Loading...

Current Issue

    Chinese Journal of Chromatography
    2026, Vol. 44, No. 1
    Online: 08 January 2026

    For Selected: Toggle Thumbnails
    Preface
    Preface for Special Issue on Advanced Molecular Imprinting Technology and its Cutting-Edge Applications
    JIA Qiong, YANG Kaiguang
    2026, 44 (1):  1-1.  DOI: 10.3724/SP.J.1123.2025.12004
    Abstract ( 27 )   HTML ( 5 )   PDF (816KB) ( 12 )  
    Perspectives
    Research progress of molecular imprinting technology in the field of disease diagnosis and therapy
    ZHU Ran, CAI Ganping, ZHENG Haijiao, JIA Qiong
    2026, 44 (1):  2-16.  DOI: 10.3724/SP.J.1123.2025.06036
    Abstract ( 32 )   HTML ( 5 )   PDF (3815KB) ( 3 )  

    Disease biomarkers play important roles in modern medicine, enabling early disease diagnosis, precise subtyping, prognostic evaluation, and targeted therapy. Conventional biorecognition elements, such as antibodies and aptamers, offer high specificity but suffer from inherent limitations, including high production costs, instability in complex biological matrices, and significant batch-to-batch variation. Collectively, these constraints restrict their scalability and versatility for high-throughput, cost-effective, and multi-scenario clinical applications. Molecularly imprinted polymers (MIPs), prepared via molecular imprinting technology (MIT), have emerged as highly robust and promising synthetic receptors. During their formation, functional monomers assemble around a target molecule, and highly specific binding sites are formed after polymerization and template removal. MIPs exhibit a unique combination of advantages, ranging from cost-effectiveness to high selectivity, as well as high affinity comparable to natural counterparts, and outstanding physicochemical stability under harsh conditions. Driven by their highly flexible and customizable design capabilities, MIP development has witnessed remarkable advancements in recent years. These polymers are suitable for analyzing different types of disease biomarkers, ranging from proteins, peptides, and saccharides to complex biological entities such as whole cells and extracellular vesicles. Moreover, MIPs can be functionally engineered to integrate signal transduction or stimuli-responsive features, facilitating the creation of intelligent biomedical platforms. This review systematically summarizes the progress in applying MIT for disease diagnostics and therapeutics. It first elaborates on diverse imprinting techniques specifically tailored for different biomarker classes, including proteins, peptides, saccharides, cells, and extracellular vesicles. Subsequently, the article provides a comprehensive overview of their applications in diagnostics, encompassing biosensing, bioimaging, and bioseparation, as well as therapeutic applications, including drug delivery, photothermal and photodynamic therapy, biotoxin removal, and cell behavior regulation. Additionally, critical challenges hindering clinical translation are discussed, such as biocompatibility, long-term toxicity, high large-scale manufacturing costs, and the lack of standardized clinical validation protocols. Finally, promising future directions are outlined, emphasizing the development of biodegradable materials, integration with artificial intelligence, and adoption of green synthesis strategies. These synergistic approaches are expected to stimulate innovation, enabling the safe, reliable, and scalable translation of MIPs into real-world biomedical and clinical applications. In summary, MIPs represent a versatile, robust, and economically viable alternative to conventional biorecognition elements. Their customizable nature, combined with functional engineering capabilities, positions MIPs as a promising technology in disease diagnosis and therapy. Future efforts focusing on clinical translation, sustainability, and intelligent platform integration are likely to accelerate their adoption across diverse biomedical fields.

    Reviews
    Advances in application of cell imprinting technology in biomedical field
    ZHAO Xinmiao, ZHANG Zhiyuan, SUN Wenjing, QING Guangyan
    2026, 44 (1):  17-29.  DOI: 10.3724/SP.J.1123.2025.04007
    Abstract ( 83 )   HTML ( 3 )   PDF (5658KB) ( 39 )  

