Solid-phase Extraction Adsorbent Research Articles

Enhanced Pb(II) extraction using a novel chitosan/pectin/carbon composite adsorbent for solid-phase extraction

ABSTRACT This research aimed to present the development of chitosan/pectin/carbon (CPC) materials as adsorbents in the solid-phase extraction (SPE) of Pb(II) from river water samples. The CPC adsorbent shows active groups effectively binding Pb(II) ions. The characterisation included using Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy with Energy-Dispersive X-ray Spectroscopy (SEM-EDX) to analyse functional groups and evaluate surface morphology with elemental composition. SPE parameters were systematically optimised to enhance adsorption-desorption efficiency, including pH 4.0, Pb(II) concentration of 5 mg L−1, flow rate of 13.3 mL min−1, elution flow rate of 12.8 mL/min using nitric acid (HNO3), a sample volume of 25 mL, eluent volume of 1 mL and concentration at 1.0 M. The results showed that the implementation of the refined CPC-based SPE method for Pb(II) analysis in water samples obtained a recovery range of 101% to 103%, accompanied by a significant 25-fold concentration enrichment of Pb(II). Moreover, the adsorption concentration increased from undetectable levels to 1.27–2.48 mg L−1, reporting the efficacy of the CPC-based SPE method for sensitive and accurate Pb(II) analysis in environmental samples.

Highly selective guanidine-linked covalent organic framework for efficient removal of perfluoroalkyl carboxylic acids from water samples

In this study, guanidine-linked covalent organic framework (TPDGCl) was synthesized via a solvothermal method. The presence of guanidine groups in its structure facilitates electrostatic interactions and provides hydrogen bonding sites, enabling the selective enrichment of perfluoroalkyl carboxylic acids (PFCAs) from environmental water samples. The material exhibits rapid kinetic mass transfer, which facilitates the efficient removal of samples containing PFCAs from aqueous solutions within 5 min. Furthermore, TPDGCl exhibits several advantageous properties, including high selectivity for PFCAs, a high adsorption capacity (2005 mg/g), excellent chemical stability, and remarkable recyclability (five cycles). Additionally, density functional theory (DFT) studies have demonstrated that the adsorption of PFCAs on TPDGCl is enhanced by ion exchange, hydrophobic interactions, hydrogen bonding interactions and ordered channel structures. Finally, TPDGCl was used as an adsorbent for dispersive solid-phase extraction (d-SPE), in combination with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS), to develop an analytical method for the efficient extraction and sensitive detection of PFCAs. The developed method exhibits highly sensitivity, with detection and quantification limits of 0.64–0.85 ng/L and 2.6–3.4 ng/L, respectively. The recoveries of actual water samples ranged from 75.4 % to 113.7 %. Moreover, TPDGCl effectively reduces the levels of PFCAs in real water samples to less than 70 ng/L within only 1 h. These results indicate that TPDGCl is an effective adsorbent for removing PFCAs from environmental water samples.

A hierarchical porous Fe3O4-COOH@H-ZIF-67 composite as magnetic solid-phase extraction adsorbent for benzimidazole pesticides

A hierarchical porous structural magnetic zeolite imidazolate framework-67 composite (Fe3O4-COOH@H-ZIF-67) was prepared through directly mixing the H-ZIF-67 and glutaric anhydride functionalized Fe3O4 nanospheres, of which the H-ZIF-67 was synthesized through a double template pore size regulation method. The successful preparation of Fe3O4-COOH@H-ZIF-67 composite was confirmed based on the material characterization using different techniques. The prepared composite was applied in the efficient removal of four benzimidazole pesticides (BZDs) in water using magnetic solid-phase extraction (MSPE) process. The results of static and dynamic adsorption experiments indicate that the adsorption of BZDs on Fe3O4-COOH@H-ZIF-67 follow pseudo-second-order kinetics, the Langmuir model fitted well with the adsorption data (R2 are all higher than 0.9969), and the maximum adsorption capacity for BZDs are 7.44–31.11 mg/g. Meanwhile, the adsorption mechanism study indicate that both hydrogen bonding and coordination play important roles during the adsorption process of BZDs. Finally, the developed MSPE method was combined with HPLC analysis and applied in the removal of BZDs from simulated pesticides wastewater. The removal rate was 82.76–96.18 %, and the treated samples met the requirements of the maximum residue limits of CBZ in the national standard GB 21523–2008. In addition, the adsorbent can be used at least three times and the extraction efficiency changed within 3 % after being stored in dry atmosphere at room temperature for 90 days. The results of this work manifested that Fe3O4-COOH@H-ZIF-67 composite can be used for removal and analysis of BZDs in complex samples.

