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Journal of Hazardous Materials Mar 2023Sulfate radical (SO)-based heterogonous advanced oxidation processes (AOPs) show promising potential to degrade emerging contaminants, however, regulating the electron...
Modulating the electron structure of Co-3d in CoO/WO for boosting peroxymonosulfate activation and degradation of sulfamerazine: Roles of high-valence W and rich oxygen vacancies.
Sulfate radical (SO)-based heterogonous advanced oxidation processes (AOPs) show promising potential to degrade emerging contaminants, however, regulating the electron structure of a catalyst to promote its catalytic activity is challenging. Herein, a hybrid that consists of CoO nanocrystals decorated on urchin-like WO (CoO/WO) with high-valence W and rich oxygen vacancies (OVs) used to modulate the electronic structure of Co-3d was prepared. The CoO/WO that developed exhibited high catalytic activity, activating peroxymonosulfate (PMS), and degrading sulfamerazine (SMR). With the use of CoO/WO, 100 % degradation of SMR was achieved within 2 min, at a pH of 7, with the reaction rate constant k = 3.09 min. Both characterizations and density functional theory (DFT) calculations confirmed the formation of OVs and the promotion of catalytic activity. The introduction of WO greatly regulated the electronic structure of CoO. Specifically, the introduction of high-valence W enabled the Co-3d band centre to be closer to the Fermi level and enhanced electrons (e) transfer ability, while the introduction of OVs-Co in CoO promoted the activity of electrons in the Co-3d orbital and the subsequent catalytic reaction. The reactive oxygen species (ROS) were identified as •OH, SO, and singlet oxygen (O) by quenching experiments and electron spin resonance (EPR) analysis. The DFT calculation using the Fukui index indicated the reactive sites in SMR were available for an electrophilic attack, and three degradation pathways were proposed.
PubMed: 37055981
DOI: 10.1016/j.jhazmat.2022.130576 -
Talanta Jun 2023In reality, various sulfonamides (SAs) were alternately used in animal husbandry to avoid generating drug resistance. Thus, it is crucial to develop simple and...
In reality, various sulfonamides (SAs) were alternately used in animal husbandry to avoid generating drug resistance. Thus, it is crucial to develop simple and high-throughput methods for detecting multiple or groups of SAs to realize rapid screening of total SAs residues in foods. We herein developed a sensitive and efficient MnO nanosheets-mediated etching of gold nanobipyramids (AuNBPs), which can generate more vivid color changes, and further fabricated a high-throughput multicolor immunosensor for the visual screening/semi-quantitative detection of 6 different SAs including sulfamethazine (SMZ), sulfamethoxydiazine (SMD), sulfisomidine (SIM), sulfamerazine (SMR), sulfamonomethoxine (SMM) and sulfaquinoxaline (SQ) by using AuNBPs as signal and broad-specificity anti-SAs antibody as a bio-receptor. The immunosensor displays more vivid color changes, and has a lower visual detection limit and excellent specificity. It can be applied to detect as little as 1.0 ng/mL of SMZ, SMD, SMR and 2.0 ng/mL of SIM, SMM, SQ by bare eye observation, and 0.2 ng/mL of above 6 SAs by UV-visible spectrophotometry. The visual detection limit of the immunosensor is much lower than the maximum residue limit of total SAs (100 μg/kg) in edible tissues. The immunosensor was successfully applied to detect SMZ, SMD, SIM, SMR, SMM and SQ in milk with a recovery of 84%-106% and a RSD (n = 5) < 8%. The success of this study provided a promising assay for the on-site rapid screening of SMZ, SMD, SIM, SMR, SMM and SQ in food by bare eye observation. Importantly, the immunosensor may be expended as a general method for the visual screening/semi-quantitative detection of the group of other antibiotics by using the corresponding broad-specificity antibody as a bio-receptor.
Topics: Animals; Sulfonamides; Manganese Compounds; Oxides; Gold; Biosensing Techniques; Immunoassay; Sulfanilamide
PubMed: 36924640
DOI: 10.1016/j.talanta.2023.124449 -
Chemosphere Jun 2023The removal of antibiotics in wastewater has attracted increasing attention. Herein, a superior photosensitized photocatalytic system was developed with acetophenone...
