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Chinese Journal of Chromatography
2026, Vol. 44, No. 10
Online: 08 October 2026

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Preface for Special Issue on Porous Framework Materials: Frontiers and Analytical Applications YAN Xiuping, GU Zhiyuan, QIAN Hailong 2026, 44 (10):  1103-1104.  DOI: 10.3724/SP.J.1123.2026.09004 Abstract ( 44 )   HTML ( 11 )   PDF (443KB) ( 24 )

Reviews

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Recent progress in constructions and applications of chiral porous framework-based chromatographic stationary phases LONG Shen, CHEN Jiayu, YUAN Chen, HOU Xiandeng 2026, 44 (10):  1105-1117.  DOI: 10.3724/SP.J.1123.2026.01009 Abstract ( 149 )   HTML ( 9 )   PDF (1693KB) ( 37 )   Chirality， as an inherent property of nature， plays a central role in the complexity and precision of biological systems. The stereochemistry of molecules profoundly impacts their pharmacological activities， metabolic pathways， and toxicological effects. Enantiomers， which are mirror-image forms of the same compound， often exhibit significantly different behaviors， making the accurate separation and trace analysis of racemates crucial in modern pharmaceutical research， as well as in the production of high-value chiral intermediates. The precise enantioseparation of compounds has therefore become an essential component of drug development， environmental monitoring， and chemical synthesis. Among various separation methods， chiral chromatography has emerged as the most dominant technique due to its high efficiency， versatility， and rapid analytical capabilities. Conventional chiral stationary phases （CSPs） have been primarily based on materials such as polysaccharides， proteins， and synthetic polymers. However， recent advancements in materials science have led to the development of chiral porous frameworks， particularly metal-organic frameworks （MOFs） and covalent organic frameworks （COFs）， which offer remarkable advantages. These materials feature ultra-high surface areas， well-ordered porous structures， and tunable chiral microenvironments， making them ideal candidates for the next generation of chiral stationary phases in chromatography. This review provides a comprehensive summary of the recent progress made by domestic scholars from 2023 to 2025 on the application of MOFs and COFs in chiral separation， specifically in high performance liquid chromatography （HPLC）， gas chromatography （GC）， and capillary electrochromatography （CEC）. It begins by discussing the construction strategies for these chiral porous frameworks， highlighting their synthesis and functionalization methods. Next， it focuses on the preparation techniques for incorporating these materials into chromatographic stationary phases， emphasizing the challenges and innovations involved in optimizing their performance. The review then examines the practical applications of MOFs and COFs in the separation of racemates， showcasing their use in the enantioseparation of pharmaceuticals， agrochemicals， and natural products. The separation performance is evaluated based on key metrics such as resolution， selectivity， and enantioselectivity. Comparisons with traditional commercial columns highlight the superior performance of MOF- and COF-based stationary phases， including their higher efficiency， broader selectivity， and better adaptability to a wider range of compounds. Finally， the review discusses the future directions and challenges in the field. These include the need for scalable synthesis methods， enhancing the stability of MOFs and COFs under practical chromatographic conditions， and improving the selectivity of these materials. Future research may also focus on hybrid MOF-COF composites， further functionalization techniques， and the integration of these materials with advanced detection technologies to broaden their applications. Indeed， this review aims to provide an insightful summary of the current state of chiral separation materials， particularly MOFs and COFs， offering a valuable resource for researchers in this field. We hope this work will inspire future innovations， driving the advancement of chiral separation technologies to new levels of precision and efficiency.

