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  • Cheng YANG, Weixia ZHU, Yafeng LIU, Wei WEI, Fang ZHAO, Kai HU, Wenjie ZHAO
    Chinese Journal of Chromatography. 2025, 43(9): 1045-1052.

    Isoxazoline drugs (ISOs) are a class of five-membered heterocyclic compounds containing N and O atoms. They can inhibit γ-aminobutyric acid gated chloride channels and are widely used in the treatment of parasitic diseases in poultry. The intake of animal-derived foods by humans is an important way to come into contact with ISOs. Excessive use of ISOs can lead to their residues in animal-derived foods, thereby threatening human health and causing neurotoxicity and hepatotoxicity. To address the safety issues caused by ISO residues in animal-derived foods, an ultra-high performance liquid chromatography-quadrupole/linear ion trap mass spectrometry (UHPLC-Q/Trap MS) analytical method for four novel ISOs (fluralaner, sarolaner, afoxolaner, lotilaner) in bovine-origin foods (including milk, beef and bovine liver) was established. The sample was first extracted with acetonitrile and then purified with PRiME HLB solid phase extraction (SPE) column. Using 5 mmol/L ammonium acetate aqueous solution and acetonitrile as the mobile phase, after separation by Shim-pack GIST C18-AQ (100 mm×2.1 mm, 2.7 μm) chromatography column, the analysis was carried out in the multi-reaction monitoring (MRM) mode by information-dependent acquisition (IDA), enhanced product ion scanning (EPI) and spectral library retrieval, and quantification was performed using the external standard method. The results showed that the four ISOs had good linear relationships within their respective mass concentration ranges. The correlation coefficients (r) were all ≥0.993 6, and the limits of detection (LODs) and quantification (LOQs) were 0.2-0.5 μg/kg and 0.5-1.0 μg/kg, respectively. Under the low, medium and high spiked levels (1, 2 and 10 μg/kg), the recoveries of the four ISOs ranged from 67.6% to 118.9%, and the relative standard deviations (RSDs) ranged from 2.0% to 20.0%. In addition, in this study, qualitative screening and analysis of the target compounds were conducted through MRM-IDA-EPI combined with spectral library retrieval. Dual qualitative analysis of the target compounds was carried out based on information such as retention time and EPI fragment ions, which improved the accuracy of qualitative analysis and effectively eliminated the interference of false positive results. This method features low LODs and good recoveries. It is also simple and rapid to operate, with high sensitivity and accuracy. It can achieve qualitative and quantitative analysis of new ISOs residues in bovine-origin foods. This study can provide technical support for food safety agencies to implement preventive measures against new ISOs in animal foods.

  • Le ZHAO, Xianjun LIU, Hao ZHANG, Jian LI, Liang CAI, Xiang FAN, Tanyao LI, Dongyang CHEN
    Chinese Journal of Chromatography. 2025, 43(9): 1053-1062.

