Molecularly imprinted polymers-coated magnetic covalent organic frameworks for efficient solid-phase extraction of sulfonamides in fish.

In this study, covalent organic frameworks (COFs) were grown in situ on magnetic nitrogen-doped graphene foam (MNGF), and the resulting composite of COFs-modified MNGF (MNC) was wrapped by molecularly imprinted polymers (MNC@MIPs) for specifically capturing SAs. A magnetic solid phase extraction (MSPE) method for SAs was established using MNC@MIPs with good magnetic responsiveness. The adsorption performance of MNC@MIPs was superior to that of non-molecularly imprinted polymers (MNC@NIPs), with shorter adsorption/desorption time and higher imprinting factors. A high-efficiency SAs analytical method was developed by fusing HPLC and MNC@MIPs-based MSPE. This approach provides excellent precision, a low detection limit, and wide linearity. By analyzing fish samples, the feasibility of the approach was confirmed, with SAs recoveries and relative standard deviations in spiked samples in the ranges of 77.2-112.7 % and 2.0-7.2 %, respectively. This study demonstrated the potential use of MNC@MIPs-based MSPE for efficient extraction and quantitation of trace hazards in food.

Sodium salicylate as a green fluorescent probe for ultrasensitive determination of vonoprazan fumarate via fluorescence switch off strategy; greenness assessment.

A green, simple and sensitive spectrofluorometric approach for determining vonoprazan fumarate in bulk and pharmaceutical dosage form by turning off the fluorescence of sodium salicylate is developed. The addition of vonoprazan fumarate reduced linearly the fluorescence intensity of 0.4 mM sodium salicylate at λem 408 nm and at λex 330 nm. The approach was found to be linear in the 50.0-3000.0 ng/mL range. The limits of detection and quantification were 10.97 and 33.23 ng/mL, respectively. The presented method proved its suitability in determination of vonoprazan fumarate in its pure and pharmaceutical dosage form. This method employs water as the exclusive solvent and utilizes safe reagents, evaluated using the Analytical Eco Scale, Green Analytical Procedure Index (GAPI), and carbon footprint. In contrast, previous methods relied on toxic reagents and required extended heating times, resulting in higher environmental impact. The novel method not only enhances analytical efficiency but also aligns with green chemistry principles, offering a sustainable solution for routine pharmaceutical analysis.

Occurrence and risk assessment of quinolones and sulfonamides in freshwater aquaculture ponds in Northeast Zhejiang, China.

Antibiotics play an essential role in the aquaculture industry, but their overuse and weak degradability inevitably lead to light to severe residues in natural and aquaculture environments. Most studies were interested in the occurrence, distribution, and ecological risks of a limited number of antibiotics in natural environments (rivers, lakes, and coastal regions) with a minor focus on antibiotic presence in either water, sediments, or organisms in aquaculture environments located in specific regions. In this study, we conducted a comprehensive investigation into the occurrence and distribution of up to 32 antibiotics [including 15 quinolones (QNs) and 17 sulfonamides (SAs)] in organisms and their corresponding environmental matrices from 26 freshwater aquaculture ponds in Northeast Zhejiang, China. A total of 13, 9, 7, and 7 antibiotics were detected in pond water, sediments, feeds, and aquaculture organisms, respectively, with concentration ranges of 0.6-92.2 ng/L, 0.4-1169.3 ng/g dw,

Novel phenazine-based microporous organic network for selective and sensitive determination of trace sulfonamides in milk samples.

