[Sulfonated magnetic graphite carbon nitride solid-phase extraction-ultra performance liquid chromatography-tandem mass spectrometry for screening malachite green and leucomalachite green in freshwater fish].

Malachite green (MG) and its metabolite, leucomalachite green (LMG), exert toxic effects on the human body. The use of these dyes is illegal, but they are still detected in aquatic products. Freshwater fish are aquatic products with the high non-qualified rates. Therefore, the sensitive screening of MG and LMG in freshwater fish is of great importance to ensure the safety of aquatic products. Owing to the low contents of MG and LMG in fish and the complex matrix of actual samples, sample preparation is required before detection to purify impurities and enrich the target compounds. Graphite carbon nitride (GCN), a polymer material composed of C, N, and H, has good chemical and thermal stability, a large specific surface area, and a large number of active sites. It has a wide range of application prospects in adsorption and can be used in food safety testing when compounded with Fe3O4 to form magnetic graphite carbon nitride (MGCN). In this study, sulfonated magnetic graphite carbon nitride (S-MGCN) was prepared by further functionalizing MGCN with sulfonic acid. After characterization by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), and vibrating sample magnetometry (VSM), a magnetic solid-phase extraction (MSPE) method based on S-MGCN was established to extract MG and LMG from freshwater fish. The targets were screened using ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Following sulfonic acid functionalization, S-MGCN showed increased electrostatic interactions based on the MGCN adsorption mechanism, which includes hydrogen bonds and π-π interactions; thus, its adsorption efficiency was significantly improved. The matrix effects were -42.21% and -33.77% before functionalization, -11.40% and -7.84% after functionalization, thus confirming that S-MGCN has significant matrix removal ability. Given that S-MGCN demonstrated excellent efficiency as an MSPE adsorbent, the adsorption conditions for S-MGCN were optimized. The optimal conditions were as follows: adsorbent dosage, 15 mg; adsorption time, 2 min; solution pH, 5; and ionic strength, not adjusted. Under these conditions, the adsorption efficiency of S-MGCN could reach 94.2%. Different organic solvents were used to elute adsorbed MG and LMG, and the desorption efficiency peaked when 1%(v/v) ammonia acetonitrile was used as the elution solvent. The elution volume was also optimized, and a maximum desorption efficiency of 93.2% was obtained when 1 mL of 1%(v/v) ammonia acetonitrile was added to S-MGCN. The limits of detection (LODs) and quantification (LOQs) of the two targets were determined at signal-to-noise ratios (S/N) of 3 and 10, respectively. The LODs and LOQs were 0.075 µg/kg and 0.25 µg/kg, respectively. The linear ranges of the two target compounds were 0.25-20.0 µg/kg with correlation coefficients (r) greater than 0.998. To assess accuracy and precision, we prepared spiked samples at three levels (low, medium, and high) with six parallel samples per level (n=6). The recoveries ranged from 88.8% to 105.9%. The intra- and inter-day relative standard deviations were 5.4%-13.7% (n=6) and 3.3%-11.1% (n=3), respectively. Compared with the national standard method, the proposed method features simpler sample pretreatment procedures, less use of organic reagents (5 mL), and a shorter extraction time (2 min); moreover, the method does not require complicated elution steps, and the eluent can be directly analyzed by UPLC-MS/MS. The test results of actual samples were consistent with those obtained via the national standard method, thus confirming the practical feasibility of the developed method. The proposed MSPE method based on S-MGCN is an efficient and environmentally friendly method that could provide a new methodological reference for the sensitive screening of MG and LMG in actual samples.

Polyvinyl alcohol electrospun nanofiber membrane based solid-phase extraction for monitoring administered aminoglycoside antibiotics in various animal-derived foods.