    Pesticide residues in fruits and vegetables are becoming a serious issue. These residues can affect the quality of agricultural products and people’s health. Therefore, it has become crucial to effectively monitor and control pesticide residues in the food safety field. In this study, a rapid and effective QuEChERS-ultra performance liquid chromatography-tandem mass spectrometry (QuEChERS-UPLC-MS/MS) method was established for the simultaneous determination of 79 typical pesticides in vegetables and fruits, including organophosphates, carbamates, and pyrethroids. The pretreatment, UPLC, and MS/MS conditions were optimized. The fruit and vegetable samples were extracted with frozen acetonitrile after pulverization and homogenization, cleaned up by the QuEChERS method, filtered through a centrifugal membrane, and analyzed by UPLC-MS/MS. The separation was carried out on an ACQUITY UPLC HSS T3 column (100 mm×2.1 mm, 1.8 μm) with gradient elution. The aqueous and organic phases were water-methanol (98∶2, v/v) and methanol-water (98∶2, v/v) respectively, both with 5 mmol/L ammonium acetate and 0.1% formic acid. A triple quadrupole mass spectrometer was used in positive-ion electrospray ionization (ESI+) scanning mode, with target pesticide residues quantified using the matrix-matched standard-curve method. The results showed that under the optimized conditions, the 79 target compounds were determined with good linearities in the range of 0.1-200 μg/L, and the correlation coefficients (r) were all greater than 0.990. The limits of detection (LODs) and limits of quantification (LOQs) of the 79 compounds were in the range of 0.01-4.0 μg/kg and 0.03-13.0 μg/kg. The recoveries at three spiked levels ranged from 78.2% to 119.8%, with relative standard deviations (RSDs) all less than 15.8%. The established method was successfully applied to 80 samples of fruits and vegetables from Hunan province. As a result, 19 pesticides were detected in 31 samples, and thiamethoxam, acetamiprid and clothianidin being the most highly detected with a content range of 0.012-2.62 mg/kg; According to the data of the Hunan province survey yearbook, the percentages of acceptable daily intake (%ADI) for chronic dietary exposure of the detected neonicotinoid insecticides (thiamethoxam and clothianidin) have been calculated. The results indicate that the %ADI of clothianidin in fruits and vegetables ranged from 5.74% to 0.36%, respectively, and the %ADI of thiamethoxam in fruits and vegetables ranged from 0.40% to 19.50%. The %ADI of both pesticides were found to be less than 100%, indicating they are within acceptable limits. The method is simple, sensitive, accurate, and suitable for the simultaneous determination of multiple pesticide residues in fruits and vegetables.

  • Ping HE, Liqun WANG, Shan ZHOU, Baofeng ZHANG, Xuan JIA, Yi CHI, Zhenqi XU, Wei TANG
    Chinese Journal of Chromatography. 2025, 43(9): 1063-1069.

    Antipyretic analgesics are typical pharmaceutical and personal care products (PPCPs) that are widely used in our daily life because they relieve fever and pain, and have anti-inflammatory and anti-rheumatic properties. These drugs inhibit the synthesis and release of prostaglandins (PGs) in the neurons of the anterior hypothalamus and exert therapeutic effects as a consequence. However, these drugs are relatively commonly misused and abused, often owing to a lack of proper medication guidance. As a result, these drugs enter the environment via various pathways, including wastewater treatment plants, agricultural runoff, and improper disposal, thereby posing potential threats to human health and ecosystems. The presence of these contaminants in surface water has become an environmental safety concern that necessitates the development of rapid, accurate, and high-throughput analysis methods. In this study, an analytical method was established for the determination of five antipyretic analgesics (ibuprofen, aminophenazone, antipyrine, phenacetin, and naproxen). The developed method is based on online solid phase extraction coupled with ultra-high performance liquid chromatography-tandem mass spectrometry (online SPE-UHPLC-MS/MS), which provides a high degree of automation and efficiency. Water samples were collected and filtered through 0.2-μm regenerated cellulose (RC) filter membranes, after which Na2EDTA and an internal standard were added. An aliquot (0.9 mL) of each sample was injected into the online SPE system using an automatic sampler. Samples were first adsorbed on a PLRP-S online SPE column, washed with 0.05% formic acid aqueous solution, and finally gradient-eluted with a mobile phase composed of 0.2 mmol/L ammonium fluoride solution and methanol-acetonitrile (1∶1, v/v). Analytes were separated on a ZORBAX Eclipse Plus C18 column, detected by multiple reaction monitoring with electrospray ionization in both positive- and negative-ion modes, and quantified using the internal-standard method.The five antipyretic analgesics were effectively separated under the optimized experimental conditions and showed good linearities within their respective concentration ranges, with correlation coefficients (r) greater than 0.998. The method detection limits (MDLs) ranged from 0.05 to 0.20 ng/L, and the method quantification limits (MQLs) ranged from 0.20 to 0.80 ng/L. The five antipyretic analgesics exhibited average recoveries of between 64.2% and 112%, with relative standard deviations (RSDs, n=6) of 2.06%-8.99% at low, medium, and high spiked levels. Furthermore, the method was successfully used to analyze water samples from the Hangzhou section of the Qiantang River, in which four target compounds were detected, with antipyrine found to have the highest mass concentration. This newly developed method features a high degree of automation, facilitates the injection of large volumes, and enables online enrichment, purification, and quantitative analysis in an integrated process, with minimal operational errors, high repeatability, and high sensitivity. The developed method shortens sample-analysis times, is more cost-effective, and meets the needs of large-scale sample testing, as it requires only 15 min to completely determine a sample, thereby significantly improving detection efficiency. Overall, the method features low detection limits, analyzes rapidly, and is easy to operate; hence it is suitable for rapid risk screening and the quantitative determination of antipyretic analgesics in surface water.