The removal of antibiotics in wastewater has attracted increasing attention. Herein, a superior photosensitized photocatalytic system was developed with acetophenone (ACP) as the guest photosensitizer, bismuth vanadate (BiVO) as the host catalyst and poly dimethyl diallyl ammonium chloride (PDDA) as the bridging complex, and used for the removal of sulfamerazine (SMR), sulfadiazine (SDZ) and sulfamethazine (SMZ) in water under simulated visible light (λ > 420 nm). The obtained ACP-PDDA-BiVO nanoplates attained a removal efficiency of 88.9%-98.2% for SMR, SDZ and SMZ after 60 min reaction and achieved kinetic rate constant approximately 10, 4.7 and 13 times of BiVO, PDDA-BiVO and ACP-BiVO, respectively, for SMZ degradation. In the guest-host photocatalytic system, ACP photosensitizer was found to have a great superiority in enhancing the light absorption, promoting the surface charge separation-transfer and efficient generation of holes (h) and superoxide radical (·O), greatly contributing to the photoactivity. The SMZ degradation pathways were proposed based on the identified degradation intermediates, involving three main pathways of rearrangement, desulfonation and oxidation. The toxicity of intermediates was evaluated and the results demonstrated that the overall toxicity was reduced compared with parent SMZ. This catalyst maintained 92% photocatalytic oxidation performance after five cyclic experiments and displayed a co-photodegradation ability to others antibiotics (e.g., roxithromycin, ciprofloxacin et al.) in effluent water. Therefore, this work provides a facile photosensitized strategy for developing guest-host photocatalysts, which enabling the simultaneous antibiotics removal and effectively reduce the ecological risks in wastewater.
Topics: Anti-Bacterial Agents; Photolysis; Photosensitizing Agents; Wastewater; Light; Bismuth; Vanadates; Sulfamethazine; Sulfadiazine; Sulfamerazine; Water; Catalysis
PubMed: 36905996
DOI: 10.1016/j.chemosphere.2023.138362 -
Molecules (Basel, Switzerland) Feb 2023Developing a simple and efficient method for removing organic micropollutants from aqueous systems is crucial. The present study describes the preparation and...
Developing a simple and efficient method for removing organic micropollutants from aqueous systems is crucial. The present study describes the preparation and application, for the first time, of novel MXene-decorated bismuth ferrite nanocomposites (BiFeO/MXene) for the removal of six sulfonamides including sulfadiazine (SDZ), sulfathiazole (STZ), sulfamerazine (SMZ), sulfamethazine (SMTZ), sulfamethoxazole (SMXZ) and sulfisoxazole (SXZ). The properties of BiFeO/MXene are enhanced by the presence of BiFeO nanoparticles, which provide a large surface area to facilitate the removal of sulfonamides. More importantly, BiFeO/MXene composites demonstrated remarkable sulfonamide adsorption capabilities compared to pristine MXene, which is due to the synergistic effect between BiFeO and MXene. The kinetics and isotherm models of sulfonamide adsorption on BiFeO/MXene are consistent with a pseudo-second-order kinetics and Langmuir model. BiFeO/MXene had appreciable reusability after five adsorption-desorption cycles. Furthermore, BiFeO/MXene is stable and retains its original properties upon desorption. The present work provides an effective method for eliminating sulfonamides from water by exploiting the excellent texture properties of BiFeO/MXene.
Topics: Sulfonamides; Bismuth; Sulfanilamide; Water; Nanocomposites; Adsorption; Water Pollutants, Chemical; Kinetics
PubMed: 36838529
DOI: 10.3390/molecules28041541 -
Journal of Hazardous Materials Apr 2023Although the effect of Cu on antibiotic removal during photocatalytic reaction has been studied in depth, there is less known about the effect of antibiotics on Cu...
