Solid-phase Extraction Adsorbent Research Articles

Synthesis of a cysteine functional covalent organic framework via facile click reaction for the efficient solid phase extraction of substituted p-phenylenediamine-derived quinones

N,N′-Substituted p-phenylenediamine quinones (PPD-Qs) are the emerging toxicant, which transform from the rubber tire antioxidant N,N′-substituted p-phenylenediamines (PPDs). Because of their potential toxic and widespread occurrence in the environment, PPD-Qs have received great attention. However, efficiently extracting PPD-Qs from complex samples is still a challenge. Herein, a cysteine functional covalent organic framework (Cys-COF) designed according to the “donor-acceptor” sites of hydrogen bonding of PPD-Qs was synthesized via click reaction and then used as solid-phase extraction (SPE) adsorbent. Cys-COF can form the seven-member ring adsorption structure with PPD-Qs via hydrogen bonding. The adsorption mechanism was tentatively revealed by density functional theory (DFT). After optimizing the Cys-COF-SPE parameters, PPD-Qs were efficiently extracted from water, soil, sediment, and fish, followed by detection using ultra-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). The Cys-COF-SPE-UHPLC-MS/MS method exhibited ideal linearity (R2 ≥ 0.9932), high relative recoveries (80.4–111 %), and low limits of detection (0.0001–0.0013 ng mL−1). In addition, the bioconcentration kinetics in goldfish provides a feasible platform to investigate the toxicity and accumulated ability of PPD-Qs.

Zeolitic imidazolate framework-8 as a high-affinity adsorbent for dispersive solid-phase extraction in the analysis of plant growth regulators in fruits.

Facile and sensitive determination of plant growth regulators (PGRs) in food samples is crucial but still poses a significant challenge. In this study, to enhance the sensitivity of the HPLC-DAD method for PGR detection, a dispersive solid phase extraction (d-SPE) method using zeolitic imidazolate framework-8 (ZIF-8) as the highly effective adsorbent is developed. ZIF-8 nanoparticles are formed through the coordination of Zn2+ with 2-methylimidazole. Due to its high porosity, large surface area, abundant π electronics and nitrogen electronics, ZIF-8 exhibits a strong affinity to PGRs due to the synergistic effects of π-π interaction, van der Waals force, H-bond, and surface effect. Under the optimal d-SPE conditions, the sensitivity of the method is significantly enhanced with outstanding performances, including a wide range of linearity (2.0-200 ng g-1) with high correlation coefficients (R ≥ 0.9989), low limits of detection (LODs, 0.9-8.0 ng g-1 for all PGRs), satisfactory precision (intra-day RSDs ≤ 3.3%, inter-day RSDs ≤ 4.2%), and high accuracy (recovery: 86.6-101.5%). The developed method was successfully applied to quantitatively detect 9 PGRs in fruit samples, yielding satisfactory results. This d-SPE-HPLC-DAD method, characterized by high sensitivity, simplicity, efficiency, ease of practice and cost-effectiveness for PGR detection, shows potential for detecting PGRs in other complex samples and provides a strategy for designing target-affinity adsorbents.

Co2+ coordination-assisted molecularly imprinted covalent organic framework for selective extraction of ochratoxin A

Covalent organic frameworks (COFs) are attractive materials for sample pretreatment due to their tunable structures and functions. However, the precise recognition of contaminant in complex environmental matrices by COFs remains challenging owing to their insufficient specific active sites. Herein, we report Co2+ coordination-assisted molecularly imprinted flexible COF (MI-COF@Co2+) for selective recognition of ochratoxin A (OTA). The MI-COF@Co2+ was prepared via one-step polymerization of 3,3-dihydroxybenzidine, 2,4,6-tris(4-formylphenoxy)− 1,3,5-triazine, Co2+ and template. The flexible units endowed COFs with the self-adaptable ability to regulate the molecular conformation and coordinate with Co2+ to locate the imprinted cavities. The coordination interaction greatly improved the adsorption capacity and selectivity of MI-COF@Co2+ for OTA. The prepared MI-COF@Co2+ was used as solid phase extraction adsorbent for high-performance liquid chromatography determination of OTA with the detection limit of 0.03 ng mL−1 and the relative standard deviation of < 2.5 %. In addition, this method permitted interference-free determination of OTA in real samples with recovery from 89.5 % to 102.8 %. This work provides a simple way to improve the selectivity of COFs for the determination of hazardous compounds in complex environments.