    Cell imprinting technology, as a key technique in the field of cell-specific recognition, has become an important cornerstone of modern biomedical research. It relies on its precise recognition capability for biomarkers such as cell surface antigens and receptors. This technology is not only widely applied in basic fields, including disease marker detection and research on cell function and behavioral mechanisms, but also plays a crucial role in frontier applications like rare cell isolation and targeted drug development. It continuously promotes the innovative development of life science research. Although significant progress has been made in this technology, it still faces several urgent challenges. These specifically include optimization of the imprinting process (to enhance anti-interference ability and fidelity) and development of new methods adapted to complex biological environments. In response to these issues, researchers have achieved breakthrough progress in multiple fields through innovative material design and process optimization recently. First, in rare cell capture, this technology has significantly improved the separation efficiency of key rare cells in complex samples, providing an efficient solution for early cancer diagnosis and blood disease research. Second, in the field of cell culture, its unique imprinted surface can precisely regulate the expression of cell adhesion proteins to optimize the in vitro culture microenvironment. Finally, in biosensing, sensors developed based on this technology have demonstrated excellent sensitivity and specificity, opening up new avenues for disease monitoring. This paper systematically reviews the research status and development trends of cell imprinting technology, deeply analyzes its technical bottlenecks and breakthrough directions. The aim is to provide a comprehensive theoretical reference for related research and further promote the innovative application and leapfrog development of this technology in the biomedical field.

    Molecular imprinting strategies and advances targeting biomembranes
    YUAN Xueting, WANG Liang, CHEN Luxi, HU Lianghai
    2026, 44 (1):  30-42.  DOI: 10.3724/SP.J.1123.2025.06028
    Abstract ( 76 )   HTML ( 3 )   PDF (1433KB) ( 16 )  

    Biomembranes are selective barriers and communication interfaces between intracellular and extracellular environments. They are crucial for signal transduction, energy transfer, and material exchange. Composed of lipids, proteins, glycans, and other components, biomembranes are central platforms for cell recognition and communication. Their specific recognition and binding abilities show great potential in early disease diagnosis, targeted drug delivery, environmental monitoring, and more. Molecularly imprinted polymer (MIP) has emerged as a robust tool for recognizing and binding biomolecules on biomembranes. This article summarizes recent technological advancements in MIP for biomembrane-associated lipids, proteins, and glycans. Lipids are a key part of biomembranes, crucial for maintaining membrane fluidity and stability. In lipid imprinting, lipid bilayers serve as templates. Functional monomers interact with lipid molecules and, upon polymerization, form a polymeric shell on the bilayer. Template removal leaves behind complementary binding sites. This strategy has been exploited to fabricate lipid-imprinted nanoparticles for drug delivery. These nanoparticles selectively recognize lipid components on cell membranes, thereby enabling targeted drug delivery. Proteins constitute another critical class of biomembrane components and execute diverse functions. Protein-imprinted MIPs selectively recognize membrane proteins such as cell-surface receptors, bacterial outer-membrane proteins, and viral capsid proteins. This enables precise identification and binding of specific proteins, which is useful in disease diagnosis and drug development. MIP can detect specific membrane protein biomarkers on cancer cells, allowing for early cancer detection and monitoring. Glycans also play a key role in biomembranes, particularly in cell recognition and immune responses. Carbohydrate-imprinted MIPs recognize specific glycan structures for use in disease diagnosis and therapy. Cancer cells have different glycan structures on their membranes compared to normal cells. These abnormal glycans serve as biomarkers for early cancer detection and monitoring. The article also emphasizes the potential of MIP in various applications. In disease diagnosis, MIP can develop biosensors for fast and accurate detection of disease biomarkers, enabling early treatment. In drug delivery, MIP can create targeted systems that deliver drugs directly to diseased cells, minimizing off-target effects and enhancing therapeutic efficacy. In cell imaging, MIP can specifically label cells or biomolecules, providing detailed images of cellular processes and aiding in understanding disease mechanisms. In biosensing, MIP can serve as efficient recognition elements to construct biosensors for detecting specific biomarkers in biological samples. The specific binding sites formed by molecular imprinting technology enable MIP-based biosensors to detect target molecules with high sensitivity and selectivity, providing a powerful tool for early disease diagnosis and real-time monitoring. However, the development of MIP still faces challenges, including complex synthetic procedures, incomplete template removal, limited scalability, and the need for performance optimization. The synthesis process is complex, requiring precise control of parameters like functional monomers, cross-linkers, and initiators. Incomplete template removal compromises binding affinity and selectivity. Scaling-up while maintaining batch-to-batch reproducibility is challenging, and the binding capacity, selectivity, and stability of MIPs must be optimized for each application. For glycan imprinting, monosaccharide templates have low specificity, glycan chain templates are difficult to synthesize and purify, and there is a lack of efficient O-glycan cleavage tools. To break through the bottleneck, the study improves template removal efficiency, synthetic optimization and structural controllability through controllable free radical/photo-initiated polymerization, magnetic material integration, microfluidics, artificial intelligence, machine learning and 3D printing; meanwhile, virtual templates, glycopeptide substitution templates, and solid-phase imprinting strategies are used to solve the scarcity of glycan templates. In addition, optimization of biocompatible materials, surface modification to reduce toxicity, and combination with computer simulation and automated preparation can accelerate clinical translation. In conclusion, MIP technology is highly promising for biomembrane research with broad applications in disease diagnosis, drug delivery, cell imaging, and extracellular vesicle enrichment. With continued development and optimization, MIP are expected to play an increasingly important role in biomedical and life sciences, offering more powerful tools and solutions for disease diagnosis, treatment, and monitoring.