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Recent advances in porous materials based silica stationary phases for liquid chromatography HUANG Zexin, TANG Sheng 2026, 44 (10):  1118-1128.  DOI: 10.3724/SP.J.1123.2025.12022 Abstract ( 91 )   HTML ( 5 )   PDF (1083KB) ( 29 )   Recent years have seen significant progress in nanoscience and materials chemistry， driving the development of novel porous materials such as metal organic frameworks （MOFs）， covalent organic frameworks （COFs）， and porous organic cages （POCs）. MOFs form through coordination bonds between metal ions and organic bridging ligands， COFs result from strong covalent linkages connecting predesigned organic building blocks into extended crystalline networks， and POCs are three-dimensional cage-like organic molecules with well-defined intrinsic cavities. Nowadays， the use of porous materials as stationary phases in high-performance liquid chromatography （HPLC） continues to draw sustained research interest. By precisely designing the building blocks of porous materials， researchers can flexibly modulate separation selectivity in terms of pore size， pore morphology， and interlayer stacking patterns， thus enabling the efficient separation of complex samples， particularly for positional isomers and chiral compounds. Despite their considerable promise for chromatographic applications， the direct use of porous materials as stationary phases is constrained by inherent limitations. A primary challenge lies in synthesizing pure porous materials with both regular morphology and uniform particle size. Irregular particle shapes combined with broad size distributions typically result in high column pressure and low column efficiency， which severely restricts the practical application of porous materials in HPLC. To overcome these limitations， combining porous materials with silica gel （SiO2） supports has become a widely adopted strategy. As the most mature stationary phase support in HPLC， SiO2 offers excellent mechanical strength， chemical stability， and a readily functionalizable surface， thereby providing a robust structural platform for porous materials. By immobilizing porous materials onto the silica surfaces， their mechanical robustness and packing uniformity can be significantly improved while retaining their selective adsorption capability， thus promoting their reliable use in chromatographic applications. Furthermore， in order to further enhance separation efficiency and selectivity， researchers have proposed the co-modification of silica gel with porous materials and other functional components such as ionic liquids， hydrogels， and carbon dots， aiming to construct multifunctional composite stationary phases. The key advantage of this strategy lies in the synergistic integration of multiple separation mechanisms， including hydrophobic effects， hydrogen bonding， π-π interactions， and chiral recognition， through material hybridization， thereby achieving higher performance and selectivity in separating complex systems. Moreover， this composite approach effectively mitigates the limitations of single-component materials， for example， by improving the aqueous stability of MOFs or extending the applicability of COFs in the analysis of polar compounds， thereby significantly broadening the application scope of stationary phases. This review systematically summarizes the research progress in silica-based composites incorporating advanced porous materials for HPLC in the last five years， and offers a comprehensive overview of prevalent synthetic methodologies used to fabricate these composite stationary phases. Furthermore， the review addresses the major challenges currently facing the field and provides perspectives on future developments.

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Research progress of metal-organic frameworks and their composite materials in solid-phase （micro）extraction techniques ZHANG Zhen, WANG Xuemei, ZHANG Xinzhong, DU Xinzhen, LU Xiaoquan 2026, 44 (10):  1129-1149.  DOI: 10.3724/SP.J.1123.2026.01015 Abstract ( 111 )   HTML ( 12 )   PDF (7645KB) ( 20 )   Sample pretreatment is the core stage of instrumental analysis. It serves to concentrate trace components， eliminate matrix interference， enhance detection sensitivity， and protect analytical instruments. It is a key step in the analysis and detection of complex environmental samples. Modern sample pretreatment techniques， such as solid-phase （micro）extraction， have the advantages of rapidity， automation， and no or minimal solvent usage， significantly improving the analysis efficiency. The core of solid-phase （micro）extraction technology is the adsorbent material， whose performance directly affects the accuracy of the analysis results. Metal-organic frameworks （MOFs） exhibit significant advantages in the field of adsorption and separation due to their exceptionally high specific surface area， tunable pore structures， nanoscale pore environments， and excellent physicochemical stability. Furthermore， building on MOFs as a foundational platform， researchers have developed different strategies for the controlled incorporation of functional components and the precise design of composite architectures. These strategies have enabled the development of MOFs and their composites. These materials allow for targeted enhancement and control over adsorption capacity， mass transfer efficiency， selectivity， stability， and unique interfacial behaviors. As a result， MOFs and their composites are well-suited to address the multifaceted challenges encountered in complex sample preparation. This review summarizes recent advances in the application of MOFs and their composites within solid-phase （micro）extraction techniques. These techniques include solid-phase extraction （SPE）， dispersive solid-phase extraction （DSPE）， magnetic solid-phase extraction （MSPE）， membrane extraction （ME）， pipette-tip solid-phase extraction （PT-SPE）， membrane-protected solid-phase extraction （MP-SPE）， fiber solid-phase microextraction （Fiber-SPME）， and in-tube solid-phase microextraction （IT-SPME）. From the dual perspectives of adsorbent material applications and methodological development， the review highlights the advantages of MOF-based composites with varied compositions and structures across different sample preparation approaches. It further summarizes the methodological strengths and specific limitations associated with each pretreatment technique. With the expanding application scope of the techniques-particularly in environmental， food， and biomedical fields， increasing demands are being placed on the green synthesis， biocompatibility， and safety of MOFs and their composites. This trend is driving the development of MOFs and related composites toward integrated functionality， environmentally friendly preparation， and application-specific adaptability. From current trends， the design philosophy of transforming powdered materials into monolithic structures represents a significant direction in the development of sample preparation technologies. Both directly and indirectly prepared monolithic materials， as well as those integrated into monolithic devices， retain the performance advantages of powdered adsorbents while offering improved recoverability， portability， and operational convenience. Building on this foundation， techniques such as fiber-SPME and IT-SPME are further advancing toward miniaturization， downsizing， high-throughput operation， and automation. This progress aims to enhance the efficiency of sample preparation and analytical detection. Finally， the future development directions of various currently developed solid-phase （micro）extraction techniques are discussed. The aim is to advance sample preparation technology toward online， high-throughput， and automated systems through comprehensive innovation in adsorbent materials and technical methodologies. Such progress is expected to accelerate the practical application of these techniques in fields such as environmental monitoring， biomedical analysis， and on-site rapid testing. In conclusion， this evolution will ultimately facilitate the transition from laboratory methods to reliable analytical tools.