  • Rui ZOU, Zixian YU, Zehua GUO, Haozheng DAI, Qiang ZHANG, Weiwen LIU, Chengxi CAO
    Chinese Journal of Chromatography. 2025, 43(9): 1070-1077.

    Specific protein detection plays a crucial role in biological analysis and clinical diagnostics, serving as an essential tool for disease diagnosis, therapeutic monitoring, and biological research. However, conventional methods such as immunofixation electrophoresis (IFE) and western blotting (WB) suffer from complex workflows, time-consuming operations, and limited quantification capabilities owing to intricate staining and de-staining procedures. In addition, these traditional immunological detection methods require extensive manual handling and specialized expertise, while low levels of automation restrict their applicability to high-throughput or large-scale analysis scenarios. Moreover, the multistep nature of these methods increases the risk of experimental errors and compromises quantification accuracy.Herein, we present a quantitative protein immune polyacrylamide gel electrophoresis (PAGE) detection method that combines immune-recognition principles with online fluorescence imaging technology, thereby offering a rapid and specific approach for quantifying target proteins. The developed method exploits the specificity of fluorescently labeled antibodies and the separation capability of PAGE, with formaldehyde crosslinking used to stabilize antigen-antibody complexes under the denaturing conditions of electrophoresis, thereby ensuring reliable quantification. The entire experimental workflow can be completed within 1.5 h and consists of three main steps. Firstly, the target protein is incubated with fluorescently labeled antibodies at room temperature for 0.5 h to form immune complexes, after which they are crosslinked using formaldehyde. The cross-linked samples are then loaded onto polyacrylamide gels and separated under optimized electrophoresis conditions (120 V, 15 min; 150 V, 15 min; 200 V, 15 min). Electrophoretic separation is finally monitored in real-time using an online fluorescence imaging system, which enables direct visualization of protein migration and eliminates the need for post-separation processing. Three distinct bands are observed on the precast gel following immune PAGE separation: the immune complexes at the uppermost position, the free fluorescent antibodies in the middle, and other proteins at the bottom. ImageJ software is used to analyze the electrophoresis pattern, and quantification is achieved based on the linear relationship between the fluorescence intensity of the free antibody and the mass concentration of the target protein. We systematically validated the performance of the method using human transferrin (TRF) as the model antigen protein and fluorescein-isothiocyanate-labeled (FITC-labeled) anti-TRF IgG antibody (anti-TRF IgG-FITC) as the detection probe, which involved analyzing three key aspects: the necessity of the formaldehyde-crosslinking step for maintaining immune complex stability, antibody recognition specificity in complex samples, and the linear correlation between the fluorescence signal and the mass concentration of the target protein. The method exhibited excellent analytical performance, with a linear range that extended between 5.0 and 200.0 mg/L and a correlation coefficient (R2) of 0.993 0. Triplicate measurements of fluorescence intensity at all mass concentration points revealed a maximum relative standard deviation (RSD) of 1.65%. The limit of detection (LOD) reaches 0.5 mg/L, with recoveries between 98.2% and 105.0%. Repeatability experiments revealed maximum intra- and inter-day RSDs of 1.21% and 1.58%, respectively. Specificity testing confirmed that the developed method accurately quantified TRF without interference from other proteins in complex samples. These results highlight the good accuracy, excellent consistency, high sensitivity, and robust specificity of the developed method, thereby confirming its reliability for use in precise protein-quantification applications. Compared to traditional PAGE methods, the immune PAGE method introduced herein provides the ability to selectively quantify specific target proteins online using real-time fluorescence imaging technology. The method exhibits several notable advantages, including high resolution, a simple workflow, strong specificity, rapid analysis, and good reproducibility. The online fluorescence imaging system eliminates the need for complex gel-dismantling, membrane-transfer, fixation, staining, and de-staining steps while effectively preventing protein band broadening, thereby enabling highly sensitive quantitative analyses with superior resolution. The cost-effectiveness of the developed method is achieved through economical fluorescently labeled antibodies and low sample consumption. Moreover, the fundamental principle of the immune PAGE method suggests that this approach is readily adaptable to the quantification of other proteins through the judicious selection of specific fluorescently labeled antibodies. Consequently, the versatility of the developed method makes it a comprehensive analytical platform suitable for pharmaceutical preparations and clinical diagnostics, in which rapid and accurate protein quantification is essential for decision-making processes. Additionally, this method is an ideal choice for high-throughput applications in both academic research and industrial settings owing to the integration of automated analysis and short operation times. The protein immune PAGE method represents a significant advancement in specific protein quantification methodology with great potential as a promising tool that is expected to be widely adopted in various biological analysis scenarios.