Preparation and evaluation of polymeric ionic liquid functionalized microparticles as the efficient adsorbent for pipette tip solid phase extraction of sulfonamides

Sulfonamides (SAs) residues are commonly found in environmental samples, which is highly concerning for public safety and environmental protection. The detection of SAs is quite important but challenging. In this work, a kind of polymeric ionic liquid functionalized microparticles (PIL-FM) was synthesized via a simple free radical polymerization reaction, and applied as the adsorbent for pipette tip solid phase extraction (PT-SPE) of three SAs from river water, milk powder and honey samples. The adsorption performance of PIL-FM on SAs were evaluated using adsorption kinetics and adsorption isotherms, and the results showed that PIL-FM had the best selectivity for SMZ with the maximum adsorption capacity was as high as 45.05 mg·g−1. The extraction process was optimized and the adsorption mechanism was preliminarily discussed. PIL-FM has the excellent selectivity for SAs mainly because of the strong π-π interaction, and the electrostatic repulsion between them in the elution step also has a positive impact. Under optimal conditions, combined with HPLC, this PT-SPE method had wide linearity (0.2–100 μg·L−1, R2 ≥ 0.9998) and low limits of detection (0.06–0.08 μg·L−1). The intra-day and inter-day repeatability were found to be 3.7 %–4.6 % and 4.5 %–6.2 %, respectively. The suggested PT-SPE method is simple, low cost, rapid, and efficient to extract SAs, and can be applied for the monitoring of SAs residues in the aquatic environment and in food.

Polypyrrole as Adsorbent in Magnetic Solid Phase Extraction for Progesterone Determination from Human Plasma.

A straightforward and effective chromatographic method has been created for the analysis of progesterone from human plasma using a composite based on polypyrrole/magnetic nanoparticles in the sample preparation procedure. The quantification of progesterone is necessary due to its importance in human development and fertility. The employed conditions used acetonitrile:ultrapure water (70:30, v/v) as the mobile phase at 1.0 mL min-1 and an octadecyl silane column (Phenomenex Gemini, 250 mm × 4.6 mm, 5 μm) at a wavelength of 235 nm. The composite and its precursors were synthesized and properly characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy/energy dispersive spectroscopy, thermogravimetric analysis, and point of zero charge. The main factors affecting the extraction recovery of progesterone from pool human plasma samples employing magnetic solid phase extraction have been studied, such as sample pH (without adjustment), sample volume (1000 μL), washing solvent (ultrapure water), eluent (acetonitrile), eluent volume (1000 μL), and amount of adsorbent (10 mg). The extraction recoveries ranged from 98% to 102%, and linearity ranged from 5 to 3000 ng mL-1. The correlation coefficient (r) was ≥0.99, and acceptable relative standard deviation (precision), relative error (accuracy), and p-values (robustness) were observed. Lastly, the plasma samples from pregnant women were successfully analyzed by the validated method.

Development of amphiphilic hypercrosslinked porous polymers for magnetic extraction of multiple environmental pollutants in water