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Structural features and regulation of adsorption/separation properties of photoresponsive metal-organic frameworks LIU Limeng, XIE Wenzhe, QU Yanying, CAI Tianpei, LI Donghao, SHANG Haibo 2026, 44 (10):  1150-1161.  DOI: 10.3724/SP.J.1123.2026.01025 Abstract ( 146 )   HTML ( 4 )   PDF (1546KB) ( 21 )   Metal-organic frameworks （MOFs） are attractive porous materials with periodic network structures， which are constructed via the self-assembly of metal ions （or metal clusters） and bridging organic ligands. MOFs have some unique advantages of designability， ordered pore structure， high specific surface area and modifiability. Photoisomerization refers to the phenomenon in which， under light of specific wavelengths， the molecular structures of certain compounds undergo reversible interconversion due to photoexcitation. Both isomeric forms can exist stably under certain conditions and exhibit distinct chemical and physical properties. On this basis， photoresponsive MOFs （PMOFs） are proposed as a class of smart materials constructed by integrating photoactive molecules into MOFs. PMOFs combine the inherent superior porous structure of MOFs with the dynamic tunability enabled by photo-induced isomerization and exhibit unique advantages in many fields， including catalysis， drug release， separation， anti-counterfeiting， etc. PMOFs， for instance， can precisely regulate adsorption/separation behaviors and enable green， energy-efficient recovery of adsorbents under photoinduction， which has attracted widespread attention. This review summarizes common types and properties of photoactive molecules， including azobenzene， spiropyran， diarylethene， spirooxazine， fulgide， Schiff base， etc.， as well as three main integration strategies of photosensitive units/molecules with MOFs frameworks. Backbone incorporation involves using the entire photoactive organic molecule as an organic ligand within the MOF framework. For side-group grafting， the photoactive moiety is attached as a side group or through post-synthetic modification of the organic ligand， effectively grafting it onto the MOF backbone. Guest encapsulation is referred to embedding photoactive molecules as independent guest species within the cavities or pores of the MOF. By analyzing the differences in isomerization of various photoactive groups and the structural features of different integration modes， the multidimensional modulations of MOF are illustrated in pore size， surface properties， host-guest interaction， “hiding” and “exposure” of adsorption active sites， and framework geometry via photoisomerization. Furthermore， from a structure-performance perspective and with representative case studies， this review discusses the regulatory mechanisms and application potential of PMOFs in the adsorption and separation of small-molecule gases， metal ions， and organic dyes. The key limitation of PMOFs lies in whether the MOF framework is robust enough to tolerate the molecular mechanical forces produced by photoswitch configurational rearrangements. The cyclic photo‑switching performance of PMOFs is often unsatisfactory， which is primarily attributed to the molecular mechanical forces generated during repeated photoisomerization， which may cause local microscopic distortion， phase transitions， or even framework collapse in MOFs. In addition， the photo‑response efficiency of PMOFs is inadequate， which is obviously lower than photosensitive molecules in solution. This is likely due to limited optical penetration depth， steric hindrance within the pores， and framework‑induced quenching of the excited‑state configuration. The above challenges are summarized in this paper， with the aim of facilitating discussions among researchers and promoting their multidimensional exploration and development.