BACKGROUND: Sulfonamide (SA) residues in food of animal origin possess a potential threat to human health and environment. However, due to the polar and ionic characteristics and trace level of SAs and the complexity of food matrices, direct measurement of SAs in these samples is still very difficult. Development of efficient sample pretreatment method for sensitive and selective extraction of trace SAs is of great significance and urgently desired. Therefore, rational design and synthesizing advanced and selective extractants is quite important. RESULTS: In this work, a novel phenazine-based microporous organic network (MON) named TEPM-DP is reasonably synthesized and employed as a packing material for selective solid phase extraction (SPE) and sensitive determination of four typical SAs in milk samples. Phenazine-based monomer with aromatic and heteroaromatic ring and numerous N atoms is chosen to construct TEPM-DP adsorbent to provide π-π, hydrogen bonding, hydrophobic, and electrostatic extraction sites for SAs. The proposed method owns wide linear ranges, low limits of detection, high enrichment factors, and good precisions and recoveries for SAs in complex milk samples. The recoveries of SAs on TEPM-DP are much higher than those of commercial C18 and activated carbon. The extraction mechanisms are also elucidated via FT-IR, XPS, and comparative experiments. SIGNIFICANCE: This work reports the first example of design and synthesizing phenazine-based MON in SPE via a simple and rapid solvothermal method. The results reveal the great prospects of TEPM-DP for enriching polar and ionic SAs in complex samples and uncover the potency of phenazine-based MON in sample pretreatment, which will promote the development of MON.

Stability Indicating UPLC Method Development and Validation for the Quantitative Estimation of Pazopanib in Pure form and Marketed Pharmaceutical Dosage form.

An analytical, accurate, precise, specific, efficient and simple Ultra-Performance Liquid Chromatography method has been developed and validated for the determination of Pazopanib in bulk and was applied on marketed Pharmaceutical Dosage form. The mobile phase used for the chromatographic runs consisted of 0.1% OPA Buffer and Acetonitrile in the ratio of 30:70% v/v. The separation was achieved on a BHEL UPLC column using isocratic mode. Pazopanib Drug peak were well separated and were detected by a PDA detector at 256 nm. The developed method was linear at the concentration range 6-14 µg/ml for Pazopanib. The method has been validated according to ICH guidelines with respect to system suitability, specificity, precision, accuracy and robustness. The LOD and LOQ for the Pazopanib were found to be 0.5853 µg/ml and 1.7738µg/ml respectively. The developed method is simple, precise, specific, accurate and rapid, making it suitable for estimation of Pazopanib in bulk and marketed pharmaceutical dosage form dosage form.

Understanding Environmental Fate: Soil Variability and Rainfall Influence on Triafamone and Ethoxysulfuron Leaching.

Considering the environmental impact of triafamone and ethoxysulfuron, it is crucial to investigate their leaching behaviour under different geographical conditions. The present study evaluates the effects of application rate, soil properties and rainfall conditions on leaching of these herbicides and their metabolites. Ethoxysulfuron leached up to 50-60 cm with 82.95 to 89.23% detected in leachates while triafamone leached only to 10-20 cm and was < 0.01 µg mL-1 in leachates. Highest leachability was observed in loamy sand followed by sandy loam and clay loam soil. M1 metabolite (N-(2-((4,6-dimethoxy-1,3,5-triazin-2-yl) (hydroxy) methyl) -6-fluorophenyl) -1,1-difluoro-N-methyl methane sulfonamide) was majorly present in 0 to 10 cm soil depth. With increase in rainfall, downward mobility of both parent and M1 increased. Amendment of loamy sand soil with farmyard manure reduced the leachability indicating it could mitigate groundwater pollution. However, the effect of different exogenous OM amendments on leaching behaviour of herbicides needs to be evaluated.

Study on the Rapid Limit Test for Six Sulfonamide Residues in Food Based on the TLC-SERS Method.

Sulfonamides are not only widely applied in clinics but also highly valued in animal husbandry. Recently, it has become common for sulfonamide residues to exceed the standard limits in food, which can affect human health. Current regulations limit these residues. Therefore, we constructed a new limit test method to rapidly determine the levels of sulfonamide residues. Six sulfonamides were detected using the latest method called TLC-SERS, namely, sulfamethasone (A), sulfamethazine (B), sulfadoxine (C), sulfamethoxydiazine (D), sulfamethoxazole (E), and sulfathiazole (F). The optimal conditions for SERS detection were investigated for these six drugs, and the separation effects of different TLC spreaders on them were compared. Then, we successfully established a separation system using dichloromethane-methanol-ammonia in a ratio of 5:1:0.25 (v/v/v), which provided good separation effects on the six drugs. The residues were preliminarily separated via TLC. A silver sol solution was added to the spot on the silica gel G plate at the corresponding specific shift values, and SERS detection was performed. The sample solution was placed on the spot under a 532 nm laser, and the SERS spectrum was collected and analyzed for the six sulfonamides. The results showed obvious variations in the SERS spectrum among the six sulfonamides, with the LODs being 12.5, 6.4, 6.3, 7.1, 18.8, and 6.2 ng/mL from A to F, respectively, and an RSD of <3.0%. Within 48 h, the SERS signal for each sulfonamide drug was kept stable, with an RSD of <3.0%. The detection results of 20 samples using the TLC-SERS method were consistent with those obtained by UPLC-MS/MS. The established TLC-SERS method is simple and fast, providing a useful reference for the rapid detection of residue limits in food.

