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.

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.

Preparation of cylindrical Chitosan/ß-Cyclodextrin/MIL-68(Al) foam column for solid-phase extraction of sulfonamides in water, urine, and milk.

This study describes the preparation of a cylindrical polymer foam column termed Chitosan/ß-Cyclodextrin/MIL-68(Al) (CS/ß-CD/MIL-68(Al)). An ice template-freeze drying technique was employed to prepare the CS/ß-CD/MIL-68(Al) foam column by embedding MIL-68(Al) in a polymer matrix comprising cross-linked chitosan (CS) and ß-cyclodextrin (ß-CD). The cylindrical CS/ß-CD/MIL-68(Al) foam was subsequently inserted into a syringe to develop a solid phase extraction (SPE) device. Without the requirement for an external force, the sample solution passed easily through the SPE column thanks to the porous structure of the CS/ß-CD/MIL-68(Al) foam column. Moreover, the CS/ß-CD/MIL-68(Al) foam column was thought to be a superior absorbent for SPE since it included the adsorptive benefits of CS, ß-CD, and MIL-68(Al). The SPE was utilized in conjunction with high-performance liquid chromatography to analyze six sulfonamides found in milk, urine, and water. With matrix effects ranging from 80.49 % to 104.9 % with RSD values of 0.4-14.0 %, the method showed high recoveries ranging from 80.6 to 107.4 % for water samples, 93.4-105.2 % for urine, and 87.4-100.9 % for milk. It also demonstrated good linearity in the range of 10-258 ng·mL-1 with the limits of detection ranging from 1.88 to 2.58 ng·mL-1. The cylindrical CS/ß-CD/MIL-68(Al) foam column prepared in this work offered several advantages, including its simple fabrication, excellent water stability, absence of pollutants, biodegradability, and reusability. It is particularly well-suited for SPE. Furthermore, the developed SPE method, employing CS/ß-CD/MIL-68(Al) foam column, is straightforward and precise, and its benefits, including affordability, ease of preparation, lack of specialized equipment, and solvent economy, underline its broad applicability for the pretreatment of aqueous samples.

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.

Fabrication and characterization of magnetic mesoporous nanoparticles for efficient determination and magnetic separation of sulfonamides in food samples.

A magnetic, mesoporous core/shell structured Fe3O4@SiO2@mSiO2 nanocomposite was synthesized and employed as a magnetic solid phase extraction (MSPE) sorbent for the determination of trace sulfonamides (SAs) in food samples. The synthesized nanocomposite was characterized by transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, thermogravimetric analysis, X-ray diffraction, N2 sorption analysis and vibrating sample magnetometry. The results showed that Fe3O4@SiO2@mSiO2 possessed a mesoporous structure with a large surface area. Batch experiments were carried out to investigate the adsorption ability for SAs. Fe3O4@SiO2@mSiO2 showed fast kinetics and high adsorption capacity, and the pseudo-second-order model and Langmuir adsorption isotherm are well fitted with the experimental data, indicating that chemical adsorption might be the rate-limiting step. Moreover, the high adsorption capacity can be maintained for at least 8 runs, indicating excellent stability and reusability. The proposed method exhibited good linearity in the range of 0.2-500 µg L-1, the R2 values of all the analytes were greater than 0.99 and the LODs were all lower than 0.2 µg L-1. Furthermore, real food samples were successfully analyzed with Fe3O4@SiO2@mSiO2 and high recoveries varying from 89.7% and 110.6% were obtained with low relative standard deviations ranging from 1.78% to 6.91%. The Fe3O4@SiO2@mSiO2 magnetic nanocomposite is a promising sorbent for the efficient extraction of SAs from complex food samples.

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.

Introduction of an electrospun nanofibrous membrane incorporated by metal-organic framework-199 (MOF-199) with Lewis acid property for efficient extraction of sulfonamides in on-chip electromembrane extraction.