Facile preparation of covalent-organic framework composites for magnetic solid-phase extraction of naphthaleneacetic acid in food prior to HPLC-UV analysis

Novel magnetic covalent organic frameworks (COFs) were prepared by one-pot synthetic strategy and employed as an efficient adsorbent for magnetic solid-phase extraction (MSPE) of naphthaleneacetic acid (NAA) in food samples. Depending on the predesigned the hydrogen bonding, π-π and hydrophobic interactions of magnetic COFs, the efficient and selective extraction process for NAA was achieved within 15 min. The magnetic COFs adsorbent combined with HPLC-UV was devoted to develop a novel quantitative method for NAA in complex food. The method afforded good coefficient in range of 0.002-10.0 μg mL-1 and low limit of detection was 0.0006 μg mL-1. And the newly established method afforded less adsorbent consumption, wider linearity and lower LODs than the reported analytical methods. Ultimately, the method was successfully applied to determine NAA in fresh pear, tomato and peach juice. The magnetic COFs based MSPE coupled with HPLC-UV method provided a simple, efficient and dependable alternative to monitor trace NAA in food samples.

Magnetic multi-template molecularly imprinted polymers for selective simultaneous extraction of chlorophenols followed by determination using HPLC

Magnetic multi-template molecularly imprinted polymers (M-mt-MIPs) were successfully synthesized by surface imprinting and multi-template imprinting strategy, using polydopamine coated magnetic multi-walled carbon nanotubes as supporting materials, five typical chlorophenols (CPs) as templates, methacrylic acid as functional monomer and ethylene glycol dimethacrylate as cross-linker. Compared to non-imprinted polymers (NIPs), the as-prepared M-mt-MIPs showed high adsorption capacity (32.58‒80.63 mg g−1), rapid mass transfer and specific selectivity for the five targeted CPs, which were applied as magnetic solid-phase extraction (MSPE) adsorbents. Parameters affecting MSPE efficiency were detailed investigated, such as adsorbents dosage, sample pH, extraction time, type and volume of desorption solvent and salt effect. Combined with HPLC-DAD, a simple, rapid and sensitive method was established, showing good linearity (2‒200 μg L−1), low limits of detection (0.32‒0.49 μg L−1), and high enrichment factors (35.2‒108). The developed M-mt-MIPs-MSPE-HPLC method was applied to enrich and determine CPs in tannery wastewater, wet-blue and crust leather, and satisfactory spiking recoveries were attained in the range of 73.95‒109.7% with relative standard deviations (RSDs) of 2.13–8.48%. This study provided a new alternative material and method to rapid simultaneously extract and analyze low concentration of typical CPs in complicated matrices.

Conjugated microporous polymer for solid-phase extraction of neonicotinoid insecticides from environmental water samples

Conjugated microporous polymers (CMPs) have unique characteristics and have been used in a range of fascinating applications in separation sciences. In this study, a CMP, designated as CMP-1, was synthesized via the Sonogashira-Hagihara coupling reaction using 1,3,5-triphenylbenzene and 1,4-dibromobenzene as building blocks. CMP-1 features a large surface area, abundant micropore structures, and excellent stability, making it a promising solid-phase extraction adsorbent for the efficient enrichment of neonicotinoid insecticides (NEOs). Under the optimized conditions, CMP-1 was combined with high-performance liquid chromatography and diode array detection to enable the detection of NEOs with a wide linear range (0.5–200 μg·L–1), a low detection limit (0.26–0.58 μg·L–1), and acceptable precision. The developed method was applied to determine spiked NEOs in three types of environmental water samples, with recoveries of 73.7%–112.0% and relative standard deviations of 0.6%–9.4%.

Synthesis of green nanosorbent from bovine serum albumin and curcumin for magnetic solid phase extraction of pesticides from food samples

For the first time, a magnetic carbon nanocomposite was synthesized using one-step hydrothermal procedure, employing bovine serum albumin, curcumin, and ferric ammonium citrate. Additionally, the application of this novel composite as an adsorbent for magnetic dispersive solid phase extraction of fungicides and pesticides from water and food samples is a unique aspect of this study. Under optimum conditions (salt concentration: 5.0% w/v, pH: 7.0, desorption solvent: ethanol, sorbent amount: 20 mg, extraction time: 20 min, desorption time: 3 min, stirring rate: 500 rpm, sample volume: 30 mL, extraction temperature: room temperature, and desorption solvent volume: 150 μL) linearity (2.5 to 1400 ng mL−1), coefficients of determination (R2 ≥ 0.997), limits of detection (0.75 to 1.5 ng mL−1), and limits of quantification (2.5 to 5.0 ng mL−1) were achieved. The method validation results showed extraction recovery ranging from 71.2% to 93.4%, and preconcentration factors ranging from 142.5 to 186.1.