Under the principle of similar compatibility, researchers have developed various polarity extractants corresponding to a class of chemicals. Separating different polarities chemicals with one extractant effectively has become a novel research trend in separation science. Given the complexity of environmental sample matrices and the significant differences in polarity and solubility of various compounds, the introduction of hydrophilic groups to hydrophobic material skeletons can lead to sorbents with hydrophilic-lipophilic balance (HLB) property and thus improve their extraction performance for substances with different polarities. In this work, a hypercrosslinked polymer (HCPPz-TPB), designated as HLB, was synthesized by incorporating polar pyrazine and nonpolar triphenylbenzene molecules within each other. Subsequently, a core-shell magnetic composite material was obtained by encapsulating magnetic Fe3O4 nanoparticles in HCPPz-TPB. The material was applied as an adsorbent for magnetic solid phase extraction (MSPE) and combined with a high-performance liquid chromatography-photodiode array detector (HPLC-PDA) to enrich, separate, and detect seven polar contaminants in environmental water samples. The proposed approach, Fe3O4@SiO2@HCPPz-TPB−MSPE-HPLC-PDA, is characterized by its outstanding high sensitivity, low detection limits, wide linear range, and good reproducibility. The method demonstrated satisfactory linearity in the range of 0.05–2 μg mL-1 with R2 values between 0.9969 and 0.9997; the limits of detection (LOD) were observed to be within the range of 0.0019–0.016 μg L-1, and limits of quantification (LOQ) was observed to be within the range of 0.0064–0.054 μg L-1 range with good precision. The recoveries of the different contaminants in the environmental samples ranged from 83.61 to 116.46% (RSD≤10.56, n = 5). The new hydrophilic-lipophilic balance extractant is highly efficient, sensitive, and precise for extracting different polar pollutants. The findings demonstrate that the Fe3O4@SiO2@HCPPz-TPB display a remarkable affinity for multiple targets, driven by complex interactions including multi-stackings and hydrogen bonding as a sorbent. The synthesized Fe3O4@SiO2@HCPPz-TPB may be employed in diverse applications, including extraction, removal, and determination of diverse trace multi-target analytes in complex media.

Preparation of Polydopamine-Based Electrospun Nanofibers as an Efficient Adsorbent for Solid-Phase Extraction of Trace Mycotoxins Followed by HPLC

Preparation of Polydopamine-Based Electrospun Nanofibers as an Efficient Adsorbent for Solid-Phase Extraction of Trace Mycotoxins Followed by HPLC

Preparation of an imidazolium-based poly(ionic liquid) functionalized magnetic three-dimensional graphene oxide for magnetic solid phase extraction of pyrethroids from tea samples

In this work, an imidazolium-based poly(ionic liquid) (poly(1-dodecyl-3-vinyl-imidazolium bromide) functionalized magnetic three-dimensional graphene oxide (Fe3O4@3D-GO@poly(ImC12+Br−)) was synthesized via a vacuum freezing-drying method and used as a magnetic solid phase extraction (MSPE) adsorbent for the efficient extraction of pyrethroid pesticides from tea samples. The prepared Fe3O4@3D-GO@poly(ImC12+Br−) was confirmed by scanning electron microscopy (SEM), Fourier transform infrared spectrometry (FT-IR), vibrating sample magnetometer (VSM) and X-ray photoelectron spectrogram (XPS). Due to its large specific surface area and the ability to offer multiple intermolecular interactions, including π-π stacking, hydrophobic and hydrogen bond interactions, the prepared Fe3O4@3D-GO@poly(ImC12+Br−) showed high extraction efficiency for pyrethroids. The experimental parameters were optimized by a combination of single-factor method and Box-Behnken design to improve the extraction efficiency. Under the optimum conditions, coupled with high performance liquid chromatography (HPLC), a sensitive analytical method was developed for the determination of pyrethroids, and the proposed method showed wide linear ranges (1.00–100 μg L−1) with correlation coefficients (R) ranging from 0.9980 to 0.9994, low limits of detection (0.100 μg L−1) and good repeatability with intra-day relative standard deviations (RSDs) in the range of 2.90–5.53 % and inter-day RSDs in the range of 1.83–7.76 %. Moreover, the developed method was successfully applied to the determination of pyrethroids in tea samples and satisfactory recoveries ranging from 82.37 % to 114.34 % were obtained. The results showed that the developed Fe3O4@3D-GO@poly(ImC12+Br−) was an ideal, effective and selective material for the extraction and enrichment of pyrethroids from tea samples.