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Recent advances in the applications of covalent organic frameworks for strategic critical metal recovery： focusing on rare earths and dispersed metals ZHANG Shuang, SUN Mingxia, QIU Hongdeng, CHEN Jia 2026, 44 (10):  1162-1174.  DOI: 10.3724/SP.J.1123.2026.01027 Abstract ( 140 )   HTML ( 3 )   PDF (2706KB) ( 28 )   Strategic critical metals， such as rare earths and dispersed metals， are indispensable key raw materials for high-tech industries， including new energy and electronics. Although China is rich in mineral resources （especially rare earth minerals）， the supply has always been a concern due to extremely uneven distribution and the significant environmental pressures caused by the mining process. At the same time， with the rapid development of related industries， the amount of waste equipment containing these metals （such as discarded batteries and used NdFeB magnets） and industrial wastewater has increased sharply. Therefore， efficiently recovering strategic critical metals from secondary resources is of great importance. Among various recovery processes， solvent extraction and precipitation methods have been widely applied in systems with conventional concentrations and relatively simple components due to their mature technology and relatively high separation efficiency. However， these methods face challenges such as low efficiency， poor selectivity， and high environmental burden when treating low-concentration， multi-component systems. Adsorption methods， with their simple operation， low energy consumption， and environmentally friendly characteristics， have become one of the most promising methods for recovering and processing strategic critical metals in extreme industrial systems. By designing or selecting specific adsorbent materials （such as ion-imprinted polymers， functionalized porous materials）， specific adsorption of target metal ions can be achieved， especially enabling efficient separation of desired metals in complex multi-metal solutions. However， this method demands higher requirements for the performance and stability of the adsorbents. Therefore， developing novel adsorbent materials with high selectivity， high adsorption capacity， and environmental friendliness has become a key bottleneck that urgently needs to be overcome in this field. Covalent organic frameworks （COFs） are a fascinating class of crystalline porous organic materials constructed via strong covalent bonds from light elements including carbon， hydrogen， nitrogen， oxygen， and boron. COFs integrate multiple superior properties. They not only possess ultra-high specific surface areas and tunable pore sizes but also exhibit excellent structural designability. Their pore sizes can be adjusted from the nanometer scale to the angstrom level， allowing for the sieving of ions of different sizes through size exclusion effects. Moreover， the organic monomers of COFs contain abundant functional groups， enabling selective recovery based on differences in affinity for metal ions. At the same time， their fully organic frameworks endow numerous COFs with excellent stability in harsh environments such as acids and bases. Thanks to these unique characteristics， COFs have emerged as promising candidates for the highly selective and high-capacity recovery of critical metals in low-concentration， multi-component systems.This review systematically summarizes recent advances in the application of COFs for the recovery of rare earth and dispersed metals， with a focus on the introduction of specific functional groups through direct synthesis and post-modification strategies to achieve efficient recognition and capture of target metal ions. The performance of COFs in terms of adsorption capacity， selectivity， and cycling stability is outlined， and their adsorption mechanisms， as well as desorption and regeneration methods， are discussed. Finally， challenges in structural design， scalable synthesis， and environmental adaptability for practical applications are analyzed， and future research directions are proposed. This review aims to provide a reference for researchers in this field and to promote further development of COF materials in resource recovery applications.