In this study, a new supporting polymeric membrane having Lewis acid nature was introduced for immobilizing organic solvent in on-chip electromembrane extraction (on-chip EME). For this aim, a polymeric nanofibrous membrane incorporated by a copper based metal-organic framework (MOF-199), with coordinatively unsaturated metal sites and Lewis acid property, was prepared by electrospinning a mixture of polycaprolactone (PCL) and MOF-199. Based on the field emission scanning electron microscopy images, the obtained polymeric membrane consisted of intertwined nanofibers having empty space between the fibers which could provide a suitable place for immobilizing the organic solvent. To demonstrate remarkable extractability of the proposed membrane (PCL/MOF-199 nanofibers) via executing Lewis acid-base interactions, three sulfonamide drugs was selected as anionic polar analytes with Lewis base feature. The parameters affecting the extraction efficiency of the method were optimized through the experimental design method using the orthogonal and rotatable central composite design (CCD). Under optimum conditions, the extraction recoveries ranging from 35.5 to 71.2 %, the relative standard deviations (RSD%) less than 6.45 %, and the detection limits in the range of 0.2-0.5 µg L-1 were achieved. The comparison of the extraction efficiency of the on-chip EME method using the electrospun PCL/MOF-199 nanofibers and PCL nanofibers membranes indicated that the proposed membrane was more efficient for extraction of sulfonamides because of the significant Lewis acid-base interactions of sulfonamides with copper uncoordinated open sites in MOF-199. Finally, the performance of the proposed method for extraction and determination of sulfonamides in three real samples was assayed.

Determination of sulfonamide antibiotics by magnetic porous carbon solid-phase extraction coupled with capillary electrophoresis.

Sulfonamide antibiotics (SAs) have been widely used as antibacterial drugs for the prevention and treatment of livestock and poultry diseases, but they seriously threaten human health because they can accumulate in humans. Therefore, it is highly important to develop methods for monitoring sulfonamide residues in aquaculture and food. In this research, based on the generation of porous carbon (PC) by the pyrolysis of sodium citrate, magnetic porous carbon (PC@Fe3O4) was synthesized by a solvothermal method and used as an adsorbent for the magnetic solid-phase extraction of SAs. The effects of the proportion of PC in PC@Fe3O4, adsorbent dosage, adsorption time, eluent type, extraction pH, salt concentration and eluent dosage on the extraction efficiency were systematically studied. The adsorption performance and behavior of PC@Fe3O4 on SAs were evaluated using adsorption kinetics and adsorption isotherms, and the adsorption mechanism was preliminarily discussed. Under optimal conditions, combined with capillary electrophoresis diode array detection, a sensitive detection method for SAs was developed. The proposed method can be used for the determination of six SAs in fishpond water and milk samples, with a linear range of 0.5-200 ng mL-1, detection limits of 0.24-0.34 ng mL-1, and spiked recoveries of 85.9-109.0 %.

Preparation of molecularly imprinted resin/polydopamine nanofibers mat for the highly efficient extraction and determination of sulfonamides in environmental water.

With polyacrylonitrile nanofibers mat (PAN NFsM) as a template, molecularly imprinted resin/polydopamine nanofibers mat (MIR/PDA NFsM) was synthesized for the extraction of sulfonamides (SAs) in water. The specific surface area and pore volume were increased obviously due to the functionalization of MIR. The adsorption efficiencies of MIR/PDA NFsM under optimized conditions for SAs were 92.3-99.3%. Possible adsorption mechanisms of imprinting recognition and hydrogen bond interactions were also put forward. Compared with MIR particles, the MIR/PDA NFsM exhibited much superior adsorption performance. Particularly, the outstanding mass transfer efficiency of MIR/PDA NFsM was much higher than the other reported adsorbents for SAs. Finally, a new method based on the solid-phase extraction (SPE) of MIR/PDA NFsM was successfully developed for the detection of five SAs in environmental water with HPLC-MS/MS and applied to the analysis of actual samples. Under the selected conditions, the enrichment factors of MIR/PDA NFsM of SCP, SMT, SMZ, SMR, and SMX were between 23.0 and 25.0. Low detection limits (0.26-0.76 ng L-1), broad linear range (1.0 ng L-1 to 10.0 µg L-1), and satisfactory recoveries (82.8-115.6%) and precisions (RSDs < 7.2%) were obtained. Moreover, the excellent reusability properties and storage stability endowed MIR/PDA NFsM with great value for practical applications.

Development of Novel Quinoline-Based Sulfonamides as Selective Cancer-Associated Carbonic Anhydrase Isoform IX Inhibitors.