Hydrophilic molecularly imprinted thermal-responsive polymers based sorbent for ambient ionization mass spectrometric analysis of sulfonamide antibiotics from food samples.

The thermal-responsive magnetic molecularly imprinted polymer (TrMMIP) sorbent was synthesized by surface imprinting method, and then used for magnetic solid-phase extraction (MSPE) and subsequent integrated into the ion source for elution and ionization. The shrinking-strength states change of the thermal-responsive polymer chain on TrMMIP alters the wettability of the sorbent when the working temperature crosses the lower critical solution temperature (LCST) of the polymer, and thus affects its behavior of in the extraction and clean-up process. The targeted analytes could be effectively extracted due to the high selectivity of MIPs and well dispersibility of polymer chain under the open state. Additionally, a hydrophilic polymer chain wrapped on the sorbent surface further protected target substances from co-elution during cleanup. Analytical methods for sulfonamide antibiotics (SAs) detection in complex food samples (milk, honey, fish) were developed, demonstrating potential for rapid and sensitive SAs analysis in diverse food and biological samples.

Highly sensitive chemiluminescent sensor for detecting o-toluenesulfonamide and sulfamethoxazole using Cu-doped carbon dots.

In this study, Cu doped carbon dots (Cu-CDs) of uniform particle size and good water solubility was synthesized using Angelica Sinensis Radix as precursor materials through a one-step hydrothermal. The Lucigenin-(Cu-CDs) chemiluminescence sensor allows the simultaneous determination of o-toluenesulfonamide (TFA) and sulfamethoxazole (STZ) concentrations. Under optimal conditions, the sensor demonstrates the capability to detect TFA and STZ within the ranges of 50 µM-800 µM and 15 µM-120 µM, respectively. The limits of detection (LOD) for TFA and STZ are determined as 0.09 µM and 0.05 µM, respectively. While the limits of quantification (LOQ) are established at 0.3 µM and 0.17 µM, respectively. The feasibility of the method for determining TFA and STZ content in chicken samples was substantiated, demonstrating spiked recovery rates ranging from 97.5% to 102.3 % and 97.5%-99.8 %, respectively. The possible reaction mechanism was clarified based on chemiluminescence, UV-vis measurement and free radical analysis results. The newly established system is characterized by stability, convenience, and robust anti-interference capabilities, thus expanding the application of carbon dots and offering a promising strategy for the detection of TFA and STZ.

Europium functionalized porphyrin-based metal-organic framework heterostructure and hydrogel for visual ratiometric fluorescence sensing of sulfonamides in foods.

Protecting human health and ensuring food security require the swift and accurate detection of sulfonamides (SAs) residues in foods. Herein, we proposed an Eu-postfunctionalized bimetallic porphyrin metal-organic framework (PCN-221(Zr/Ce)@Eu-DPA-H4btec) synthesized solvothermally for fluorescence sensing. The PCN-221(Zr/Ce)@Eu-DPA-H4btec fluorescent sensor demonstrated excellent stability and high selectivity to SAs, and the detection limits of sulfamethazine (SM2), sulfamerazine (SMR), and sulfamethoxydiazine (SMD) were as low as 56 nmol/L, 45 nmol/L, and 56 nmol/L, respectively. The PCN-221(Zr/Ce)@Eu-DPA-H4btec fluorescent sensor was successfully applied for the detection of SM2, SMR, and SMD in real pork and milk samples, with satisfactory recoveries (81.2-118.3%) and high precisions (RSDs <8.2, n = 3). Combining the optical properties of the nanohybrids, PCN-221(Zr/Ce)@Eu-DPA-H4btec integrated fluorescent hydrogels were innovatively prepared for visual sensing of SM2, SMR, and SMD. This study provides an uncomplicated and sensitive method for SAs detection in food matrices.