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Research progress of magnetic microporous organic networks in magnetic solid-phase extraction WANG Jinshuang, YANG Chengxiong 2026, 44 (10):  1175-1189.  DOI: 10.3724/SP.J.1123.2025.12010 Abstract ( 115 )   HTML ( 4 )   PDF (1454KB) ( 27 )   Recently， magnetic microporous organic networks （MMONs） have emerged as a novel class of adsorbents in magnetic solid-phase extraction （MSPE）. By integrating the unique properties of microporous organic networks （MONs） and magnetic nanoparticles， MMONs exhibit advantages such as designable structures， facile synthesis， diverse architectures， high specific surface area， and excellent stability， garnering widespread attention in the field of sample pretreatment. The current strategies for preparing MMONs mainly include in-situ growth， post-synthetic modification （PSM）， and composite preparation. Among these， the in-situ growth method can be further categorized into direct in-situ growth， indirect in-situ growth， and co-doping methods. The direct in-situ growth method is straightforward to operate， enabling the construction of MMONs with well-defined core-shell structures. It also allows flexible control over the functionality and shell thickness of MMONs by adjusting the type and concentration of monomers， making it the most commonly used preparation method for MMONs. In contrast， the indirect in-situ growth method involves the introduction of an intermediate bridging layer， which complicates the synthesis process. However， the intermediate coating layer and the MONs shell can work synergistically to enhance the extraction efficiency of MMONs for targets. Although PSM requires additional reaction steps and poses challenges in controlling the modification rate and distribution of functional groups， it increases the variety and quantity of modifying groups and molecules， thereby expanding the application range of MMONs in MSPE. Furthermore， MMON composites can integrate the respective advantages of both MMONs and polymers， further broadening the applicability of MMONs. Therefore， each of the three methods mentioned above has its own advantages and disadvantages. Researchers can select the appropriate synthesis method based on the specific requirements of MSPE to prepare the desired MMONs. This review also provides a detailed discussion on the applications of MMONs in the MSPE of various organic pollutants， including pharmaceuticals， pesticides， endocrine-disrupting chemicals， mycotoxins， food additives， and per- and polyfluoroalkyl substances， and elucidates the extraction mechanisms （e.g. hydrophobic interaction， π-π stacking， electrostatic attraction， hydrogen-bonding interaction， ion pair interaction， fluorine-fluorine interaction， and π-CF interaction） between MMONs and analytes. In response to the current challenges of MMONs， future research should focus on the following areas： （1） Designing and expanding low-cost functional monomers to enrich the variety and quantity of existing functional monomers， providing other effective PSM methods for synthesizing functionalized MMONs， and introducing other functional composites to prepare MMON composites. （2） Developing target-oriented structural design or functionalization strategies to construct functionalized MMONs， with the aim of improving their selectivity toward specific targets. （3） Advancing other advanced characterization and mechanism investigation techniques to understand the extraction mechanisms of MMONs and guide their structural design or functionalization. In summary， this review aims to deepen the understanding of MMONs-based MSPE methods in the enrichment and detection of various organic pollutants， while offering guidance for the synthesis and application of MMONs.

Mini-reviews

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Recent progress on sample pretreatment methods of emerging pollutants in food based on porous framework materials HUANG Jiaqi, HAN Yangxia, HA Wei, ZHANG Yingshan, SHI Yanping 2026, 44 (10):  1190-1202.  DOI: 10.3724/SP.J.1123.2026.01023 Abstract ( 149 )   HTML ( 4 )   PDF (2327KB) ( 41 )   Emerging pollutants （ECs） generally refer to chemicals or microorganisms that have known potential toxicity and health hazards. The defining characteristics of ECs include environmental persistence， bioaccumulation and biological toxicity. Primary categories of ECs comprise endocrine disrupting chemicals （EDCs）， persistent organic pollutants （POPs） and antibiotics. Dietary intake represents a predominant pathway for human exposure to ECs. This necessitates the development of highly sensitive and reliable analytical methods. Conventional analytical instruments are fundamental for ECs determination. These include high performance liquid chromatography （HPLC）， liquid chromatography-tandem mass spectrometry （LC-MS/MS）， and gas chromatography-tandem mass spectrometry （GC-MS/MS）. However， the direct analysis of ECs in food remains a significant challenge. This is due to their wide sources， numerous types， complex structures， and ultra-low concentrations alongside substantial matrix interferences. Consequently， it is urgent to develop efficient sample pretreatment techniques to extract， enrich and purify ECs in food， in order to reduce matrix interference and construct the foundation for establishing highly sensitive， accurate， and stable analytical methods. Among various pretreatment techniques， solid-phase extraction （SPE） has gained prominence. It offers notable advantages over liquid-liquid extraction （LLE）. These advantages include simple operation， low consumption of organic solvents and higher enrichment factors. To address specific analytical needs， several advanced SPE modalities have been developed， including magnetic solid-phase extraction （MSPE）， solid-phase microextraction （SPME）， dispersive solid-phase extraction （dSPE）， and stir bar sorptive extraction （SBSE）. Each variant offers unique benefits in terms of automation， speed， or selectivity. The performance of any SPE-based method is fundamentally governed by the adsorbent material. In recent years， porous framework materials have emerged as a revolutionary class of sorbents. They offer exceptional properties for extraction technology. Porous framework materials mainly include metal organic frameworks （MOFs）， covalent organic frameworks （COFs）， and， hydrogen-bonded organic frameworks （HOFs）. These materials are distinguished by their high specific surface area， tunable pore size and abundant sites for functionalization. Their structural periodicity and designability enable precise interaction with target analytes. This review provides a comprehensive and systematic overview of recent progress. It focuses on MOFs， COFs， and HOFs as next-generation adsorbents for ECs analysis. The article begins by introducing the fundamental structures and general properties of these three material classes. It details the synthesis strategies for both pristine materials and their composites. A major emphasis is placed on rational design principles. These principles aim to enhance adsorption performance. Key strategies discussed include ligand functionalization， defect engineering， and the construction of composite/hybrid materials. The review explains how these strategies modulate the adsorption mechanism， including size-exclusion， electrostatic interaction， π-π stacking， hydrogen bonding， and coordinative interaction. Subsequently， the application progress of these designed materials is thoroughly summarized. It is organized according to major ECs categories： EDCs， POPs， and antibiotics. For each category， representative studies from the past three years are highlighted. The discussion covers material design， extraction format （MSPE， dSPE， SBSE， SPME， etc.）， analytical technique coupling， and key performance metrics. Metrics include adsorption capacity， selectivity， and reusability. The successful determination of ECs in complex food samples is demonstrated. Finally， the review critically examines significant outstanding challenges and suggests corresponding directions for future research. These include the long-term stability of some frameworks in complex matrices. Scalable and green synthesis methods are also needed. Furthermore， seamless integration of these materials into automated， online analytical platforms requires development. Future research should prioritize several areas. Deeper mechanistic understanding via in-situ characterization and computational modeling is essential. The development of robust， environmentally friendly synthesis pathways is crucial. Enhancing material stability and selectivity for real-world applications is a key goal. Finally， translating powdered materials into practical， engineered devices is an important step. In conclusion， porous framework materials hold immense promise. They are poised to redefine sample pretreatment for food safety analysis. This review aims to serve as a valuable reference. It is intended for researchers developing new adsorbent materials and analytical methods for ECs.