    Progress in electric field assisted molecular imprinting technology
    WU Jiangyi, HUANG Xiaojia
    2026, 44 (1):  43-52.  DOI: 10.3724/SP.J.1123.2025.05006
    Abstract ( 48 )   HTML ( 4 )   PDF (1491KB) ( 9 )  

    Molecular imprinting technology (MIT) simulates the specific recognition mechanism between antibodies and antigens, and can construct separation media with specific recognition performance, demonstrating unique advantages in the fields of separation, purification, and trace detection in complex sample matrices. Molecularly imprinted polymers (MIPs), the core of MIT, form three-dimensional imprinting cavities matching the spatial structure and chemical properties of the target substance via three key steps: template self-assembly with functional monomer, cross-linking polymerization, and template elution. The prepared MIPs present highly selective extraction and recognition of the target substance. However, traditional MIT faces critical challenges in material preparation and application. During MIPs synthesis, due to the randomness of polymerization reactions, the resulting MIPs often have uneven distribution of imprinting sites and lack molecular orientation. This not only reduces the mechanical performance of MIPs, but also affects their specific recognition performance. In addition, incomplete removal of template molecules severely reduces the number of effective imprinting sites and may interfere with the accuracy of subsequent detection results. In the pre-treatment application of MIPs adsorbents, the mass transfer rate of the target substance in the sample solution is slow, which prolongs the adsorption equilibrium time of MIPs on it. In the sensor detection based on MIPs, there are inherent issues such as fluorescence quenching and insufficient signal amplification, which further limit the detection sensitivity. These challenges significantly limit the application of MIT in fields like environmental monitoring, biomedical diagnostics, and food safety analysis. In recent years, the cross fusion of electric field assisted technology and MIT has provided innovative strategies to solve the above-mentioned problems. During MIPs preparation, an external electric field can be applied to provide electrophoretic driving force to assist in regulating the directional self-assembly of functional monomers and template molecules. This can promote the ordered arrangement of imprinting sites at the micro level of MIPs prepared, achieving material uniformity of MIPs. For template molecule elution, applying an electric field can provide electrostatic repulsion between MIPs and template molecules. This can effectively weaken the inter-molecular forces between MIPs and template molecules, facilitate the diffusion of template molecules into the desorption solution, reduce the residual template molecules, and avoid the detection of “false positives”. During the sample pretreatment process, electrophoretic force significantly enhances the mass transfer rate of the target substance, prompting it to aggregate around the MIPs adsorbent and achieve the purpose of pre-concentration. This can not only shorten the adsorption equilibrium time of MIPs for target substances, achieve rapid enrichment, but also effectively drive away interfering substances with opposite electrical properties, improving the selective extraction performance of MIPs for target substances. In the detection and analysis stages, the signal enhancement effect induced by the electric field can significantly improve the response sensitivity of the sensor. Combining with electrochemical and fluorescence detection methods, ultra sensitive detection of the target substance can be achieved. Moreover, MIP-based sensors can be integrated with microfluidic technology to achieve rapid detection and analysis of trace samples, greatly expanding the practicality of MIPs in on-site detection and analysis applications. The present review systematically elaborates the mechanism of electric field in the three key links of MIPs preparation, sample pretreatment and detection analysis. At the same time, it summarizes the application prospects of electric field assisted MIT in environmental monitoring, biomedical, food safety and other fields. In addition, the future development direction of electric field assisted MITs is proposed.