[Occurrence and environmental risks of antibiotics in surface water of China].

Antibiotics as emerging pollutants are frequently detected in surface water, raising concerns about the associated risk of antibiotic resistance genes (ARGs). Despite the widespread apprehension, there are still research gaps in the occurrence of antibiotic pollution in surface water and the associated ecological risks to aquatic organisms in China. Here, we established a dataset of antibiotic pollution in surface water in China during 2018-2022, which encompassed 3 368 concentration values of 128 antibiotics reported in 124 articles. Our analysis showed that antibiotic concentrations were predominantly in the ng/L-µg/L range, reaching up to 26 µg/L. Notably, sulfonamides (e.g., sulfamethoxazole) and quinolones (e.g., ciprofloxacin) were frequently reported at high concentrations. The pollution degree of antibiotics represented by sulfamethoxazole, ciprofloxacin, roxithromycin, and tetracycline exhibited no significant variation across different years but was lower in summer than that in spring and autumn. Additionally, distinct spatial distribution characteristics of the pollution were observed. According to calculation results of the aquatic ecological risk assessment model and the weighted frequency, we proposed a list of priority antibiotics including clarithromycin, erythromycin, sulfamethoxazole, ofloxacin, and oxytetracycline in surface water. Last but not least, this study points out the deficiencies in current research on the occurrence and ecological risks of antibiotics in surface water of China and provides viable screening strategies and monitoring recommendations in this context.

Fluorimetric determination of Vonoprazan via quenching of nitrogen and sulfur co-doped carbon quantum dots: A rapid and sustainable analytical approach.

In this study, an environmentally sustainable fluorimetric method for determination of Vonoprazan fumarate (VON) in dosage forms using nanoprobes consisting of nitrogen and sulfur co-doped carbon quantum dots (N, S-CQDs). The N, S-CQDs were prepared through a microwave-assisted method in 30 s. The resulting N, S-CQDs were characterized using transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). They exhibit fluorescence emission at 460 nm after excitation at 385 nm with a high quantum yield (60%). The analytical approach for VON determination relies on the quenching effect exerted by VON on the native fluorescence intensity of CQDs. The quenching mechanism was investigated using Stern-Volmer plots. The proposed method demonstrates linearity across a concentration range 10-80 µM (4.6-36.8 µg/mL) with corresponding limits of detection and quantitation calculated as 2.17 µM (0.99 µg/mL) and 6.58 µM (3.02 µg/mL), respectively. The method has been effectively utilized for the determination of VON in the pharmaceutical samples. Statistical comparison with reported RP-HPLC has been performed to verify the accuracy and precision of the developed method. The environmental sustainability of the developed method has been thoroughly examined through various greenness metrics.

Distribution characteristics of sulfonamide antibiotics between water and extracellular polymeric substances in municipal sludge.

The interaction between extracellular polymeric substances (EPS) in municipal sludge and antibiotics in wastewater is critical in wastewater treatment, resource recovery, and sludge management. Therefore, it is increasingly urgent to investigate the distribution coefficient (Log K) of sulfonamide antibiotics (SAs) in EPS, particularly in sludge-derived dissolved organic carbon (DOC) and aqueous phase systems. Herein, through balance experiments, the concentrations of SAs were determined using alkaline extraction EPS (AEPS) and alginate-like extracellular polymer (ALE) systems, and the Log KDOC values were determined. The results showed that the Log KDOC of AEPS was higher than that of ALE, which exhibited a negative KDOC value, indicating an inhibitory effect on dissolution. For the three SAs studied, the Log KDOC values were in the following order: sulfamethoxazole > sulfapyridine > sulfadiazine. This order can be attributed to the differing physicochemical properties, such as polarity, of the SAs. Three-dimensional excitation-emission matrix fluorescence spectra and fitting results indicated a lack of aromatic proteins dominated by tryptophan and humus-like substances in ALE. Meanwhile, the hydrophobic interaction of aromatic proteins dominated by tryptophan was the main driving force in the binding process between AEPS and SAs.