  • Yuhan ZHANG, Junyao HE, Shujing LIN, Bingjian AI, Hongyi ZHANG, Zhihong SHI, Hongyi ZHANG
    Chinese Journal of Chromatography. 2025, 43(9): 1078-1085.

    This study developed a GeoGebra platform-based interactive pedagogical tool focusing on plate theory to address challenges associated with abstract theory transmission, unidirectional knowledge delivery, and low student engagement in chromatography teaching in instrumental analysis courses. This study introduced an innovative methodology that encompasses theoretical model reconstruction, tool development, and teaching-chain integration that addresses the limitations of existing teaching tools, including the complex operation of professional software, restricted accessibility to web-based tools, and insufficient parameter-adjustment flexibility. An improved mathematical plate-theory model was established by incorporating mobile-phase flow rate, dead time, and phase ratio parameters. A three-tier progressive learning system (single-component simulation, multi-component simulation, and retention-time-equation derivation modules) was developed on a cloud-based computing platform. An integrated teaching chain that combined athematical modeling (AI-assisted “Doubao” derivation), interactive-parameter adjustment (multiple adjustable chromatographic parameters), and visual verification (chromatographic elution-curve simulation) was implemented. Teaching practice demonstrated that: (1) The developed tool transcends the dimensional limitations of traditional instruction, elevating the classroom task completion rate to 94% and improving the student accuracy rate for solving advanced problems to 76%. (2) The dynamic-parameter-adjustment feature significantly enhances learning engagement by enabling 85% of the students to independently use the tool in subsequent studies and experiments. (3) The AI-powered derivation and regression-analysis modules enable the interdisciplinary integration of theoretical chemistry and computational tools. The process of deriving chromatographic retention-time equations through this methodological approach proved more convincing than the current textbook practice of directly presenting conclusions. The developed innovative “theoretical-model visualizable-model-parameter adjustable-interactive-knowledge generating” model provides a new avenue for addressing teaching challenges associated with chromatography theory, and its open-source framework and modular design philosophy can offer valuable references for the digital teaching reform in analytical chemistry.

  • Lingxin CHEN, Jinhua LI
    Chinese Journal of Chromatography. 2025, 43(8): 839-840.
  • Jingying HUANG, Jingyi YAN, QI Ji, Lingxin CHEN, Jinhua LI
    Chinese Journal of Chromatography. 2025, 43(8): 841-856.