    Research progress in the application of molecular imprinting technology in catalysis
    YE Weimin, HE Dongcheng, CUI Xinjiang, MA Haowen, QIAN Bo, SHI Feng
    2026, 44 (1):  53-77.  DOI: 10.3724/SP.J.1123.2025.05019
    Abstract ( 48 )   HTML ( 5 )   PDF (2895KB) ( 11 )  

    The synergistic enhancement of catalytic activity and selectivity constitutes a critical challenge in modern heterogeneous catalysis, which directly influences target product yield, reaction energy efficiency, and process economics. Molecular imprinting technology (MIT) has demonstrated exceptional potential in overcoming this limitation by enabling the rational design of molecularly imprinted catalysts (MICs) with high activity, superior selectivity, and favorable thermal stability. These advanced catalysts combine biomimetic recognition with heterogeneous catalysis, wherein precisely engineered imprinted cavities integrate two key structural features, including catalytically active sites with tailored electronic properties and molecular imprinting cavities with specific structure. These imprinted cavities endow MIC exhibit exceptional molecular recognition capabilities, enabling selective binding to substrates, intermediates, and products via reversible covalent bonds, electrostatic interactions, hydrogen bonding, and other noncovalent forces. This precise recognition facilitates the mediation of specific reaction pathways, ensuring high-selectivity synthesis of target compounds. The preparation of MIC typically involves three sequential steps: template molecule assembly, template configuration fixation, and template molecule elution. In the template assembly stage, reversible interactions are commonly employed to drive the self-assembly of template molecules (target-structured molecules) with functional monomers, forming stable imprinted complexes. For template configuration fixation, cross-linking polymerization or surface engineering techniques are predominantly utilized to immobilize the assembled structure, ensuring the preservation of cavity geometry after template removal. Subsequent elution of the template molecules generates imprinted cavities on the MIC surface. By optimizing template assembly methodologies and fixation strategies based on application-specific requirements, both the cavity structure and catalytic binding modes can be precisely modulated, thereby enhancing catalytic activity and selectivity for tailored catalyst design. Additionally, the introduction of precious metals (e.g., Rh, Ru, Au, Ag) and non-precious metals (e.g., Fe) as catalytic active sites further augments MIC performance. Despite the promising application potential of MICs in chemical synthesis, their preparation and characterization remain challenged by several key limitations, like the sub-nanostructured imprinted cavities hindering detailed structural elucidation of binding sites, template molecules encapsulation within the polymer matrix during cross-linking resulting in incomplete elution, quantitative analysis of metal species in polymer-based MICs lacking standardized methodologies. To address these challenges and guide design of high-performance MICs, researchers have integrated advanced characterization techniques to comprehensively evaluate MIC structure, including morphology, elemental composition, active site distribution, chemical bonding information, and metal coordination environments. Currently, MICs exhibit tremendous application potential in the synthesis of various fine chemical products, but related review articles focusing on MIC are relatively scarce. This review focuses on the applications of MIT in thermal catalysis, systematically discussing its fundamental principles, theoretical foundations, and historical development. Next, various typical synthetic strategies for MICs, including bulk, suspension, precipitation, and surface imprinting polymerization are summarized. Then series of key characterization methods, such as Fourier transform infrared spectroscopy (FT-IR), elemental analysis (EA), and high-resolution mass spectrometry (HRMS) are described to analyze the structure of MICs. Moreover, different types of MICs (noble metal, non-noble metal, and metal free MICs) are used in catalytic reactions, including hydrolysis, oxidation, reduction, coupling, and polymerization. In addition, the photo-/electrocatalysis, artificial enzyme design, sensing, and adsorption/separation are also discussed as emerging applications of MIT. Finally, the research challenges and future directions are proposed in this field.