Unraveling the Pollution and Discharge of Aminophenyl Sulfone Compounds, Sulfonamide Antibiotics, and Their Acetylation Products in Municipal Wastewater Treatment Plants.

Aminophenyl sulfone compounds (ASCs) are widely used in various fields, such as the pharmaceutical and textile industries. ASCs and their primary acetylation products are inevitably discharged into the environment. However, the high toxicity of ASCs could be released from the deacetylation of acetylation products. Still, the occurrence and ecological risks of ASCs and their acetylation products remain largely unknown. Here, we integrated all of the existing ASCs based on the core structure, together with their potential acetylation products, to establish a database covering 1105 compounds. By combining the database with R programming, 45 ASCs, sulfonamides, and their acetylation products were identified in the influent and effluent of 19 municipal wastewater treatment plants in 4 cities of China. 13 of them were detected for the first time in the aquatic environment, and 12 acetylation products were newly identified. The cumulative concentrations of 45 compounds in the influent and effluent were in the range of 231-9.96 × 103 and 26-2.70 × 103 ng/L, respectively. The proportion of the unrecognized compounds accounted for 60.6% of the influent and 62.8% of the effluent. Furthermore, nearly half of the ASCs (46.7%), other sulfonamides (49.9%), and their acetylation products (46.2%) were discharged from the effluent, posing a low-to-medium risk to aquatic organisms. The results provide a guideline for future monitoring programs, particularly for sulfadiazine and dronedarone, and emphasize that the ecological risk of ASCs, sulfonamides, and their acetylation products needs to be considered in the aquatic environment.

Isolation of aptamers with excellent cross-reactivity and specificity to sulfonamides towards a ratiometric fluorescent aptasensor for the detection of nine sulfonamides in seafood.

Sulfonamides (SAs) is a class of antibiotics that extensively used for treating infectious diseases in livestock industries and aquaculture. Thus, it is urgent need to obtain the bio-receptor, which has excellent cross-reactivity and specificity to SAs, for developing high-throughput methods for the determination of multiple SAs even all commonly-used SAs, to realize the quick screening/detection of total SAs in animal-derived foods. We herein isolated several SAs-specific cross-reactive aptamers by using a library-immobilized SELEX with multi-SAs parallel selection strategy. Two of the isolated aptamers (Sul-01 and Sul-04) can specifically recognize and bind seven SAs respectively with higher binding affinity and no interference of non-sulfonamide antibiotics, and thus can be applied as bio-receptors for developing high-throughput aptasensors for the quick screening/detection of multiple SAs. By using the mixture of Sul-01 and Sul-04 as bio-receptor, a ratiometric fluorescent aptasensor was created for the quick detection of nine SAs including sulfamethoxydiazine (SMD), sulfapyridine (SPD), sulfaquinoxaline (SQ), sulfathiazole (ST), sulfamonomethoxine (SMM), sulfamerazine (SMR), sulfaguanidine (SG), sulfamethazine (SMZ) and sulfadiazine (SD) with a detection limit (LOD) of 0.10-0.50 µM, or total of above nine SAs with a LOD of 0.20 µM. The fluorescent aptasensor was successfully applied to detect each or total of SMD, SPD, SQ, ST, SMM, SMR, SG, SMZ and SD in fish samples with a recovery of 83 %-92 % and a relative standard deviation (RSD, n = 5) < 5 %. This study not only provided several promising bio-receptors for the development of diverse high-throughput aptasensors to achieve the quick screening of multiple SAs residues, but also provided a simple, stable and sensitive method for the quick screening of SMD, SPD, SQ, ST, SMM, SMR, SG, SMZ and SD in seafood.

Nitrogen stable isotope analysis of sulfonamides by derivatization-gas chromatography-isotope ratio mass spectrometry.