This work aims to develop a widely applicable method to monitor administered AGs in various animal-derived food samples to ensure food safety. A polyvinyl alcohol electrospun nanofiber membrane (PVA NFsM) was synthesized and employed as solid-phase extraction (SPE) sorbent, in combination with UPLC-MS/MS, for the simultaneous detection of ten AGs in nine types of animal-derived food samples. PVA NFsM exhibited excellent adsorption performance for the targets (with an adsorption rate of over 91.09%), good matrix purification ability (with a reduction of 7.65%-77.47% in matrix effect after SPE), and good recyclability (can be reused 8 times). The method displayed a linear range of 0.1-25000 µg/kg and attained limits of detection for AGs were 0.03-15 µg/kg. Spiked samples demonstrated a recovery of 91.72%-100.04% with a precision of<13.66%. The practicality of the developed method was verified by testing multiple actual samples.

Efficient adsorptive removal of aminoglycoside antibiotics from environmental water.

Aminoglycoside antibiotics (AGs) in environmental water are emerging pollutants that must be removed to protect human health and the ecosystem. However, removing AGs from environmental water remains a technical challenge due to high polarity, stronger hydrophilicity and unique characteristics of polycation. Herein, a thermal-crosslinked polyvinyl alcohol electrospun nanofiber membrane (T-PVA NFsM) is synthesized and firstly leveraged as the adsorptive removal of AGs from environmental water. The thermal crosslinking strategy is demonstrated to enhance both the water resistance and hydrophilicity of T-PVA NFsM, thereby effectively interacting with AGs with high stability. Experimental characterizations and analog calculations indicate that T-PVA NFsM utilizes multiple adsorption mechanisms, including electrostatic and hydrogen bonding interactions with AGs. As a result, the material achieves 91.09%-100% adsorption efficiencies and a maximum adsorption capacity of 110.35 mg g-1 in less than 30 min. Furthermore, the adsorption kinetics follow the pseudo-second-order model. After eight consecutive adsorption-desorption cycles, T-PVA NFsM with a simplified recycling process maintains a sustainable adsorption capability. Compared with other forms of adsorption materials, T-PVA NFsM has significant advantages such as less consumption of adsorbent, high adsorption efficiency and fast removal speed. Therefore, T-PVA NFsM-based adsorptive removal holds promise for eliminating AGs from environmental water.

A nanofiber-mat-based solid-phase sensor for sensitive ratiometric fluorescent sensing and fine visual colorimetric detection of tetracycline.

Sensitive and real-time tetracycline (TC) monitoring method is of great significant for food safety and human health. Herein, a novel TC dynamic sensing mode based on a solid-phase nanofiber mat (NFM) sensor SP@COF/SDBS/PS NFM was constructed for the first time, where spiropyran-modified covalent organic framework (SP@COF) with red emissions (λem = 620 nm) was used as the reference fluorescence. Utilizing the adsorptive interaction between SP@COF/SDBS/PS NFM and TC, a PS-TC-SDBS supramolecular complex with a large rigid structure was formed, thus enhancing the fluorescence of TC (λem = 550 nm). The dynamic solid-phase sensing mode is unique and can be employed to selectively adsorb TC, with reduced interference by impurities in complex samples, and thus the sensitive TC ratiometric fluorescent sensing with a detection limit of 2.14 nM, and fine visual colorimetric detection with polychromatic wide color range (red-orange-yellow-green) was realized.

Electrospun chitosan/polyethylene oxide nanofibers mat loaded with copper (II) as a new sensor for colorimetric detection of tetracycline.

Using electrospun chitosan/polyethylene oxide nanofibers mat (CS/PEO NFM) as carrier, Cu@CS/PEO NFM, a new tetracycline (TC) solid-state colorimetric sensor, were simply prepared by directly immobilizing Cu2+ on surface of CS/PEO NFM. After immersing in TC solutions, Cu@CS/PEO NFM can display visible color changes to the naked eye within 5.0 min, and the TC concentration-dependent color changes can also be quantitatively analyzed with a smartphone. Because Cu2+ can enhance the adsorption of CS/PEO NFM for TC, Cu@CS/PEO NFM possess a more sensitive response ability to TC, ensuring that the colorimetric sensing detection will not be interfered by other coexisting drugs. Due to the reversible combination of chitosan and Cu2+, the colorimetric sensing ability of Cu@CS/PEO NFM can be regenerated even after being reused at least 4 times. In addition, the naked eye detection limit of Cu@CS/PEO NFM-based colorimetric sensing is 65 µg kg-1, which does not exceed the maximum residue limit in milk samples set by China (100 µg kg-1). The obtained results fully indicated the practical application value of this method in preventing the hazard of TC residues.

