Simultaneous monitoring of multiple prohibited drugs in various aquatic products.

Both sedative and antipathogenic drugs are often found to be illegally used in aquaculture, but there is a lack of simultaneous monitoring methods. A method for simultaneously monitoring multiple prohibited drugs in various aquatic product samples was developed in this work, including fish, shrimp, crab, and shellfish. Sulfonic acid-functionalized magnetic graphitic carbon nitride (S-MGCN) was synthesized and validated to efficiently co-extract all targets (adsorption efficiency over 90.07%) through various adsorption mechanisms such as electrostatic interaction, hydrogen bonding, and π-π interaction while demonstrating good sample matrix purification ability (matrix effect below 13.60%). A new magnetic solid-phase extraction method based on S-MGCN was subsequently established. Coupled with UPLC-MS/MS, the detection limits were 0.030.075 µg /kg, and the recoveries ranged from 88.76% to 111.74% with the RSDs lower than 14.60%, indicating that the developed method has good sensitivity, accuracy, and precision. Further validation of its practicality was achieved through actual sample analysis.

[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.

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.

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.