The continuous introduction of micropollutants into the environment through livestock farming, agricultural practices, and wastewater treatment is a major concern. Among these pollutants are synthetic sulfonamide antibiotics such as sulfamethoxazole, which are not always fully degraded and pose a risk of fostering antimicrobial resistance. It is challenging to assess the degradation of sulfonamides with conventional concentration measurements. This study introduces compound-specific isotope analysis of nitrogen isotope ratios at natural abundances by derivatization-gas chromatography hyphenated with isotope ratio mass spectrometry (derivatization-GC-IRMS) as a new and more precise method for tracing the origin and degradation of sulfonamides. Here, sulfamethoxazole was used as a model compound to develop and optimize the derivatization conditions using (trimethylsilyl)diazomethane as a derivatization reagent. With the optimized conditions, accurate and reproducible δ15N analysis of sulfamethoxazole by derivatization-GC-IRMS was achieved in two different laboratories with a limit for precise isotope analysis of 3 nmol N on column, corresponding to 0.253 µg non-derivatized SMX. Application of the method to four further sulfonamides, sulfadiazine, sulfadimethoxine, sulfadimidine, and sulfathiazole, shows the versatility of the developed method. Its benefit was demonstrated in a first application, highlighting the possibility of distinguishing sulfamethoxazole from different suppliers and pharmaceutical products.

Development and performance evaluation of a microbiological method for screening and LC-MS/MS for conformation of sulfonamides in animal-derived foods.

This study developed a highly sensitive microbiological method utilizing a novel microtiter plate to screen 10 sulfonamides in chicken muscles, eggs, and prawns. This plate was fabricated from agar incorporating trimethoprim and spread with Bacillus megaterium. After residue detection by bioassay, the same test solutions were analyzed by LC-MS/MS for accurate identification and quantification. It also proved eco-friendly compared to using other quantitative methods. The residual drugs were extracted with McIlvaine buffer and purified using an Oasis® MCX cartridge. A triethylamine/methanol/water (0.5:75:24.5, v/v/v) mixture was used as the eluate. The obtained LOD values of the bioassay ranged from 5 to 25 µg kg-1 allowing the detection of the target drugs at the MRLs established in Japan. Adhering to ISO/IEC 17025 standards, the performance of the bioassay was evaluated. Based on the inhibition zone size in bioassay results, quality control yielded a Z score within ±2, indicating reasonable control over the screening process. Proficiency testing of a chicken muscle sample spiked with sulfadimidine demonstrated the inhibition zone detection of the bioassay and quantified value alignment of LC-MS/MS with reference values. In a surveillance study of 91 samples, sulfamethoxazole was detected in one prawn sample.

Zr-based multivariate metal-organic framework for rapid extraction of sulfonamide antibiotics from water and food samples.

Based on multiple ligands strategy, a series of multivariate metal organic frameworks (MTV-MOFs) named as PCN-224-DCDPSx were prepared using one-pot solvothermal method to extract and remove sulfonamide antibiotics (SAs). The pore structure and adsorption performance can be further regulated by modulating the doping ratios of medium-tetra(4-carboxylphenyl) porphyrin and 4,4'-dicarboxydiphenyl sulfones. The MTV-MOFs of PCN-224-DCDPS1.0 possesses very large specific surface area (1625 m2/g). Using PCN-224-DCDPS1.0 as sorbent, a dispersive solid-phase extraction method was developed to extract and preconcentrate SAs from water, eggs, and milk prior to high performance liquid chromatography analysis. The limits of detection of method were determined between 0.17 and 0.27 ng/mL with enrichment factors ranging 214-327. The adsorption can be finished within 30 s, and the recovery rate remains above 80 % after 10 repeated uses. The adsorption capacities of sorbent were determined from 300 to 621 mg/g for sulfadiazine, sulphapyridine, sulfamethoxydiazine, sulfachlorpyridazine, sulfabenzamide, and sulfadimethoxine. The adsorption mechanisms were investigated and can be attributed to π-π interactions, hydrogen bonds, and electrostatic interactions. This work represents a method for preparation of MTV-MOFs and uses as sorbent for extraction and enrichment of trace pollutants from complex samples.

Levels and spatial profile of per- and polyfluoroalkyl substances in edible shrimp products from Japan and neighboring countries; a potential source of dietary exposure to humans.