Although the effect of Cu on antibiotic removal during photocatalytic reaction has been studied in depth, there is less known about the effect of antibiotics on Cu removal. In this study, we report for the first time that, during the photocatalytic purification of sulfamerazine (SMZ) and Cu combined pollution, Cu concentration showed an obvious five-stage fluctuation, which was completely different from the simple promotion or inhibition reported in previous studies. By employing HPLC-MS analysis and density functional theory (DFT) calculation, the repeated fluctuation of Cu concentration was found to be closely related to the SMZ degradation process, mainly resulting from solution pH drop and formation of Cu-containing intermediates which acted as sacrificial agents for Cu reduction. In addition, compared with the SMZ-free system, the presence of SMZ can greatly enhance the deep removal of Cu (minimum Cu concentration was only 0.17 mg/L vs. 1.28 mg/L without SMZ), and there was a wide time interval to ensure the efficient recovery of Cu metal. More interestingly, the in-situ obtained Cu-decorated TiO photocatalyst performed well in water splitting, nitrogen fixation and bacterial sterilization. Results of this study confirmed the great potential of photocatalytic technology in purifying antibiotic-heavy metal combined pollution.
Topics: Sulfamerazine; Anti-Bacterial Agents; Metals, Heavy; Environmental Pollution
PubMed: 36640508
DOI: 10.1016/j.jhazmat.2023.130768 -
Food Chemistry Jun 2023A lanthanide terbium/europium metal-organic framework (TbEu-MOF) was prepared by one-step solvothermal method at room temperature. A series of characterizations...
A lanthanide terbium/europium metal-organic framework (TbEu-MOF) was prepared by one-step solvothermal method at room temperature. A series of characterizations including scanning electron microscopy, powder X-ray diffraction spectra, Fourier transform infrared spectra and X-ray photoelectron spectroscopy were carried out to clarify the physical characteristics of the synthesized material. The data clarified that the prepared TbEu-MOF possessed rod-like morphology with a width of 1-2 μm, and had good crystal structure, good stability, response speed and excitation-independent emission feature. The bunchy TbEu-MOF was then used to construct fluorescent sensors for rapid identification of malachite green and sulfamerazine. It was revealed that the detection mechanism was inner filter effect. The effects of different parameters such as excitation wavelength and incubation times were investigated on the fluorescence analysis performance. The data clarified that the optimal excitation wavelength and incubation time was 240 nm and 3 min, respectively. The detection platform exhibited the high sensitivity and selectivity toward malachite green in the linear range of 2-180 μM and determined limit of detection was 1.12 μM. Besides, the proposed sensor allowed sensitive detection of sulfamerazine in the linear range of 2-140 μM with a low detection limit of 0.1 μM. Meaningfully, a smartphone application was designed to assist the proposed sensor to realize visual, intelligent and rapid detection of malachite green and sulfamerazine. Furthermore, the practical application of the proposed sensor has been also verified by high performance liquid chromatography, showing good accuracy, sensitivity and satisfactory recoveries. The results suggested that the TbEu-MOF-based ratiometric fluorescent sensor had the potential to become a promising technique for rapid detection of malachite green or sulfamerazine with smartphone application. Therefore, the prepared TbEu-MOF is one kind of efficient and cost-effective potential materials for developing fluorescent sensor for rapid, sensitive and selective detection of sulfamerazine and malachite.
Topics: Lanthanoid Series Elements; Sulfamerazine; Fluorescent Dyes
PubMed: 36623454
DOI: 10.1016/j.foodchem.2023.135390 -
Environmental Pollution (Barking, Essex... Jan 2023The widespread coexistence of hydrophilic organic compounds and microplastics (MPs) in the environment has greatly increased their associated environmental problems. To...