Fast and simple determination of estrogens in milk powders by magnetic solid-phase extraction using carbon nitride composites prior to HPLC.

A graphitic carbon nitride (g-C3N4/Fe3O4)-based magnetic solid-phase extraction (MSPE) approach was established for fast and simple analysis of estrogens in milk powders. The composites were characterized by X-ray diffractometer, scanning electron microscope, and Brunauer-Emmett-Teller surface area and pore size distribution analyzer. Compared with the bulk g-C3N4, g-C3N4/Fe3O4 gave a narrower distribution of mesopores and provided an enhanced surface area from 77.1 to 113.7 m2/g. Polar analytes of estrogens were selected as model compounds and the extraction of four estrogens was achieved in n-hexane using 15 mg of adsorbent within only 2 min. Possible extraction mechanism of g-C3N4/Fe3O4 for these estrogens was explored in terms of the polarity of the analytes and the adsorption performance of the adsorbent. The hydrophobicity and the hydrogen-bond interaction between the estrogens and g-C3N4 were responsible for the efficient adsorption. Combined with HPLC, MSPE with the prepared adsorbent gave the enhancement factors of 20 to 24 and the linear ranges of 2-200 µg/kg for 17ß-estradiol and 17α-ethinylestradiol, 1.5-150 µg/kg for estrone, and 3-300 µg/kg for hexestrol. The detection limits and quantification limits for the estrogens in milk powders were 0.5-0.9 µg/kg and 1.5-3.0 µg/kg, respectively. The recoveries varied from 75.1 to 97.2%, with the intra-day and inter-day precisions ≤ 14.2%. Furthermore, the enrichment of the analytes and the clean-up of fat and protein interferences were achieved simultaneously with one-step g-C3N4-based MSPE. The present method was convenient, fast, and sensitive, and therefore could be successfully applied for the determination of estrogens in milk powders. Graphical abstract.

A hybrid material composed of graphitic carbon nitride and magnetite (Fe3O4) for magnetic solid-phase extraction of trace levels of hydroxylated polycyclic aromatic hydrocarbons.

Magnetic carbon nitride composites were synthesized via a solvothermal reaction and developed as an effective adsorbent for magnetic solid-phase extraction of trace hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) from urine samples prior to their determination by HPLC. The sorbent was characterized by Fourier transform infrared spectrometry, X-ray diffractometry, scanning electron microscopy, vibrating sample magnetometry and solvent stability experiments. The adsorption of hydroxy-PAHs is better by a factor or 20 to 49 compared to bare Fe3O4 and comparable that of a commercial C18 sorbent. The adsorbent amount, adsorption time and eluting solvent and volume were optimized. The complete extraction for the OH-PAHs at a level of 40 ng·mL-1 and by using 4 mg sorbent is completed within 3 min. With an enzymatic hydrolyzed urine sample loading volume of 2 mL, enhancement factors in the range of 9-10, and a limit of detection (at S/N = 3) of 0.08 ng·mL-1 were achieved. The method showed a linear response in the 0.25-250 ng·mL-1 hydroxy-PAH concentration range, and intra-day and inter-day precisions are 1.5-7.7% and 2.2-8.7%, respectively. The recovery from spiked urine samples ranged from 90.1% to 102%. The sorbent was stable over 10 successive cycles of extraction/desorption of urine sample without significant loss of extraction efficiency. The method was successfully applied for the determination of OH-PAHs in urine samples of smoking volunteers. Graphical abstract Schematic presentation of the preparation of graphitic carbon nitride (g-C3N4)/magnetite (Fe3O4) using a solvothermal reaction, and application for magnetic solid-phase extraction of three trace hydroxy polycyclic aromatic hydrocarbons (OH-PAHs) in urine samples of smoking volunteers.