Correction: Facile and rapid preparation of magnetic octadecylamine nanocomposite and its application as a capable adsorbent in magnetic dispersive solid phase extraction of some polycyclic aromatic hydrocarbons from wastewater samples

Correction: Facile and rapid preparation of magnetic octadecylamine nanocomposite and its application as a capable adsorbent in magnetic dispersive solid phase extraction of some polycyclic aromatic hydrocarbons from wastewater samples

Harnessing an amide-based covalent organic framework in solid-phase extraction for chlorophenol analysis in industrial wastewaters.

An amide-based covalent organic framework (COF) was successfully synthesized using the reaction between 1,3,5-trimesoyl chloride and ethylenediamine. The structure and morphology of the COF were characterized using Fourier-transform infrared spectra, nuclear magnetic resonance spectroscopy, X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and Brunauer-Emmett-Teller surface area analysis. The COF was employed as a solid-phase extraction adsorbent for the sampling and preconcentration of chlorophenols from industrial wastewater samples prior to high-performance liquid chromatography with ultraviolet detection. The experimental parameters influencing the extraction efficiency including type and volume of eluent solvent, sample solution volume, salt concentration, sample flow rate, and sample solution pH were investigated and optimized using a response surface methodology employing Box-Behnken-design. Under optimized conditions, calibration curves exhibited good linearities over the range of 0.003-10µg/mL with determination coefficients (R2) ranging from 0.9982 to 0.9999. The method's limits of detection ranged from 0.001 to 0.01µg/mL. Good repeatability was achieved with relative standard deviations below 4.7%. The developed procedure utilizing the COF adsorbent was successfully applied to determine chlorophenols accurately and precisely in various industrial wastewater samples.

Hollow multi-shelled MOF derivative adsorbent for efficient magnetic solid-phase extraction of several typical endocrine disrupting compounds from water

Bisphenols and benzophenones are two typical kinds of endocrine-disrupting compounds (EDCs) that have been extensively detected in water environments, posing unanticipated risks to aquatic organisms and humans. It is urgent to develop efficient sample pretreatment methods for precise measurement of such EDCs. In this study, a magnetic and multi-shelled metal-organic framework derivative material has been prepared to extract and enrich trace bisphenols and benzophenones from water. Via a solvothermal reaction induced by sodium citrate followed by a carbonization treatment, a ZIF-67@ZIF-8 derived CoZn-magnetic hierarchical carbon (CoZn-MHC) material has been synthesized as a high-performance magnetic solid-phase extraction (MSPE) adsorbent. This adsorbent exhibited a good specific surface area (213.80 m2⋅g−1) and a saturation magnetization of 63.2 emu·g−1. After the optimization of several parameters (including adsorbent dosage, extraction time, pH, ionic strength, desorption solvent, and solvent volume), an efficient MSPE method for several EDCs (comprising bisphenols and benzophenones) was developed with a good linear range (R2 ≥ 0.990), a high sensitivity range (LODs: 0.793–5.37 ng⋅L−1), and good reusability (RSD ≤4.67 % in five consecutive tests). Furthermore, the material exhibited commendable resistance to matrix interference in natural water samples with the recovery rates of target compounds ranging from 74.8 % to 107 %. We envision that the preparation strategy of this functional metal-organic framework (MOF)-based adsorbent for EDCs may provide insights for relevant research in the future.

Effectiveness of Water Hyacinth Biochar as a Potential Adsorbent in Solid-Phase Extraction Together with Liquid Chromatography-Mass Spectrometry for Determination of Pesticide Residues in Lager Beer

Effectiveness of Water Hyacinth Biochar as a Potential Adsorbent in Solid-Phase Extraction Together with Liquid Chromatography-Mass Spectrometry for Determination of Pesticide Residues in Lager Beer

Revolutionizing medicine: Molecularly imprinted polymers as precision tools in cancer diagnosis and antibiotic detection.