    Articles
    Fabrication of high-degradation-efficiency molecularly imprinted photocatalysts and its selective degradation performance
    ZHANG Junjie, SONG Yafei, LIU Yan, TIAN Xuemeng, GAO Ruixia
    2026, 44 (1):  78-91.  DOI: 10.3724/SP.J.1123.2025.06001
    Abstract ( 33 )   HTML ( 3 )   PDF (2550KB) ( 3 )  

    Molecularly imprinted photocatalysts (MIPCs), which integrate specific molecular recognition with photocatalytic degradation capabilities, hold great promise for the selective and efficient removal of trace pollutants from complex environmental matrices. However, conventional surface-imprinting layers coated on photocatalysts often cause light-shielding effects, thereby reducing the photocatalytic efficiency of MIPCs. To overcome this limitation, the present study proposes a heterojunction-based interfacial in-situ imprinting strategy. In this approach, molecular imprinting cavities are directly constructed at the interface of composite photocatalysts. This design not only avoids the negative impact of surface shielding but also facilitates interfacial charge transfer, thus achieving a synergistic enhancement of both molecular recognition selectivity and photocatalytic efficiency. Based on this concept, a highly efficient molecularly imprinted photocatalyst, BiOBr-Cu/ppyr-MIPs, was successfully fabricated. The synthesis utilized surface molecular imprinting technology with the organic pollutant acid orange (AO) as the template molecule, and BiOBr-Cu/polypyrrole (ppyr) composite as the heterojunction matrix. Polypyrrole, introduced as a conductive polymer, served as the imprinting layer that promotes charge migration. The synthesis conditions, including monomer amount and polymerization time, were systematically optimized to maximize imprinting efficiency and photocatalytic performance. The obtained BiOBr-Cu/ppyr-MIPs were comprehensively characterized. Scanning electron microscopy (SEM) revealed a well-defined morphology with uniformly distributed imprinted layers. X-ray diffraction (XRD) analysis confirmed that the introduction of the polypyrrole-based imprinting layer did not significantly alter the crystal structure of the BiOBr-Cu composite. Fourier-transform infrared spectroscopy (FTIR) showed characteristic peaks attributable to the pyrrole ring, such as C-H in-plane bending, C-H stretching, and C=N stretching vibrations, indicating successful incorporation of the polypyrrole framework. X-ray photoelectron spectroscopy (XPS) further confirmed the formation of the imprinted layer, with increased proportions of C-N and O=C bonding components observed in the C 1s and O 1s spectra, respectively. Optical and photoelectronic properties were also evaluated. UV-vis diffuse reflectance spectroscopy (DRS) revealed a significant red-shift and broader light absorption in the visible range, attributed to the presence of the polypyrrole layer. Photoluminescence (PL) spectroscopy demonstrated a marked decrease in emission intensity, indicating that the recombination of photogenerated electron-hole pairs was effectively suppressed, which correlates with enhanced charge separation. Adsorption experiments indicated that BiOBr-Cu/ppyr-MIPs exhibited rapid adsorption kinetics, reaching equilibrium within 30 min and fitting a pseudo-second-order kinetic model. The maximum adsorption capacity was determined to be 40.9 μmol/g, consistent with the Freundlich isotherm model, suggesting a heterogeneous adsorption process with multilayer adsorption behavior. Photocatalytic degradation studies, optimized by adjusting catalyst dosage, initial pollutant concentration, and solution pH, showed a 2.04-5.79-fold enhancement in degradation efficiency compared to reference materials. The composite also exhibited excellent reusability, maintaining 90.7% of its initial performance after five consecutive cycles. Importantly, the material demonstrated strong molecular recognition capability, with an imprinting factor (IF) of 2.96 and a selectivity coefficient (Kselectivity) exceeding 1.79, indicating effective discrimination between the template molecule and structural analogs. Mechanistic investigations revealed that the interfacial polypyrrole imprinting layer not only contributed to selective adsorption but also facilitated targeted degradation pathways, thus achieving integrated selectivity and catalytic activity. In summary, this work introduces a novel interfacial in-situ imprinting strategy that overcomes key limitations of conventional MIPCs. The proposed design offers a generalizable approach for developing molecularly imprinted photocatalysts with both superior degradation efficiency and selectivity.