    The coastal zone, a critical ecotone where marine and terrestrial environments converge, contains complex ecosystems, is subjected to highly intense human activity, and is experiencing escalating threats from anthropogenic pollutants. Rapid industrial and urban development has witnessed the continual entry of new pollutants(NPs), such as persistent organic pollutants(POPs), endocrine-disrupting chemicals(EDCs), antibiotics, and microplastics, into coastal zones. These NPs are present in low concentrations in the environment, are structurally diverse and chemically complex, and pose severe risks to biodiversity and human health. Methods for effectively screening, recognizing, and precisely determining NPs are urgently required to understand their environmental fate and toxicological impact, and to formulate abatement-control strategies. However, the intrinsic complexities of coastal matrices, as characterized by heterogeneous media(such as water, sediments, soil, biological components, and the atmosphere), high salinity, and interference from a variety of species, demands advanced sample-pretreatment methodologies coupled with highly sensitive chromatography or chromatography-mass spectrometry(MS) techniques. Functional-material-based solid-phase extraction(SPE) has become an important sample-pretreatment method. Molecularly imprinted polymers(MIPs) that operate through “lock-and-key” molecular recognition, have become very popular in the SPE space. Nevertheless, MIPs suffer from issues such as template-molecule residues and/or leakage, low adsorption capacities, low mass-transfer rates, and poor complex-substrate adaptabilities, which restrict their practical applications. Recent years have seen the introduction of metal/covalent-organic framework(MOF/COF) materials with high specific surface areas and adjustable pore sizes that have provided new avenues for improving MIP performance in a manner that significantly enhances adsorption capacity, the mass-transfer rate, and applicability. Consequently, MOF/COF-MIP composite materials are attracting increasing levels of attention because SPE adsorbents play important roles when screening and identifying NPs in coastal zones. Herein, we review recent advances in MOF/COF-MIP composite materials for use in SPE-pretreatment applications prior to chromatography or chromatography-MS for the screening and identification of NPs in coastal zones. Firstly, MIP synthesis methods are briefly summarized, and key factors, such as adsorption capacity, the binding kinetics mass-transfer rate, selectivity, and anti-interference ability, are discussed in detail. Adsorption capacity depends on recognition-site density and accessibility, which can be optimized through controlled polymerization and MOF/COF-MIP hybridization. The mass-transfer rate, which is influenced by surface hydrophilicity/hydrophobicity and pore architecture, dictates the analyte-diffusion rate to the binding sites. Advanced imprinting strategies, such as those involving restricted access materials(RAMs) and multi-template imprinting, are critical for minimizing nonspecific interactions in complex matrices. Imprinting and selectivity factors(IFs and SFs, respectively), as key indicators, need to be rationally provided to deliver MIPs that are highly and reliably selective. In addition, this paper discusses methods used to prepare MOF-MIP and COF-MIP composites, focusing on the structural advantages of MOFs and COFs, including designability. MOF/COF-MIP syntheses leverage structural and functional synergies between the framework and the MIP. MOFs, with their metallo-organic coordination networks, serve as stable substrates for surface imprinting, whereas COFs, which contain covalent linkages, enable functional groups to be precisely tailored. Techniques such as radical polymerization and sol-gel processes are employed to balance crosslinking density and structural integrity. Room-temperature and microemulsion polymerization strategies enhance sensitive-template compatibility, thereby preserving recognition-site fidelity. Emerging methodologies include magnetic composite fabrication, streamlined separation processes, and improved operational efficiencies in field applications. MOF/COF-MIP-SPE coupled with CMS, which is typically used to detect coastal NPs, including POPs, antibiotics, EDCs, and microplastics, is summarized. These composites are highly proficient in isolating trace-level NPs from heterogeneous matrices by leveraging their tailored porosities and selective binding abilities. Enhanced chemical stability ensures consistent performance under fluctuating pH and high ionic-strength conditions, whereas the hierarchical pore structure facilitates rapid analyte transport. These molecularly imprinted SPE-based(MISPE-based) composites deliver detection sensitivities that surpass those of conventional SPE coupled with chromatography or chromatography-MS, which underscores their significant potential for efficiently enriching and purifying NPs in complicated coastal media. In addition, we discuss possible challenges faced when analyzing NPs in coastal samples using MOF/COF-MIP composite-based SPE, including regeneration-efficiency limitations, long-term stability under harsh conditions, and synthesis-protocol scalability. Repeated use in dynamic coastal environments often leads to pore fouling or MIP-layer degradation, necessitating durable composite design innovation. Looking forward, we discuss future prospects for the synthesis and application of composites, emphasizing the keen pursuit of multifunctional MOF/COF-MIP composites that are capable of simultaneously adsorbing, recognizing, enriching, and catalytically degrading NPs. Interdisciplinary approaches, especially ones that use artificial intelligence to energize and sustainably develop, including machine-learning-guided material design, while abiding by green-chemistry principles, have been proposed to accelerate the development of next-generation composites. Computational models capable of predicting framework-pollutant interactions can streamline the creation of new composites, while sustainable synthesis routes, such as those that employ aqueous solvents and biodegradable components, are expected to minimize environmental impacts. In conclusion, this review aims to bridge the gap between fundamental research and the practical applications of MOF/COF-MIPs for detecting NPs. By addressing current limitations through multidisciplinary collaboration and sustainable engineering, these materials are expected to be highly efficient, economical, environmentally friendly, portable, and industrializable; combined with SPE followed by chromatography or chromatography-MS, they hold significant potential for the screening and identification of NPs in coastal zones.