The widespread coexistence of hydrophilic organic compounds and microplastics (MPs) in the environment has greatly increased their associated environmental problems. To evaluate the potential carrier effect of oxygen-containing MPs on coexisting pollutants, adsorption behaviors of four hydrophilic organic compounds (benzoic acid, sulfamethoxazole, sulfamerazine and ciprofloxacin) on MPs (pristine and weathered polyamide (PA)) were studied in the aquatic environment. The results showed that the surface morphology, size, oxygen content, molecular structure, surface charge and crystallinity of PA were changed after weathering, and the weathering degree of PA treated with heat-activated potassium persulfate was the highest. The main adsorption mechanisms included hydrogen bonding, hydrophobic interaction, charge-assisted hydrogen bonding, and electrostatic interaction. Hydrogen bonding and hydrophobic interaction contributed to the adsorption, while electrostatic interaction weakened the adsorption under the specific pH conditions. The formation of charge-assisted hydrogen bonding (CAHB) was also verified through pH influence experiments, and this force can overcome the electrostatic repulsion. The high adsorption of KPA (PA weathered by KSO) under alkaline conditions was well explained by the formation of homonuclear CAHB due to the increase of oxygen-containing functional groups compared to the other three PA. Additionally, weathering did not always enhance the adsorption of hydrophilic organic compounds on PA, which was related to the changes in surface charge, crystallinity and hydrophilicity of PA. Overall, the physical and chemical properties (e.g., specific surface area, oxygen content, molecular structure) of PA after weathering and its trend of adsorption were different from other oxygen-free MPs in this study. This work can provide basic data for environmental risk of MPs and contribute to clarify and understand the processes of oxygenated MPs in the aquatic environment.
Topics: Microplastics; Plastics; Nylons; Adsorption; Water Pollutants, Chemical; Organic Chemicals; Hydrophobic and Hydrophilic Interactions
PubMed: 36481467
DOI: 10.1016/j.envpol.2022.120818 -
The Science of the Total Environment Feb 2023The effect of various hydrogen bonds with different strength on the environmental behaviors of PPCPs remains unclear. In this study, three pharmaceutical pollutants...
The effect of various hydrogen bonds with different strength on the environmental behaviors of PPCPs remains unclear. In this study, three pharmaceutical pollutants including clofibric acid (CA), sulfamerazine (SMZ), and acetaminophen (ACT) with different functional groups and pK, were selected as representative of PPCPs to investigate the pivotal role of hydrogen bonds in adsorption/desorption and co-adsorption behaviors of PPCPs on two corn straw-derived biochars prepared at 300 °C (BCs-300) and 600 °C (BCs-600), respectively. The results indicated that charge-assisted hydrogen bond (CAHB) and ordinary hydrogen bond (OHB) with different intensities were the pivotal mechanisms responsible for the adsorption of three PPCPs on biochars, which was further confirmed by FTIR, but their immobilization effects of PPCPs on biochars were completely different. Compared with OHB formed between CA and BCs-600, the stronger CAHB (formed between CA and BCs-300, and SMZ/ACT and BCs-300/BCs-600) with covalent bond characteristics that derived from the smaller |ΔpK| (<5.0), resulted in the greater adsorption capacity (Q) and affinity (K) of the three PPCPs on BCs-300 (Q ≥ 195 μmol·g, K ≥ 1.9956) than that on BCs-600 (Q ≤ 92 μmol·g, K ≤ 0.5192), thereby making the better immobilization effect of PPCPs by biochar. In addition, in the coexisting systems, either SMZ coexisting with CA/ACT on BCs-300, or ACT coexisting with CA/SMZ on BCs-600, both implied that when the |ΔpK| between the target PPCPs and biochar is smaller than that between the coexisting compound and biochar, the target PPCPs can preferentially occupy the shared hydrogen bond sites on the biochar surface, and hard to be replaced by the coexisting compound. This work not only expand the application of designed biochar as engineering adsorbents to control and removal of the specific PPCPs in the environment, but also facilitate accurate assessment of the environmental risk of co-existing PPCPs.
Topics: Zea mays; Hydrogen Bonding; Adsorption; Charcoal
PubMed: 36460113
DOI: 10.1016/j.scitotenv.2022.160623 -
Pharmaceuticals (Basel, Switzerland) Nov 2022This study constructs a machine learning method to simultaneously analyze the thermodynamic behavior of many polymer-drug systems. The solubility temperature of...