A new series of quinoline-based benzenesulfonamides (QBS) were developed as potential carbonic anhydrase inhibitors (CAIs). The target QBS CAIs is based on the 4-anilinoquinoline scaffold where the primary sulphonamide functionality was grafted at C4 of the anilino moiety as a zinc anchoring group (QBS 13a-c); thereafter, the sulphonamide group was switched to ortho- and meta-positions to afford regioisomers 9a-d and 11a-g. Moreover, a linker elongation approach was adopted where the amino linker was replaced by a hydrazide one to afford QBS 16. All the described QBS have been synthesized and investigated for their CA inhibitory action against hCA I, II, IX and XII. In general, para-sulphonamide derivatives 13a-c displayed the best inhibitory activity against both cancer-related isoforms hCA IX (KIs = 25.8, 5.5 and 18.6 nM, respectively) and hCA XII (KIs = 9.8, 13.2 and 8.7 nM, respectively), beside the excellent hCA IX inhibitory activity exerted by meta-sulphonamide derivative 11c (KI = 8.4 nM). The most promising QBS were further evaluated for their anticancer and pro-apoptotic activities on two cancer cell lines (MDA-MB-231 and MCF-7). In addition, molecular docking simulation studies were applied to justify the acquired CA inhibitory action of the target QBS.

A nanocomposite adsorbent of metallic copper, polypyrrole, halloysite nanotubes and magnetite nanoparticles for the extraction and enrichment of sulfonamides in milk.

A composite adsorbent composed of metallic copper (Cu), polypyrrole (PPy), halloysite nanotubes (HNTs) and magnetite nanoparticles (Fe3O4) was developed to extract and enrich sulfonamides by dispersive magnetic solid phase extraction. The composite could adsorb sulfonamides via hydrogen bonding and hydrophobic, π-π and π-electron-metal interactions. The extraction conditions were optimized and the developed composite adsorbent was characterized and provided a large surface area that enhanced extraction efficiency for sulfonamides. Coupled with high performance liquid chromatography, the adsorbent was used to quantitatively determine sulfonamides found in milk samples. The response of the developed method exhibited linearity from 5.0 to 150.0 µg kg-1 for sulfathiazole, and from 2.5 to 100.0 µg kg-1 for sulfamerazine, sulfamonomethoxine and sulfadimethoxine. Limits of detection were between 2.5 and 5.0 µg kg-1. Recoveries of sulfonamides in milk samples ranged from 83.0 to 99.2% with RSDs lower than 6%. The developed composite adsorbent showed good reproducibility and reusability.

A selective and efficient microfluidic method-based liquid phase microextraction for the determination of sulfonamides in urine samples.

Liquid phase microextraction (LPME) into a microfluidic has undergone great advances focused on downscaled and miniaturized devices. In this work, a microfluidic device was developed for the extraction of sulfonamides in order to accelerate the mass transfer and passive diffusion of the analytes from the donor phase to the acceptor phase. The subsequent analysis was carried out by high performance liquid chromatography with UV-DAD (HPLC-DAD). Several parameters affecting the extraction efficiency of the method such as the supported liquid membrane, composition of donor and acceptor phase and flow rate were investigated and optimized. Tributyl phosphate was found to be a good supported liquid membrane which confers not only great affinity for analytes but also long-term stability, allowing more than 20 consecutive extractions without carry over effect. Under optimum conditions, extraction efficiencies were over 96 % for all sulfonamides after 10 minutes extraction and only 10 µL of sample was required. Relative standard deviation was between 3-5 % for all compounds. Method detection limits were 45, 57, 54 and 33 ng mL-1 for sulfadiazine (SDI), sulfamerazine (SMR), sulfamethazine (SMT) and sulfamethoxazole (SMX), respectively. Quantitation limits were 0.15, 0.19, 0.18 and 0.11 µg mL-1 for SDI, SMR, SMT SMX, respectively. The proposed microfluidic device was successfully applied for the determination of sulfonamides in urine samples with extraction efficiencies within the range of 86-106 %. The proposed method improves the procedures proposed to date for the determination of sulfonamides in terms of efficiency, reduction of the sample volume and extraction time.

Performance evaluation of silica microspheres functionalized by different amine-ligands for hydrophilic interaction chromatography.

In this work, for the first time five amine-ligands including mono-amine, di-amine, tri-amine, secondary and tertiary amine, were functionalized on mesoporous micro-silicas and developed as stationary phases for hydrophilic interaction liquid chromatography (HILIC). The investigations about the retention mechanisms, effects of different chromatographic conditions and stability were systematically conducted. Three kinds of polar and hydrophilic compounds (saccharides, sulfonamides, nucleosides and nucleobases) were selected as probe molecules to evaluate their separation performances. Among the five stationary phases, only aminopropyl-bonded silica has already gained wide developments and applications. Whereas, there are no related researches about the other four to be utilized as separation media. By a series of chromatographic evaluations, the results revealed the other four mesoporous micro-silica materials functionalized with di-amine, tri-amine, secondary and tertiary amine, had great potential to be explored as novel stationary phases of HILIC. Particularly, the two stationary phases functionalized with di-amine and tri-amine exhibited outstanding separation and retention abilities. This work offered some insights on the understanding of retention in HILIC mode and provided us possibility to explore other amine-based HILIC stationary phases.