  • Xuanyu LIU, Lei SUI, Mingyu MA, Yi BI, Zhihua SONG
    Chinese Journal of Chromatography. 2025, 43(8): 857-867.

    Carbon dots(CDs) are a new class of materials with a wide range of applications. CDs possessed the advantages of small size effect, remarkable photostability, low cytotoxicity, good biocompatibility, simple synthesis and surface modification, and abundant surface functional groups(hydroxyl groups, carboxyl groups, amino groups, etc.). Currently, CDs show ultra-high potential in various fields. Carbohydrates are one of the most diverse and important classes of biomolecules in nature and can be modified at isomeric positions and hydroxyl functional groups. The saccharides are readily available carbohydrates in nature with non-toxicity and low permeability, providing an attractive and inexpensive starting material for the synthesis of CDs with specific properties and multifunctional applications. In recent years, the preparation of CDs from bio-based saccharide sources provides a new idea for CDs synthesis due to its advantages of low cost, renewable raw materials and green environment. Depending on the carbon source, the synthesis strategy of CDs can be broadly classified into top-down and bottom-up approaches. The top-down approach refers to the decomposition of larger carbon structures into nanoscale particles(e.g. graphene, carbon nanotubes, etc.), while the bottom-up approach refers to the synthesis of CDs from smaller carbon units(e.g. saccharides, organic acids, etc.). Using saccharides as carbon source, the methods for synthesis of CDs via bottom-up approach have been carefully summarized. In detail, bottom-up approach consisted of hydrothermal, microwave-assisted, ultrasonic and pyrolysis methods. The acquired saccharide-derived CDs had the properties of good water-solubility, low-toxicity, photostable and chemically stability. What’s more, the obtained CDs had broad application prospects in various fields, such as bioimaging, biosensing, drug/gene delivery and chromatographic analysis. In bioimaging, CDs have excellent optical properties and low toxicity, and can be used as fluorescent probes for real-time imaging in cells and tissues. In biosensing, the functional groups on the surface of CDs can specifically bind to the detected substances to achieve highly sensitive detection of biomolecules or ions. In drug/gene delivery, CDs can be used as carriers for efficient delivery of drugs or genes, reducing side effects and improving therapeutic effects. In chromatographic separation, CDs can be loaded on stationary phases and interact with compounds to achieve efficient separation of compounds. Furthermore, the saccharide-derived CDs showed good performances in the separation and analysis of new contaminants including nuclides, antibiotics, etc. Additionally, the saccharide-derived CDs exhibited outstanding properties for pharmaceuticals(alkaloids, nucleoside analogues, etc.) determination. Thus, CDs provide new tools for environmental monitoring and drug analysis. In the future, the research objectives in the preparation of CDs include the following: firstly, to continue to develop low-cost and simple preparation methods for the large-scale production of physically and chemically stable CDs. Secondly, the surface functional groups of CDs are further enriched in order to improve the interaction ability of CDs with target molecules or ions and to be able to endow CDs with more functionalities, such as targeting and responsiveness. In addition, a variety of heteroatoms(e.g., nitrogen, boron, phosphorus, sulfur, etc.) are doped to improve the properties of CDs. In addition to the improvement of preparation protocols, expanding the application of CDs in chromatography and sensing analysis, as well as in-depth study of their mechanism of action still deserves attention.

