(LOD) values of 9.4 μg/kg and 0.2 μg/kg,respectively.Of all the competitive analogues,the produced pAb exhibited a high cross-reactivity to ciprofloxacin(CIP)(87%),the main metabolite of ENR in tissues.After optimization,the matrix effects can be ignored using a 10-fold dilution in beef and 20-fold dilution in pork.The overall recoveries and coefficients of variation(CVs) were in the ranges of 86%-109% and 6.8%-13.1%,respectively.It can be concluded that the established ELISA method is suitable for simultaneous detection of ENR and CIP in animal tissues.
文摘A chemically prepared carbon was synthesized from date palm leaflets via sulphuric acid carbonization at 160℃. Adsorption of ciprofloxacin （CIP） from aqueous solution was investigated in terms of time, pH, concentration, temperature and adsorbent status （wet and dry）. The equilibrium time was found to be 48 hr. The adsorption rate was enhanced by raising the temperature for both adsorbents, with adsorption data fitting a pseudo second-order model well. The activation energy, Ea, was found to be 17 kJ/mol, indicating a diffusion-controlled, physical adsorption process. The maximum adsorption was found at initial pH 6. The wet adsorbent showed faster removal with higher uptake than the dry adsorbent, with increased performance as temperature increased （25--45℃）. The equilibrium data were found to fit the Langmuir model better than the Freundlich model. The thermodynamic parameters showed that the adsorption process is spontaneous and endothermic. The adsorption mechanism is mainly related to cation exchange and hydrogen bonding.
基金the financial support of the Industry Leading Key Projects of Fujian Province(No.2015H0044)the Key Project of Young Talent of Institute of Urban Environment,Chinese Academy of Sciences(No.IUEZD201402)+1 种基金the China-Japanese Research Cooperative Program(No.2016YFE0118000)the Scientific and Technological Major Special Project of Tianjin City(No.16YFXTSF00420)
文摘In this study, used tea leaves （UTLs） were pyrolyzed to obtain used tea-leaf biochar （UTC）, and then the UTC was used as an adsorbent to remove ciprofioxacin （CIP） from aqueous solutions. Batch experiments were conducted to investigate the CIP adsorption performance and mechanism. The results showed that the CIP-adsorbing ability first increased and then declined as the UTC pyrolysis temperature increased. The UTC obtained at 450℃ presented excellent CIP-absorbing ability at pH 6 and 40℃. The maximum monolayer adsorption capacity was 238.10 mg/g based on the Langrnuir isotherm model. The pseudo-second-order kinetic equation agreed well with the CIP adsorption process, which was controlled by both external boundary layer diffusion and intra-particle diffusion. The characterization analysis revealed that the - OH groups, G=C bonds of aromatic rings, C- H groups in aromatic tings and phenolic C - O bonds play vital roles in the CIP adsorption process, and that the N - C, N - O, O- C-O and C- OH groups of UTC were consumed in large quantities. π-π interactions, hydrogen bonding and electrostatic attraction are inferred as the main adsorption mechanisms. The present work provides not only a feasible and promising approach for UTLs utilization but also a potential adsorbent material for removing high concentrations of CIP from aqueous solutions.
基金Project supported by the National High-Tech R&D Program (863) of China (No. 2007AA10Z436)the Important National Science and Technology Specific Projects of China (No. 2009ZX03012-010B)
文摘A convenient competitive enzyme-linked immunosorbent assay(ELISA) for ciprofloxacin(CPFX) was developed by using rabbit monoclonal antibodies(RabMAbs) against a hapten-protein conjugate of CPFX-bovine serum albumin(BSA).The indirect competitive ELISA of CPFX had a concentration at 50% inhibition(IC50) of 1.47 ng/ml and a limit of detection(LOD) of 0.095 ng/ml.The mAb exhibited some cross-reactivity,however,not so high with enrofloxacin(28.8%),ofloxacin(13.1%),norfloxacin(11.0%),fleroxacin(22.6%),and pefloxacin(20.4%).And it showed almost no cross-reactivity with other antibiotics or sulfonamides evaluated in this study.The competitive ELISA kit developed here could be used as a screening tool to detect and control illegal addition of CPFX in food products.This kit had been applied to milk detection and the recovery rates from samples spiked by CPFX were in a range of 63.02%-84.60%,with coefficients of variation of less than 12.2%.
基金Supported by the National Natural Science Foundation of China(Nos.30700617,31101298)the National Special Research Fund for NonProfit Sector(No.nyhyzx07-046)
文摘Turbot Scophthalmus maximus, an important aquaculture species in China, currently suffers from epizootic diseases because of high density aquaculture. Enrofloxacin has been used to treat various systemic bacterial fish infections. However, studies concerning the pharmacokinetics of enrofloxacin in turbot are limited. In this study, the pharmacokinetics of enrofloxacin and its metabolite ciprofloxacin, were investigated in the turbot following intravenous and oral administration at 10 mg enrofloxacin/kg body weight, at 16℃ and 10℃ water temperatures. The concentrations of enrofloxacin and ciprofloxacin in the main tissues （plasma, muscle, liver and kidney） were detected by HPLC. The results show that the plasma concentration-time data for enrofloxacin were best described as a two-compartment open model after intravenous and oral administration. Three pharmacokinetic equations were established between the concentrations and temperatures. The kinetic profile of enrofloxacin was temperature dependent. The absorption half-life of enrofloxacin was 1.99 h and 2.17 h after oral administration, whereas the elimination half-life of the drug was 98.63 h and 136.59 h at 16℃ and 10℃, respectively. The peak concentration of enrofloxacin in plasma and tissues was higher at 16℃ than that at 10℃, and the peak plasma concentration time in the liver was the shortest at both temperatures among those of other tissues. The plasma ℃/MIC ratio varied between 11.08 and 5 540.00 at 16℃; and between 7.92 and 3 960.00 at 10℃. The AUC/MIC ratio was 467.82-280 690.00 at 16℃, and 359.48-215 690.00 at 10℃. These ratios indicate that it is possible to obtain therapeutic efficacy. Very low levels of ciprofloxacin were detected. The AUC ratios of ciprofloxacin and enrofloxacin in plasma suggest that plasma ciprofloxacin might play a minor role in enrofloxacin treatment for turbot.