Molecularly imprinted polymers (MIPs) are pivotal in medicine, mimicking biological receptors with enhanced specificity and affinity. Comprising templates, functional monomers, and cross-linkers, MIPs form stable three-dimensional polymer networks. Synthetic templates like glycan and aptamers improve efficiency, guiding the molecular imprinting process. Cross-linking determines MIPs' morphology and mechanical stability, with printable hydrogels offering biocompatibility and customizable properties, mimicking native extracellular matrix (ECM) microenvironments. Their versatility finds applications in tissue engineering, soft robotics, regenerative medicine, and wastewater treatment. In cancer research, MIPs excel in both detection and therapy. MIP-based detection systems exhibit superior sensitivity and selectivity for cancer biomarkers. They target nucleic acids, proteins, and exosomes, providing stability, sensitivity, and adaptability. In therapy, MIPs offer solutions to challenges like multidrug resistance, excelling in drug delivery, photodynamic therapy, photothermal therapy, and biological activity regulation. In microbiology, MIPs serve as adsorbents in solid-phase extraction (SPE), efficiently separating and enriching antibiotics during sample preparation. They contribute to bacterial identification, selectively capturing specific strains or species. MIPs aid in detecting antibiotic residues using fluorescent nanostructures and developing sensors for sulfadiazine detection in food samples. In summary, MIPs play a pivotal role in advancing medical technologies with enhanced sensitivity, selectivity, and versatility. Applications range from biomarker detection to innovative cancer therapies, making MIPs indispensable for the accurate determination and monitoring of diverse biological and environmental samples.

Magnetic dispersive solid-phase extraction of clarithromycin and azithromycin by Fe3O4@ionic salt g-C3N4 adsorbent and HPLC-UV

In this study, Fe3O4@ionic salt g-C3N4 was synthesized as a new adsorbent for magnetic dispersive solid phase extraction (MDSPE) of two antibiotics (clarithromycin and azithromycin) in biological samples followed by HPLC-UV. The new nanocomposite was characterized by Fourier-transform infrared (FT-IR), field emission-scanning electronic microscope (FE-SEM), transmission electron microscope (TEM), nitrogen adsorption–desorption analysis, X-ray powder diffraction (XRD), and vibrating sample magnetometer (VSM). Box-Behnken design (BBD) and response surface methodology (RSM) were used for the optimization and design of experiments. The method had a suitable linear range (1–300 µg/L), a high coefficient of determination (R2; 0.9988 and 0.9993), and a low detection limit (0.33 and 0.42 µg/L) for clarithromycin and azithromycin, respectively. The applicability of the method was evaluated by estimating the recovery of analytes from urine and blood serum samples. Recovery of more than 90.0 % and RSDs of less than 5.2 % show the acceptable accuracy and precision of the proposed method.

Development of a NiFe2O4 covalent organic framework based magnetic solid-phase extraction approach for specific capture of quinolones in animal innards prior to UHPLC–Q–Orbitrap HRMS detection

This study aimed to present a selective and effective method for analyzing quinolones (QNs) in food matrix. Herein, a NiFe2O4-based magnetic sodium disulfonate covalent organic framework (NiFe2O4/COF) was prepared using a simple solvent-free grinding method, and was adopted as a selective adsorbent for magnetic solid phase extraction of QNs. Coupled with UHPLC–Q–Orbitrap HRMS, an efficient method for simultaneous detection of 18 kinds of QNs was established. The method exhibited good linearity (0.01–100 ng g−1), high sensitivity (LODs ranging from 0.0011 to 0.0652 ng g−1) and precision (RSDs below 9.5%). Successful extraction of QNs from liver and kidney samples was achieved with satisfactory recoveries ranging from 82.2% to 108.4%. The abundant sulfonate functional groups on NiFe2O4/COF facilitated strong affinity to QNs through electrostatic and hydrogen bonding interactions. The proposed method provides a new idea for the extraction of contaminants with target selectivity.

Valorisation of coal gasification slag and fly ash to mesoporous activated carbon @zeolite socony mobil-5 composite for preconcentration of pharmaceuticals and their removal