High throughput detection of veterinary drug residues in chicken and eggs

Co-extraction of multiple types of target substances is the key to achieve high throughput detection. In this work, PDA@MOF-808/PAN NFsM was prepared by co-modified polyacrylonitrile nanofiber membrane (PAN NFsM) with polydopamine (PDA) and metal-organic framework-808 (MOF-808), and its potential as a solid-phase extraction (SPE) adsorbent was investigated by using the most typical nine veterinary drug residues in eggs and chicken as model target substances. The results show that PDA@MOF-808/PAN NFsM could effectively co-extract all the target substances (adsorption efficiency ranged from 81.46 % to 96.78 %), and had good capability of sample matrix purification (matrix effect was lower than −15.26 %), so a new SPE method has been established. Combined with UPLC-MS/MS, the detection limits were 0.3 to 3.1 μg/kg, the recoveries were between 71.02 % and 106.48 %, and the relative standard deviations were lower than 12.03 %, indicating that the method has considerable good sensitivity, accuracy and precision.

COF-COOH@MIP as solid-phase extraction adsorbent for selective and sensitive detection of metamitron in environmental water

Metamitron (MET) is a selective herbicide widely used in agriculture but can persist in the environment and potentially contaminate water resources. This study reports the successful synthesis of a composite adsorbent, COF-COOH@MIP, specifically designed for MET preconcentration via solid-phase extraction (SPE) before high-performance liquid chromatography (HPLC) analysis. COF-COOH@MIP integrates the advantages of covalent organic frameworks (COFs) with their high surface area and stability and molecularly imprinted polymers (MIP) with their tailored recognition cavities. The adsorbent achieved a maximum adsorption capacity of 4.67 μg mg−1. The SPE column packed with COF-COOH@MIP demonstrated excellent reusability, with recovery rates of MET around 100 % after six consecutive cycles. The limit of detection (LOD) and limit of quantification (LOQ) of the established method were remarkably low, at 2.94 ng mL−1 and 9.80 ng mL−1, respectively. The linearity was credible within 0.03-400 μg mL−1 (R2 = 0.9999). The method’s applicability to real-world samples was validated by analyzing water from a farm, a ditch, and a river. This method offers a valuable tool for environmental monitoring programs to safeguard water quality from MET pollution.

Cyano-functionalized porous hyper-crosslinked cationic polymers for efficient preconcentration and detection of phenolic endocrine disruptors in fresh water and fish

Sensitively analyzing phenolic endocrine-disrupting chemicals (EDCs) in environmental substrates and aquatic organisms provides a significant challenge. Here, we developed a novel porous hyper-crosslinked ionic polymer bearing cyano groups (CN-HIP) as adsorbent for the highly efficient solid phase extraction (SPE) of phenolic EDCs in water and fish. The CN-HIP gave an excellent adsorption capability for targeted EDCs over a wide pH range, and the adsorption capacity was superior to that of several common commercial SPE adsorbents. The coexistence of electrostatic forces, hydrogen bond, and π-π interactions was confirmed as the main adsorption mechanism. A sensitive quantitative method was established by coupling CN-HIP based SPE method with high-performance liquid chromatography for the simultaneously determining trace bisphenol A, bisphenol F, bisphenol B and 4-tert-butylphenol in fresh water and fish. The method afforded lower detection limits (S/N = 3) (at 0.03–0.10 ng mL−1 for water and 0.8–4.0 ng g−1 for fish), high accuracy (the recovery of spiked sample at 88.0%–112 %) and high precision (the relative standard deviation < 8.5 %). This work provides a feasible method for detecting phenolic EDCs, and also opens a new perspective in developing functionalized cationic adsorbent.

Fabrication of sulfur-based functionalized activated carbon as solid phase extraction adsorbent for selective analysis of selenite in water