MOF-74@SiO2 core-shell stationary phase: Preparation and its applications for mixed-mode chromatographic separation.

The development of versatile mixed-mode stationary phase materials is of important meanings for solving the increasing demands for real sample analysis. Herein, with 2,5-dihydroxyterephthalic acid as the organic ligand and nickel as the metal centre, MOF-74 nanocrystal materials were facilely grafted on the surface of carboxyl-functionalized silica gel via layer-by-layer assembling technique. The structures of the monodisperse MOF-74@SiO2 material were proved by Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, elemental analysis, thermogravimetric analysis, and Brunauer-Emmett-Teller specific surface area and pore size analyzer, respectively. Because the introduced 2,5-dihydroxyterephthalic acid is of hydrophilic carboxyl and hydroxyl groups, the packed MOF-74@SiO2 column reveals hydrophilic interaction/reversed-phase mixed-mode retention properties. Compared with commercial C8 column or silica-based column, the MOF-74@SiO2 column shows distrinct separation selectivity in short separation time for polycyclic aromatic hydrocarbons, phenolic compounds and polar sulfonamide compounds. The developed MOF-74@SiO2 column was further successfully applied for the separation and detection of illegal addition of glucocorticoid in children's face cream as well as sulfonamides veterinary drug residues in pure milk. The research provides a simple and convenient approach to prepare multifunctional MOFs-based stationary phase materials.

Inhibition of α-, ß- and γ-carbonic anhydrases from the pathogenic bacterium Vibrio cholerae with aromatic sulphonamides and clinically licenced drugs - a joint docking/molecular dynamics study.

The binding mode of aromatic sulphonamides and clinically licenced drugs to the three carbonic anhydrase (CA, EC 4.2.1.1) isoforms from the human pathogen V. cholerae was here thouroghly characterised by a joint docking and molecular dynamics in silico protocol. In fact, VchCA, VchCAß, and VchCAγ are crucial in the pathogen life cycle and growth and represent innovative targets to fight V. cholerae proliferation overcoming the spreading chemoresistance to the available drugs. A set of 40 sulphonamides/sulfamates VchCAs inhibitors was studied using the proteins homology built 3 D models unveiling the key and stable interactions responsible for a potent CA inhibition. This study has the aim to offer insights and guidelines for the future rational design of potent and selective inhibitors targeting CA isoforms from V. cholerae or other human pathogens.

Covalent organic framework Schiff base network-1-based pipette tip solid phase extraction of sulfonamides from milk and honey.

In this work, a covalent organic framework Schiff base network-1 (SNW-1), was synthesized based on the Schiff base reaction between terephthalaldehyde and melamine and characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction and nitrogen adsorption-desorption isotherm analyses. The prepared SNW-1 was employed as pipette tip solid phase extraction adsorbent for the extraction of sulfonamides (SAs) prior to high performance liquid chromatography analysis. The parameters affecting the extraction efficiency, including the salt concentration, sample pH, amount of adsorbent, and types and volume of eluent were investigated in detail. Good linearities were obtained between the peak area and SAs concentration ranging from 5 to 500 ng mL-1 with correlation coefficients (R2) higher than 0.9998. The limits of detection and RSDs were lower than 0.25 ng mL-1 and 1.9 %, respectively. The developed method was further applied for the determination of SAs in milk and honey samples with recoveries in the range of 85.8 % - 118.0 % and RSDs less than 9.5 %. The results demonstrate that the SNW-1 shows great potential for the enrichment of trace SAs in complex matrices.

A graphene oxide-molybdenum disulfide composite used as stationary phase for determination of sulfonamides in open-tubular capillary electrochromatography.

A graphene oxide-molybdenum disulfide (GO-MoS2) composite was synthesized and utilized as the highly efficient stationary phase of open-tubular capillary electrochromatography (OT-CEC). The characterization results indicated that GO-MoS2 composite was successfully synthesized. The GO-MoS2-coated capillary column was prepared by covalent immobilization method for the determination of seven sulfonamides. The baseline separation of seven sulfonamides was achieved by GO-MoS2-coated capillary column. The linear range was 0.05-100 µg/mL for sulfisomidine, sulfathiazole, sulfamerazine, phthalylsulfathiazole and sulfacetamide, 0.1-100 µg/mL for sulfamonomethoxine and sulfachloropyridazine with a satisfactory correlation coefficients (R2) > 0.9994. This developed OT-CEC method was successfully applied to determinate of seven sulfonamides in environmental water and milk samples with good recoveries of 85.77% - 109.10% and 80.03% - 109.97%, respectively. These results indicated that GO-MoS2-coated capillary column possessed good stability and repeatability.