This study constructs a machine learning method to simultaneously analyze the thermodynamic behavior of many polymer-drug systems. The solubility temperature of Acetaminophen, Celecoxib, Chloramphenicol, D-Mannitol, Felodipine, Ibuprofen, Ibuprofen Sodium, Indomethacin, Itraconazole, Naproxen, Nifedipine, Paracetamol, Sulfadiazine, Sulfadimidine, Sulfamerazine, and Sulfathiazole in 1,3-bis[2-pyrrolidone-1-yl] butane, Polyvinyl Acetate, Polyvinylpyrrolidone (PVP), PVP K12, PVP K15, PVP K17, PVP K25, PVP/VA, PVP/VA 335, PVP/VA 535, PVP/VA 635, PVP/VA 735, Soluplus analyzes from a modeling perspective. The least-squares support vector regression (LS-SVR) designs to approximate the solubility temperature of drugs in polymers from polymer and drug types and drug loading in polymers. The structure of this machine learning model is well-tuned by conducting trial and error on the kernel type (i.e., Gaussian, polynomial, and linear) and methods used for adjusting the LS-SVR coefficients (i.e., leave-one-out and 10-fold cross-validation scenarios). Results of the sensitivity analysis showed that the Gaussian kernel and 10-fold cross-validation is the best candidate for developing an LS-SVR for the given task. The built model yielded results consistent with 278 experimental samples reported in the literature. Indeed, the mean absolute relative deviation percent of 8.35 and 7.25 is achieved in the training and testing stages, respectively. The performance on the largest available dataset confirms its applicability. Such a reliable tool is essential for monitoring polymer-drug systems' stability and deliverability, especially for poorly soluble drugs in polymers, which can be further validated by adopting it to an actual implementation in the future.
PubMed: 36422535
DOI: 10.3390/ph15111405 -
Environmental Pollution (Barking, Essex... Jan 2023Various hydrogen bonds, especially charge-assisted hydrogen bond (CAHB), is considered as one of vital mechanisms affecting the environmental behavior and risk of...
Various hydrogen bonds, especially charge-assisted hydrogen bond (CAHB), is considered as one of vital mechanisms affecting the environmental behavior and risk of pharmaceutical contaminants (PCs). Herein the sorption/desorption of three PCs including clofibric acid (CA), acetaminophen (ACT), and sulfamerazine (SMZ) on three Oxygen-rich (O-rich) nanoparticles (nano-silica: Nano-SiO, nano-alumina: Nano-AlO, and oxidized carbon nanotubes: O-CNTs) were investigated to explore the effect of various hydrogen bonds with different strengths on environmental behaviors of PCs. The results indicated that although solvent-assisted CAHB, solvent-uninvolved CAHB, and ordinary hydrogen bond (OHB) all played a crucial role in sorption of PCs on three O-rich nanomaterials, they showed significantly different effects on the desorption behaviors of PCs from three sorbents. Compared with OHB (hysteresis index ≤0.0766), the stronger CAHB (hysteresis index ≥0.1981) between PCs and O-rich nanoparticles having comparable pK with PCs, caused obvious desorption hysteresis of PCs, resulting in their better immobilization on O-rich nanomaterials. The FTIR characterization found that both solvent-assisted and solvent-uninvolved CAHB formation resulted in a new characteristic peak appeared in the high frequency (3660 cm for Nano-SiO, 3730 cm for Nano-AlO, and 3780 cm for O-CNTs). Also, density functional theory (DFT) calculation verified that the smaller |ΔpK| between PCs and O-rich sorbents, the shorter bond length, and the larger bond angle resulted in the stronger hydrogen bond formed, thereby leading to the greater immobilization of PCs. These results provide in-depth understanding of the environmental behavior and risk of PCs, and light new idea for designed materials to control PCs pollution in the environment.
Topics: Hydrogen Bonding; Adsorption; Nanotubes, Carbon; Oxygen; Silicon Dioxide; Solvents; Pharmaceutical Preparations
PubMed: 36335784
DOI: 10.1016/j.envpol.2022.120572