    Controlled synthesis of high-capacity bisphenol A molecularly imprinted polymer and its application to the detection of environmental water samples
    CHENG Yun, LIN Yule, TIAN Miaomiao
    2026, 44 (1):  92-100.  DOI: 10.3724/SP.J.1123.2025.04029
    Abstract ( 72 )   HTML ( 4 )   PDF (1424KB) ( 32 )  

    Bisphenol A (BPA) is an endocrine-disrupting chemical that mimics estrogen, thereby interfering with human hormonal balance and leading to reproductive abnormalities, developmental disorders, and increased risks of obesity, diabetes, and cancer. Commonly found in plastic products and food packaging materials, BPA can readily leach from packaging under thermal stress or exposure to acidic/alkaline conditions, subsequently migrating into the environment. This results in its widespread presence in surface water, groundwater, and drinking water systems. Prolonged exposure poses significant health threats, while conventional wastewater treatment processes prove inadequate for its complete removal. Therefore, developing an efficient, highly specific, and reusable material for removing BPA from water systems is of substantial practical significance. Molecularly imprinted polymers (MIPs) have emerged as promising candidates for targeted pollutant removal due to their artificially created recognition sites that exhibit both structural and functional complementarity to template molecules. The unique advantages of MIPs, including their exceptional specificity, chemical stability, and reusability, make them particularly suitable for environmental applications. To address the challenge of BPA contamination in water systems, we developed a novel cobalt-nickel bimetallic metal-organic framework-based molecularly imprinted polymer (CoNi-MOF-MIPs) through an innovative surface imprinting approach. The fabrication process involved multiple carefully controlled steps. Initially, a crystalline CoNi-MOF substrate was synthesized as the supporting matrix, providing high surface area and structural stability. Dopamine hydrochloride (DA) was then employed as the functional monomer, which underwent self-polymerization under weakly alkaline conditions to form a polydopamine (PDA) coating while simultaneously immobilizing BPA template molecules through synergistic hydrogen bonding and π-π interactions. Subsequent template removal using an eluent created well-defined recognition cavities on the MOF surface. For comparison, non-imprinted polymers (CoNi-MOF-NIPs) were prepared following identical procedures without BPA addition. Critical synthesis parameters were systematically optimized through comprehensive experiments. The mass ratio of functional monomer to template molecule was determined to be optimal at 5∶4 (DA∶BPA), while the polymerization duration and adsorption pH were optimized to 5 h and 4.0, respectively. Material characterization revealed crucial structural features: scanning electron microscopy (SEM) images confirmed the preservation of nanoflower-like morphology with hierarchical structures, providing abundant adsorption sites, while Fourier-transform infrared spectroscopy (FT-IR) demonstrated successful imprinting through characteristic peak shifts-notably the O-H stretching vibration migration from 3 443 cm⁻¹ to 3 752 cm⁻¹ and aromatic C=C bending transition from 1 633 cm⁻¹ to 1 457 cm⁻¹. Adsorption performance evaluation demonstrated remarkable efficiency across multiple aspects. Kinetic studies revealed rapid uptake conforming to pseudo-second-order behavior (R²=0.987 9 for CoNi-MOF-MIPs and R²=0.976 8 for CoNi-MOF-NIPs), reaching equilibrium within 30 min and suggesting that the adsorption process was controlled by the availability of binding sites rather than diffusion limitations. Isotherm analysis showed excellent agreement with the Langmuir model, indicating monolayer adsorption on homogeneous surfaces with a maximum capacity of 39.29 mg/g and an impressive imprinting factor of 3.48. Competitive adsorption experiments against structural analogs (diphenolic acid and phenol) demonstrated exceptional selectivity, with selectivity factors of 5.07 and 7.35 respectively, confirming the material’s ability to specifically recognize BPA in complex matrices. The CoNi-MOF-MIPs maintained 93.2% of their initial adsorption capacity after six consecutive adsorption-desorption cycles, demonstrating excellent reusability. When coupled with high performance liquid chromatography (HPLC), the developed analytical method exhibited a wide linear detection range (0.17-40 μg/mL, R²=0.997 4) and low detection limit (0.05 μg/mL). Practical application to environmental water samples spiked at three concentration levels (10, 20, and 30 μg/mL) achieved satisfactory recoveries of 80.3%-91.7% with excellent reproducibility (relative standard deviation<1.8%). The CoNi-MOF-MIPs material developed in this study combines the exceptional adsorption capacity of bimetallic MOFs with the molecular recognition precision of imprinted polymers. This innovative material demonstrates outstanding performance in both BPA enrichment and detection from environmental water samples, showing great promise for practical applications in water treatment and environmental monitoring.