  • Jiawen CHENG, Jiashun ZHU, Yajing LIU, Jing HUA, Shuang LI
    Chinese Journal of Chromatography. 2025, 43(8): 868-880.

    p-Phenylenediamine(PPD) compounds are widely used as antidegradants in the rubber industry due to their excellent antioxidant and antiozonant properties. However, increasing environmental concerns have arisen regarding their transformation products, especially quinone derivatives(PPD-Qs), which are formed through oxidative processes under environmental conditions. These compounds have been frequently detected in various matrices, including air, water, sediment, soil, and biota, and have demonstrated significant ecological toxicity even at trace concentration. Accurate quantification of PPDs and PPD-Qs remains a significant analytical challenge due to their low environmental concentrations, high chemical reactivity, and matrix interferences. This review critically evaluates the current state-of-the-art analytical methodologies for the determination of PPDs and PPD-Qs across various environmental compartments. Emphasis is placed on the latest advancements in sample pretreatment techniques and instrumental detection methods that are suitable for complex and heterogeneous matrices. In gaseous and particulate samples, quartz fiber filters, passive samplers, and accelerated solvent extraction(ASE) have been employed for effective compound collection and extraction, with antioxidant protection(e.g., glutathione) used to prevent analyte degradation. solid-phase extraction(SPE) based on hydrophilic-lipophilic balance(HLB) sorbents, as well as salting-out assisted liquid-liquid extraction(SALLE), have achieved high recovery rates and reduced matrix effects. Passive monitoring approaches like diffusive gradients in thin films(DGT) have enabled long-term, time-integrated assessment of waterborne PPD-Qs under varying environmental conditions. For solid or semi-solid matrices such as soil, sediment, and biological tissues, ultrasound-assisted extraction(UAE), gel permeation chromatography(GPC), and modified QuEChERS methods have been widely adopted for high-efficiency extraction and purification. Instrumentally, gas chromatography-mass spectrometry(GC-MS) and liquid chromatography-tandem mass spectrometry(LC-MS/MS) remain the gold standards for sensitive and specific quantification. High-resolution mass spectrometry(HRMS), such as Orbitrap platforms, enables non-targeted screening and structural elucidation of unknown metabolites and degradation products. In addition, emerging techniques such as condensed phase membrane introduction mass spectrometry(CP-MIMS) provide rapid, in situ detection with minimal sample pretreatment, showing great potential for real-time environmental monitoring. Electrochemical sensing platforms based on carbon-based or metal nitride-modified electrodes have also demonstrated promise due to their rapid response, cost-effectiveness, and field-deployable capabilities. However, challenges such as electrode fouling and selectivity limitations remain. In conclusion, this review integrates and evaluates a wide range of analytical approaches for detecting PPDs and PPD-Qs in complex environmental matrices. The comparative analysis of methodologies provides practical insights for optimizing analytical performance and advancing environmental surveillance. Future research should prioritize the development of automated, high-throughput, and green analytical platforms that are adaptable to field monitoring, risk assessment, and regulatory needs for emerging tire-derived contaminants.

  • Tingting LOU, Lin HUANG, Youzhi SU, Jun LIU, Haitao LI, Pinyao ZHAO
    Chinese Journal of Chromatography. 2025, 43(8): 881-893.