Upcycling industrial solid waste, such as coal gasification slag and fly ash, to functional adsorbents with unique structures for water decontamination is of great importance to achieving Sustainable Development Goal 6.0. This study used coal gasification slag and fly ash to synthesise mesoporous activated carbon @zeolite socony mobil-5 (MAC@ZSM-5) composite. Various analytical techniques were used to investigate the surface, morphological, and structural properties of the MAC@ZSM-5 composite. The MAC@ZSM-5 composite had a relatively high specific surface and was classified as a mesoporous adsorbent. The MAC@ZSM-5 composite was used as an adsorbent in ultrasound-assisted micro solid phase extraction (UA-µSPE) for effective preconcentration and removal of aspirin (ASP), ibuprofen (IBP), and paracetamol (PCT) from water samples before determination by high-performance liquid chromatography equipped with a photodiode array detector (HPLC-DAD). The Langmuir adsorption isotherm characterised the adsorptive removal method, while the kinetics followed a pseudo-second order type. Thermodynamic studies revealed that the adsorption process was endothermic, spontaneous, and chemisorption. Additionally, the UA-µSPE/HPLC-DAD method displayed a good linear range of 0.1–1000 µg/L, with a coefficient of determination greater than 0.99. The developed method had a good performance, as shown by the relatively low limits detection (LODs: 0.017–0.064 µg/L) and quantification (LOQs: 0.057–0.21 µg/L) as well as high precision (relative standard deviation (%RSD) < 5 %). The proposed method was applied successfully for preconcentration and removal of the target analytes from real water samples. The MAC@ZSM-5 composite was reusable (up to 5 cycles) and proved a promising adsorbent for effective extraction, preconcentration, and adsorptive removal of emerging contaminants from water bodies.

Covalent organic frameworks as dispersive solid-phase extraction adsorbents for β-lactam detection in aquatic environments

Currently, antibiotic residues in the environment pose a serious public health risk; therefore, new sensitive approaches for detecting the presence of antibiotics are urgently needed. Ionic-type covalent organic frameworks (TAPB-(TFIT)+Cl−-COFs) were designed and prepared in this work, and these imine-linked COFs were characterized by several techniques, proving of porous structure and rich of nitrogen. The materials were applied to the extraction of β-lactams from aqueous samples, and the important parameters of the adsorption–desorption conditions were optimized. A dispersive solid-phase extraction method coupled with ultrahigh-performance liquid chromatography-tandem mass spectrometry (TAPB-(TFIT)+Cl−-COFs-d-SPE-UPLC-MS/MS) was proposed and utilized to determine the levels of 11 antibiotics in the β-lactams in the extracted samples. Good linearity (1.0–200.0 μg·L−1, r > 0.9999) was achieved together with limits of detection and quantification of 0.01–0.92 μg·L−1 and 0.05–2.78 μg·L−1, respectively; recoveries ranged from 75.57 to 114.20 %, conferring relative standard deviations < 8.99 % and negligible matrix effects (84.88–109.40 %). The synthesized TAPB-(TFIT)+Cl−-COFs were demonstrated to have good reusability and high stability. Furthermore, the proposed method was clearly shown to be sensitive and separable for the reliable simultaneous detection of 11 β-lactam residues in aquatic environments.

UiO-66@Fe3O4 nanocomposite as an adsorbent in dispersive solid phase extraction of metformin in surface water and wastewater

Metformin, an anti-hypoglycemic medication, has been used for decades due to its efficiency and is the most consumed pharmaceutical drug worldwide. Consequently, monitoring its concentration in environmental water is important due to its suspected effect on human health and aquatic life. This study reported the extraction, preconcentration, separation and determination of metformin (MET) in waters. Dispersive solid phase extraction (dSPE) using UiO-66@Fe3O4 nanocomposite as a sorbent was used to extract and preconcentrate MET. The high-performance liquid chromatography-diode array detector (HPLC-DAD) achieved the separation and quantification of MET in the samples. Experiemental design was used to optimise influential variables in the extraction and preconcentration of MET. The linearity, limit of detection (LOD) and limit of quantification (LOQ) for MET were 0.5–100 μg L−1 (R2 = 0.9987), 0.16 μg L−1 and 0.53 μg L−1, respectively. The intraday (n = 10 same-day replicates) and interday (n = 5 consecutive days) precisions reported as relative standard deviations (RSD %) were less than 5%. The accuracy of the method expressed as percentage recovery (%R) ranged from 84 to 112%. The method was applied to extract and preconcentrate MET in wastewater and river water samples. The MET was detected in greater concentrations in wastewater than in river water samples. The validation based on specificity, trueness, linearity, precision, and application to the analysis of MET in real samples showed that the combination of dSPE and HPLC-DAD methods is applicable for MET monitoring in surface water and wastewater. Furthermore, the dSPE/HPLC-DAD method was rapid, simple and suitable for estimating the concentrations of MET in South African surface water and wastewater for the first time. Lastly, the environmental risk caused by the occurrence of MET in surface water was investigated in terms of hazard quotient (HQ). The HQ values were less than unity, suggesting a low possibility risk for the aquatic organisms.