    Efficient separation of gossypol from cotton kernels with copper mediated magnetic molecularly imprinted polymer
    YANG Shuling, CAO Yu, HE Kunlin, FENG Shun, ZHANG Chungu, SHAN Lianhai
    2026, 44 (1):  101-113.  DOI: 10.3724/SP.J.1123.2024.12006
    Abstract ( 59 )   HTML ( 4 )   PDF (2928KB) ( 17 )  

    Cotton is an economically important crop in China. Cotton fibers are widely used in the textile industry and cottonseed is a key source of edible oils and proteins. Cottonseed contains gossypol (GOS), a natural bioactive compound that exhibits medicinal properties, including antitumor and antiviral activities; it is also a potential contraceptive agent. Despite these benefits, GOS has some critical drawbacks, as it is associated with side effects such as antifertility and mammalian growth inhibition that limit the comprehensive utilization of cottonseed resources. Consequently, GOS needs to be efficiently and specifically separated for safe resource utilization. Conventional molecularly imprinted polymers (MIPs) have limitations as they often bind to targets in a manner that is too rigid or fragile, which leads to significantly lower specificities and mass-transfer rates. Accordingly, a novel copper-ion-mediated magnetic surface molecularly imprinted polymer (GOS/MIP) was designed and prepared to solve these problems. GOS/MIP integrates three key strategies: metal coordination, surface imprinting, and magnetic separation. Copper(Ⅱ) ions were introduced as functional “bridges” between the functional monomer and template, which resulted in softer and more flexible interactions and more homogeneous imprinted cavities. The imprinting sites were anchored to the surfaces of the functionalized magnetic cores, which accelerated the adsorption and desorption processes and simplified the preparation and separation steps. Free-radical polymerization enabled precise synthesis. GOS/MIP was thoroughly characterized, with scanning electron microscopy (SEM) and transmission electron microscopy (TEM) used to observe its morphology, and a vibrating sample magnetometer (VSM) used to measure magnetic properties. Energy-dispersive spectroscopy (EDS) was used to analyze the elemental composition, with Fourier-transform infrared (FT-IR) spectroscopy used to examine chemical bonding. The results confirmed the existence of a core-shell structure and that the imprinted layer had been successfully prepared. GOS/MIP was found to be composed of spherical particles 400–500 nm in diameter. The material also exhibited an excellent magnetic response, with a saturation magnetization of 47.78 emu/g, which enabled magnetic separation within only 7 s, thereby ensuring rapid recovery under practical conditions. Performance studies revealed that GOS/MIP exhibits an excellent binding ability for GOS, with equilibrium achieved in 120 min. The apparent maximum adsorption capacity and imprinting factor (IF) were determined to be 74.01 mg/g and 6.48, respectively. Selective and competitive binding experiments showed that GOS/MIP is highly specific for GOS in complex matrices, and pH binding experiments revealed that optimal binding occurs at pH 2–6, which covers most industrial processing conditions and highlights the large-scale industrial applications potential of the material. GOS/MIP retained its good adsorption capacity even after seven adsorption-desorption cycles, thereby demonstrating excellent stability and reproducibility. GOS/MIP was used as a dispersive solid-phase extraction (dSPE) adsorbent in combination with high-performance liquid chromatography (HPLC). The developed method exhibited linearity in the 5–200 μg/mL range, with a high correlation coefficient (R²>0.999) and limits of detection and quantification (LOD and LOQ) of 0.024 and 0.079 µg/mL, respectively. Average recovery rates at three spiked concentrations (0.08, 0.24, and 0.80 μg/mL) ranged between 95.1% and 98.7%, with relative standard deviations (RSDs) below 2.4%. Only 50 mL of solvent and 50 mg of GOS/MIP were required in a simulated industrial GOS-separation process, which separated 3 mg of GOS from 10 g of cottonseed. GOS-recovery rates of 77.0%–83.3% were observed. The GOS/MIP-based separation method combines specificity, sustainability, and cost-effectiveness, thereby addressing the key challenges faced by traditional GOS-separation methods. In addition, it overcomes the toxicity limitations associated with the comprehensive utilization of cottonseed. Hence, cottonseed can be safely processed and cottonseed byproducts can be used in animal feed. This study provides a potent tool for the green, fast, and specific separation of high-purity products from plants; the basic research presented herein is both innovative and is potentially industrially applicable.