    As an emerging pollutant, microplastics have become a significant component of global environmental pollution, thereby attracting growing attention from the scientific community and policymakers. Microplastics, defined as plastic particles smaller than 5 mm in diameter, are widely distributed in aquatic environments, including rivers, lakes, oceans, and even groundwater. Due to their small size and persistent nature, microplastics can be easily ingested by aquatic organisms, particularly shellfish, crustaceans, and fish, which are integral components of the aquatic food web. These aquatic products serve as a crucial source of animal protein for human consumption, making the contamination of microplastics in these organisms a direct pathway for human exposure. Once ingested, microplastics may accumulate in human tissues and organs, potentially causing irreversible harm to human health, including inflammatory responses, oxidative stress, and even carcinogenic effects. Therefore, understanding the contamination, distribution, and ecological impacts of microplastics in aquatic products is of paramount importance for both environmental protection and public health. This paper provides a comprehensive review of the current state of microplastic pollution in aquatic products, focusing on the primary sources, pollution pathways, distribution patterns, and ecological consequences. Microplastics enter aquatic environments through various routes, including the breakdown of larger plastic debris, industrial effluents, wastewater treatment plants, and agricultural runoff. Once in the water, microplastics can be ingested by aquatic organisms, either directly or indirectly through the consumption of contaminated prey. The accumulation of microplastics in aquatic organisms not only affects their growth, reproduction, and survival but also disrupts the balance of aquatic ecosystems. Furthermore, microplastics can act as carriers for other pollutants, such as heavy metals and persistent organic pollutants, exacerbating their toxic effects on aquatic life and humans. In addition to analyzing the sources and ecological impacts of microplastic pollution, this paper critically evaluates the technical progress in microplastic extraction and identification methods. Current techniques for microplastic detection include visual identification, spectroscopic methods(e.g., Fourier-transform infrared spectroscopy(FT-IR) and Raman spectroscopy, and chromatographic-mass spectrometric approaches(e.g., pyrolysis-gas chromatography-mass spectrometry(Py-GC-MS)). Each method has its advantages and limitations. For instance, visual identification is simple and cost-effective but lacks accuracy for small-sized particles, while spectroscopic methods offer high specificity and sensitivity but require expensive equipment and specialized expertise. Chromatographic-mass spectrometric techniques provide detailed chemical composition analysis but are often time-consuming and complex. This paper discusses the strengths and weaknesses of these methods, highlighting the need for standardized protocols to improve the comparability and reliability of microplastic detection data. Looking ahead, this paper prospects the future directions of microplastic identification and detection technologies in aquatic products. Emerging techniques, such as nanomaterial-based sensors, surface-enhanced Raman scattering(SERS), and machine learning-assisted image analysis, hold great promise for enhancing the sensitivity, accuracy, and efficiency of microplastic detection. Moreover, the integration of multiple detection methods, such as combining spectroscopic and chromatographic techniques, could provide a more comprehensive understanding of microplastic contamination. The development of low-cost, portable detection devices is also essential for enabling widespread monitoring and real-time assessment of microplastic pollution in aquatic environments. Finally, this paper addresses the challenges and potential prevention and control measures in microplastic research. Key challenges include the lack of standardized detection methods, difficulties in detecting small microplastics or nanoplastics, and limited knowledge of their long-term ecological and health impacts. To tackle these issues, interdisciplinary collaboration among scientists, policymakers, and industry stakeholders is crucial. Potential prevention and control measures include reducing plastic waste at the source, improving wastewater treatment technologies, and promoting public awareness of plastic pollution. By summarizing existing research findings, this paper aims to provide a theoretical foundation and technical support for the risk assessment of microplastic contamination in aquatic products and the development of effective monitoring and management strategies. The insights gained from this review will contribute to safeguarding aquatic ecosystems, ensuring the safety of aquatic products, and protecting human health from the adverse effects of microplastic pollution.