Based on the important feature of sulfur with excellent selectivity toward selenite in the presence of selenate, a simple and low-cost adsorbent of solid phase extraction known as sulfur loading activated carbon (SAC-6) was successfully prepared and applied for selenite (Se(IV)) analysis in water. Microstructure and morphological characteristics of SAC-6 had been identified by XRD, TEM, BET and FT-IR. In the static adsorption experiments, Se(IV) could be separated in a wide range of pH values (pH=3–11). The retention process of Se(IV) onto SAC-6 was characterized as spontaneous exothermic reaction. An obvious change of adsorption mechanism occurred in static and dynamic adsorption processes shown that the behaviors followed monolayer and hybrid adsorption. The theoretical maximum adsorption capacity of SAC-6 calculated by Langmuir-Freundlich was 13.48 mg/g. The microcolumn filled with SAC-6 was applied to extract Se(IV) in water solution. The detection limit of Se(IV) analytical procedure was confirmed as 0.27 μg/L within a linear range of 10–1000 μg/L. A good precision with relative standard deviation of 1.34 % (100 μg/L, n = 6) was achieved. The high adaptability and accuracy of SAC-6 microcolumn was validated by analyzing natural water samples and certified reference materials. Our work successfully excavated the application value of the sulfur selectivity, and also provided a new adsorbent for Se(IV) extraction and analysis.

Determination of Free Fatty Acids in Krill Oil during Storage Based on NH2-MMS.

In this study, amino-modified micro-mesoporous silica (NH2-MMS) with hierarchical pores was prepared by modifying micro-mesoporous silica ZSM-5 with 3-aminopropyltriethoxysilane and used as an adsorbent in solid-phase extraction to analyze free fatty acids (FFAs) in krill oil during storage for an initial time. The Brunner Emmet Teller adsorption experiment and Fourier transform infrared spectroscopy demonstrate that NH2-MMS, with a hierarchical pore structure, was successfully synthesized. The adsorption experiments, especially static adsorption, indicate that the absorption ability of the prepared NH2-MMS, with a hierarchical pore structure, toward FFAs was better than that of traditional amino-modified mesoporous silica (SBA-15) with a mesoporous structure at all temperature and concentrations. Fairly low limits of detection (0.06-0.15 μg g-1), acceptable recoveries (85.16-94.31%), and precision (0.08-5.26%) were attained under ideal circumstances. Moreover, NH2-MMS has the advantages of easy preparation and being environmentally friendly. As a result, this method offers an alternative to the current method for determining FFAs in different kinds of oil specimens.

Silver Core Coated with Molecularly Imprinted Polymer as Adsorbent in Pipet-Tip Solid Phase Extraction for Neonicotinoids Determination from Coconut Water

Silver Core Coated with Molecularly Imprinted Polymer as Adsorbent in Pipet-Tip Solid Phase Extraction for Neonicotinoids Determination from Coconut Water

A porous magnetic hydrogel-metal organic framework composite adsorbent for solvent-assisted magnetic solid-phase extraction and risk assessment of polycyclic aromatic hydrocarbons in food

A porous magnetic composite adsorbent was developed for the solvent-assisted magnetic solid-phase extraction of polycyclic aromatic hydrocarbons (PAHs). The porous magnetic composite adsorbent was created by incorporating a metal-organic framework (MOF), magnetite nanoparticles, and calcium carbonate into alginate beads. The extraction of the analytes was enabled through hydrophobic and π-π interactions between MOF-5, PAHs, and the organic solvent in the micropores. The fabricated adsorbent was characterized and optimized to improve extraction efficiency. Under the optimum conditions, good linearity was achieved with a detection limit in the range of 0.01–0.10 µg L−1. The developed method was successfully applied to extract PAHs from coffee, cocoa, and tea samples for analysis with high-performance liquid chromatography coupled with fluorescence detection (HPLC-FLD). Relative recoveries were obtained in the range of 70.3–96.1 %, with RSDs below 10 %. The developed adsorbent exhibited good stability and the extraction procedure was simple and rapid. The results obtained with the developed method were used to evaluate the incremental lifetime carcinogenic risk (ILCR) in adults from the intake of coffee, cocoa, and tea. Our calculations showed there was no cancer risk to consumers.