Determination of Sulfonamides in Milk by Cloud Point-Salting Out Extraction and Ultra-High-Performance Liquid Chromatography Tandem Mass Spectrometry.

A method involving cloud point-salting out extraction (CPSOE) coupled with UHPLC-MS/MS was developed for the determination of eleven sulfonamides in milk. In this study, the type and concentration of the surfactant, de-emulsification condition, pH value, volume of n-butanol, equilibration temperature and time were optimized. For this developed method, the linear range of SAs was from 0.05 to 50 µg L-1, and the correlation coefficients were higher than 0.997. The average recoveries for SAs were from 61.32 to 91.67%, and the LOQs were less than 0.06 µg kg-1.

Adsorption behavior of a metal organic framework of University in Oslo 67 and its application to the extraction of sulfonamides in meat samples.

In this work, a dispersive solid phase extraction (d-SPE) method for sulfonamides (SAs) has been developed using a stable and mesoporous metal organic framework (University in Oslo 67, UiO-67) as adsorbent, which was synthesized by coordination of Zr4+ ions with 4, 4-biphenyl-dicarboxylicacid (H2BPDC) through a facile one-pot method. Owing to the synergistic effects of π-π interaction, hydrogen bonding, hydrophobic interaction and size match between SAs and the adsorbent, the extraction performance of UiO-67 for SAs was obviously improved. The adsorption behavior, evaluated by the kinetic models, showed that the intraparticle diffusion was involved during the adsorption process. The proper match between the pore size of UiO-67 (3.49 nm) and the molecular sizes of SAs (1.1 nm × 0.65 nm) not only allowed SAs to diffuse intraparticle but also permitted them to adjust their configurations to form hydrogen bonding with the UiO-67. By combination with HPLC analysis, a simple, sensitive, accurate and precise method for detection of SAs has been established. The method proposed in this work showed good performances, including wide linearity (14.6-250 ng/g) with high correlation coefficients (R ≥ 0.9991), low limits of detection (LODs, 0.7-6.5 ng/g for all SAs), satisfactory precision (Intra-day RSDs ≤ 3.4%, inter-day RSDs ≤ 4.7%), and high accuracy (recovery: 83.4-103.8%). Furthermore, benefiting from the mesoporous structure and the Zr cluster center as well as the stability, UiO-67 shows great potential to be an excellent adsorbent of SPE for extraction of SAs from other complex matrices.

Magnetic solid-phase extraction of sulfonamide antibiotics in water and animal-derived food samples using core-shell magnetite and molybdenum disulfide nanocomposite adsorbent.

A molybdenum disulfide(MoS2)-based core-shell magnetic nanocomposite (Fe3O4@MoS2) was synthesized by the stepwise hydrothermal method. Two-dimension ultrathin MoS2 sheets with a thickness of approximately 20 nm were grown in situ on the surface of Fe3O4 (∼200 nm). They were employed as an adsorbent for the magnetic solid-phase extraction (MSPE) of sulfonamide antibiotics (SAs) from water samples. High-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) was used for SA quantitation. Extraction parameters, including the pH effect, amount of Fe3O4@MoS2, extraction time, temperature, and desorption conditions, were systematically investigated. The electrostatic interaction between the positively charged SAs and negatively charged MoS2 nanoparticles in the optimal extraction conditions enhanced the adsorption of SAs on the sorbent surface. Under chosen conditions, the proposed strategy achieved wide linear range of 1.0-1000 ng·L-1 SAs, low limits of detection (LOD, 0.20-1.15 ng·L-1, S/N = 3:1), good trueness (recoveries between 85.50-111.5%), satisfactory repeatability and reproducibility (relative standard deviation, <10%, n = 5), and excellent recoveries between 80.20% and 108.6% for SAs determination in spiked waste water samples. The proposed strategy was validated and successfully applied for the analysis of water, milk, pork meat and fish meat. The nanocomposites, which have the combined advantages of magnetic separation and high adsorption affinity toward SAs, are a promising sorbent for antibiotics extraction from real samples.