[Determination of three hydroxyl polycyclic aromatic hydrocarbons in urine using magnetic solid-phase extraction with magnetic carbon nitride composites coupled with high performance liquid chromatography].

A method based on the magnetic solid-phase extraction using magnetic carbon nitride composites coupled with high performance liquid chromatography-fluorescence detector (HPLC-FLD) was developed for the simultaneous determination of three hydroxyl polycyclic aromatic hydrocarbons (OH-PAHs) in urine. The synthesized sorbent was characterized by scanning electron microscope, X-ray diffractometer, vibrating sample magnetometer and surface area analyzer. The extraction parameters such as amount of sorbent, extraction time, eluting solvent and volume (single eluting volume×eluting times) were investigated in detail. Under the optimized conditions, the method showed a linear range of 0.25-250 µg/L (correlation coefficient=0.999). The limit of detection was 0.08 µg/L and the limit of quantification was 0.25 µg/L for each analyte. The proposed method gave a recovery of 90.1%-102%. The relative standard deviations for the intra-day and inter-day were 1.5%-7.7% and 2.2%-8.7%, respectively. The feasibility of the developed method was further demonstrated during the analysis of real samples. The results indicate that the magnetic carbon nitride composites can be used for the effective purification and enrichment of three OH-PAHs in urine. In addition, the method can be applied for analysis of urinary OH-PAHs in a simple, fast, and effective manner.

Rapid monitoring of plant growth regulators in bean sprouts via automated on-line polymeric monolith solid-phase extraction coupled with liquid chromatography tandem mass spectrometry.

An automated on-line solid-phase extraction (SPE) following liquid chromatography tandem mass spectrometry was established for the fast determination of plant growth regulator residues in soybean sprout and mung bean sprout. The crude extracted specimens were directly purified on a poly (2-(dimethylamino) ethyl methacrylate-co-ethylene dimethacrylate) monolithic column which was well-defined as the on-line SPE adsorbent. Under the optimized conditions, the developed method gave the linear range of 0.3-50 ng/mL for gibberellin and 2,4-dichlorophenoxyacetic acid, 0.2-50 ng/mL for 4-chlorophenoxyacetic acid, and 0.5-50 ng/mL for 1-naphthaleneacetic acid (r ≥ 0.998). The detection limits (S/N = 3) ranged from 1.0 to 2.5 µg/kg and the recoveries for spiked soybean sprout samples were in the range of 75.0-93.3%. Besides, the total time for one analysis was 16 min. The reusability of the monolith was up to 600 extractions. The proposed process facilitated fully automated SPE and accurate determination in one step with rapidity, simplicity, and reliability. Graphical abstract ᅟ.

[Determination of four hydroxyl polycyclic aromatic hydrocarbons in urine by solid-phase extraction with monolithic column coupled with high performance liquid chromatography].

A method based on monolithic column solid-phase extraction (SPE) coupled with high performance liquid chromatography (HPLC) was developed for the simultaneous determination of four hydroxyl polycyclic aromatic hydrocarbons (OH-PAHs) in urine.A poly (butyl methacrylate-co-ethylene dimethacrylate) monolithic column was prepared in a syringe and was used as the sorbent.The parameters influencing SPE, such as loading volume, washing solvent, eluent, and elution volume, were investigated in detail.Under the optimized conditions, the linearities were obtained in range of 1.2-200.0 ng/mL, and the LODs and LOQs of the analytes were 0.06-0.09 ng/mL and 0.20-0.30 ng/mL, respectively.The intra-day and inter-day relative standard deviations were 1.4%-5.3% and 2.6%-7.3%, respectively.The recoveries evaluated using the spiked (3 ng/mL) urine samples of coke oven workers ranged from 78.2% to 117.0%.The feasibility of the developed method was further demonstrated for the analysis of the real samples.The results indicated that the reusable monolithic column enabled effective purification and enrichment of the four OH-PAHs in urine, and can be applied to the analysis of OH-PAHs in urine due to its simplicity and accuracy.