Facile synthesis of magnetic ionic covalent organic framework and dispersive magnetic solid phase extraction of aromatic amino acid oxidation products in thermally processed foods

Aromatic amino acid oxidation products (AAAOPs) are newly discovered risk substances of thermal processes. Due to its significant polarity and trace level in food matrices, there are no efficient pre-treatment methods available to enrich AAAOPs. Herein, we proposed a magnetic cationic covalent organic framework (Fe3O4@EB-iCOF) as an adsorbent for dispersive magnetic solid-phase extraction (DMSPE). Benefiting from the unique charged characteristics of Fe3O4@EB-iCOF, AAAOPs can be enriched through electrostatic interaction and π-π interactions. Under the optimal DMSPE conditions, the combined HPLC-MS/MS method demonstrated good linearity (R2 ≥ 0.990) and a low detection limit (0.11–7.5 μg·kg−1) for AAAOPs. In addition, the method was applied to real sample and obtained satisfactory recoveries (86.8 % ∼ 109.9 %). Especially, we applied this method to the detection of AAAOPs in meat samples and conducted a preliminarily study on its formation rules, which provides a reliable basis for assessing potential dietary risks.

Novel polyvinyl alcohol/gum tragacanth molecularly imprinted-electrospun nanofibers as adsorbent for selective solid phase extraction of bisphenol A

A polyvinyl alcohol/gum tragacanth molecularly imprinted nanofiber fabricated by electrospinning (PVA/GT-MIN) was used as an efficient adsorbent for the solid phase extraction (SPE) of bisphenol A (BPA) in water samples. PVA and GT were functional polymers and BPA was the template for molecular imprinting. BPA was bound to the polymer matrix through hydrogen bonding. The SEM image of PVA/GT-MIN demonstrated a rough morphology with pores and a diameter of 501 nm. The data for the adsorption of BPA on PVA/GT-MIN fitted the Freundlich isotherm and pseudo-second-order kinetics models. The proposed SPE using PVA/GT-MIN coupled with high performance liquid chromatography-diode array detection presented good linearity from 50 μg/L–5 mg/L (R2 = 0.9999) and yielded a limit of detection of 21 μg/L. The PVA/GT-MIN was applied to extract bottled water for BPA analysis and recoveries were 93.1–97.7 % (RSDs ≤ 3.6 %). This study presents a novel, easily prepared PVA/GT-MIN adsorbent for the extraction of BPA in water.

Facial synthesis of fluorine-engineered magnetic covalent organic framework for selective and ultrasensitive determination of fipronil, its metabolites and analogs in food samples

To improve the adsorption affinity and selectivity of fipronils (FPNs), including fipronil, its metabolites and analogs, a magnetic covalent organic framework (Fe3O4@COF-F) with copious fluorine affinity sites was innovatively designed as an adsorbent of magnetic solid-phase extraction (MSPE). The enhanced surface area, pore size, crystallinity of Fe3O4@COF-F and its exponential adsorption capacities (187.3–231.5 mg g−1) towards fipronils were investigated. Combining MSPE with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS), an analytical method was established for the selective determination of fipronils in milk and milk powder samples. This method achieved high sensitivity (LODs: 0.004–0.075 ng g−1), satisfactory repeatability and accuracy with spiked recoveries ranging from 89.9% to 100.3% (RSDs≤5.1%). Overall, the constructed Fe3O4@COF-F displayed great potential for the selective enrichment of fipronils, which could be ascribed to fluorine‑fluorine interaction. This method proposed a feasible and promising strategy for the development of functionalized COF and broadened its application in fluorine containing hazards detection.

Boronic acid-functionalized magnetic covalent organic frameworks based solid-phase extraction coupled with hydrophilic interaction chromatography-tandem mass spectrometry for the determination of trace gentamicin residues in milk

Boric acid-functionalized magnetic covalent organic frameworks (Fe3O4-TpBD-B) with large surface area and high porosity were prepared and applied for magnetic solid-phase extraction adsorbent of gentamicin from milk before UPLC-MS/MS detection. By utilizing a new HILIC chromatographic column with zwitterionic sulfoalkyl betaine stationary phase based on ethyl bridged hybrid particles (BEH), isomers of gentamicin (C1, C1a, and C2+C2a components). The developed methods demonstrated good linearity (R2 > 0.99), acceptable accuracy and good precision (<10 %), and low limit of quantitation (1.59 ng mL⁻1 for C1, 1.52 ng mL⁻1 for C1a and 2.72 ng mL⁻1 for C2+C2a). In addition, this method has been effectively applied to the analysis of real milk samples.

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.