Exposure to per- and polyfluoroalkyl substances (PFAS) is of great concern for human health because of their persistence and potentially adverse effects. Dietary intake, particularly through aquatic products, is a significant route of human exposure to PFAS. We analyzed perfluoroalkyl sulfonic acid (PFSA with carbon numbers from 6 to 8 and 10 (C６-C8, C10)) and perfluorooctanesulfonamide (FOSA), and perfluoroalkyl carboxylic acid (PFCA with carbon numbers from 6 to 15 (C6-C15)) in 30 retail packs of edible shrimps, which included seven species from eight coastal areas of Japan and neighboring countries. The most prevalent compounds were perfluorooctane sulfonate (PFOS, C8) and perfluoroundecanoic acid (PFUnDA, C11), accounting for 46 % of total PFAS. The concentrations ranged from 6.5 to 44 ng/g dry weight (dw) (equivalent to 1.5 to 10 ng/g wet weight (ww)) and varied according to species and location. For example, Alaskan pink shrimp (Pandalus eous) from the Hokuriku coast, Japan contained high levels of long-chain PFCAs (38 ng/g dw (equivalent to 8.7 ng/g ww)), while red rice prawn (Metapenaeopsis barbata) from Yamaguchi, Japan contained a high concentration of PFOS (29 ng/g dw (equivalent to 6.7 ng/g ww)). We also observed regional differences in the PFAS levels with higher concentrations of long-chain PFCAs in Japanese coastal waters than in the South China Sea. The PFAS profiles in shrimp were consistent with those in the diet and serum of Japanese consumers, suggesting that consumption of seafood such as shrimp may be an important source of exposure. The estimated daily intake of sum of all PFAS from shrimp from Japanese coastal water was 0.43 ng/kg body weight/day in average, which could reach the weekly tolerable values (4.4 ng/kg body weight /week) for the sum of the four PFSA set by the EFSA for heavy consumers. The high concentration of PFAS in shrimp warrants further investigation.

Cyclodextrin-based ternary supramolecular deep eutectic solvents for efficient extraction and analysis of trace quinolones and sulfonamides in wastewater by adjusting pH.

BACKGROUND: Antibiotics residues can accelerate the growth of drug-resistant bacteria and harm the ecological environment. Under the effect of enrichment and biomagnification, the emergence of drug-resistant pathogenic bacteria may eventually lead to humans being ineffective to drugs in the face of bacterial or fungal disease infections in the future. It is urgent to develop an efficient separation medium and analytical method for simultaneous extraction and determination of antibiotics in the water environment. RESULTS: This work doped 2,6-Di-O-methyl-ß-cyclodextrin, randomly methyl-ß-cyclodextrin, 2-hydroxypropyl-ß-cyclodextrin with thymol:fatty acid respectively to construct non-covalent interaction-dominated pH-responsive ternary supramolecular deep eutectic solvents (SUPRADESs), which can undergo a hydrophilic/hydrophobic transition with aqueous phase to achieve an efficient microextraction. Semi-empirical method illustrated that SUPRADESs have a wide range of hydrogen bond receptor sites. We developed a SUPRADES-based analytical method combined with liquid chromatography-triple quadrupole mass spectrometry for the extraction and determination of trace quinolones and sulfonamides in wastewater. The overall limits of detection of the method were 0.0021-0.0334 ng mL-1 and the limits of quantification were 0.0073-0.1114 ng mL-1. The linearity maintained good in the spiked level of 0.01-100 ng mL-1 (R2 > 0.99). The overall enrichment factors of the method were 157-201 with lower standard deviations (≤8.7). SIGNIFICANCE: The method gave an extraction recovery of 70.1-115.3 % for 28 antibiotics in livestock farming wastewater samples from Zhejiang, China, at trace levels (minimum 0.5 ng mL-1). The results demonstrated that inducing the phase transition between SUPRADES and aqueous phase by adjusting pH for extraction is a novel and efficient pretreatment strategy. To our knowledge, this is the first application of cyclodextrin-based ternary SUPRADESs with pH-responsive reversible hydrophobicity-hydrophilicity transition behavior in wastewater analysis.