Nitrogen-doped magnetic porous carbon nanospheres derived from dual templates-induced mesoporous polydopamine coated Fe3O4 for efficient extraction and sensitive determination of volatile nitrosamines by gas chromatography-mass spectroscopy

N-nitrosamines (NAs) are highly carcinogenic compounds commonly found in food, beverages, and consumer products. Due to their wide polarity range, it is challenging to find a suitable carbon adsorbent that can simultaneously adsorb and enrich both polar and nonpolar NAs with good recovery. In this study, nitrogen-doped magnetic mesoporous carbon nanospheres (M-MCN) were prepared and employed as an adsorbent for magnetic solid-phase extraction (MSPE) to extract and concentrate four NAs. The introduction of nitrogen functional groups enhanced the hydrophilicity of the carbon material, allowing M-MCN to achieve a balance between hydrophilicity and hydrophobicity, resulting in good recovery for both polar and nonpolar NAs. A method combining MSPE with gas chromatography-mass spectrometry (GC-MS) was developed for the determination of NAs in processed meat and alcoholic beverages. The method exhibited a good linear range (1–100 ng g−1, r2 > 0.9967) and trace-level detection (0.53–6.6 ng g−1). The recovery rates for the four NAs ranged between 85.7 and 110.7 %, with intra-day precision expressed as relative standard deviation (RSD) between 4.1 and 10.7 %, and inter-day precision between 4.8 and 12.9 %. The results demonstrated not only good accuracy and precision but also provided a new adsorbent for the enrichment of trace-level NAs in processed meat and alcoholic beverage samples.

The magnetic layered double hydroxide/zeolitic imidazolate framework-8 nanocomposite coupled with HPLC-MS/MS for the detection of heterocyclic aromatic amines in thermally processed meat

In this research, a novel magnetic nanocomposite (Fe3O4@Zn/Al-LABSA-LDH/ZIF-8) was synthesized using Fe3O4 as the magnetic core, layered double hydroxide (LDH) with linear alkylbenzene sulfonic acid (LABSA) intercalation and zeolitic imidazolate framework-8 (ZIF-8) as the shell. Benefiting from the intercalation of LABSA into LDH combined with ZIF-8, the multiple interactions, including π-π stacking, hydrogen bonding, and electrostatic interactions, conferred high selectivity and good extraction capability to the material towards heterocyclic aromatic amines (HAAs). Fe3O4@Zn/Al-LABSA-LDH@ZIF-8 was used as an adsorbent for magnetic solid-phase extraction (MSPE) to enrich HAAs in thermally processed meat samples, followed by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) detection. The method exhibited a low detection limit (0.021–0.221 ng/g), good linearity (R2 ≥ 0.9999), high precision (RSD < 7.2 %), and satisfactory sample recovery (89.7 % -107.5 %). This research provides a promising approach for developing novel adsorbents in sample preparation and improving analytical performance.

Magnetic solid-phase extraction of tetracyclines from milk using metal-organic framework MIL-101(Cr)-NH2 functionalised hydrophilic magnetic nanoparticles

Novel metal-organic framework MIL-101(Cr)-NH2 functionalised hydrophilic polydopamine-modified Fe3O4 magnetic nanoparticles (Fe3O4@PDA@MIL-101(Cr)-NH2) were synthesised and used as magnetic solid-phase extraction (MSPE) adsorbents for extracting tetracyclines (TCs) from milk samples. The integrated Fe3O4@PDA@MIL-101(Cr)-NH2 exhibited convenient magnetic separation and exceptional multi-target binding capabilities. Furthermore, the PDA coating significantly enhanced the hydrophilicity and extraction efficiency of the material, thereby facilitating the extraction of trace TCs. Various factors affecting MSPE, such as adsorbent dosage, extraction time, pH value, and desorption conditions, were optimised. The developed MSPE method coupled with high-performance liquid chromatography demonstrated good linearity (R2 ≥ 0.9989), acceptable accuracy (82.2%–106.1%), good repeatability (intra-day precision of 0.8%–4.7% and inter-day precision of 1.1%–4.5%), low limits of detection (2.18–6.25 μg L−1), and low limits of quantification (6.54–18.75 μg L−1) in TCs detection. The approach was successfully used for the quantification of trace TCs in real milk samples.