Articles

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Preparation and application of heteroporous covalent organic frameworks as gas chromatography stationary phases LI Zhiquan, RAO Zirui, QIAN Hailong, YAN Xiuping 2026, 44 (10):  1203-1211.  DOI: 10.3724/SP.J.1123.2026.01035 Abstract ( 153 )   HTML ( 2 )   PDF (1693KB) ( 34 )   Chromatographic separation stands as a cornerstone technique in modern analytical chemistry， playing an indispensable role in critical areas such as chemical purification， environmental monitoring， and pharmaceutical analysis. With the increasing complexity of analytical samples， particularly regarding the efficient separation of structurally similar isomers， higher requirements have been imposed on chromatographic stationary phases. Traditional porous materials such as zeolites and silica show limited tunability in pore size distribution and surface chemistry， making it difficult to meet the urgent need for high-resolution and rapid separation of complex mixtures. Therefore， the exploration of novel ordered porous materials with precisely tunable pore structures and functionalities has become a frontier research direction in separation science. Covalent organic frameworks （COFs）， as a category of crystalline porous polymers， possess great application potential in separation science. Their prominent advantages mainly include designable periodic frameworks， easily modified functional groups， and precisely tunable pore sizes. These intrinsic merits render COFs promising candidates for next-generation chromatographic separation media. In this work， a novel strategy is proposed to regulate the pore structure of COFs via rational topological design， aiming to improve their gas chromatographic performance toward challenging isomer separation. This is achieved by constructing heteroporous COFs that integrate distinct pore size distributions within a single， ordered framework. To realize this strategy， a heteroporous COF designated as ET-COF was successfully constructed. It was synthesized via a reversible imine condensation reaction between a D2h-symmetric tetraamine monomer， 4，4′，4″，4′′′ -（ethene-1，1，2，2-tetrayl）tetraaniline （ETTA）， and a C2-symmetric linear dialdehyde linker， terephthalaldehyde （TPA）. This assembly affords a two-dimensional framework with a Kagome topology. The porous structures of material were rigorously characterized. It has been demonstrated through nitrogen adsorption-desorption experiments that ET-COF exhibits a distinct dual-pore structure， including triangular micropores of approximately 1.1 nm and hexagonal mesopores of 2.89 nm， with a specific surface area of 724 m2/g and a pore volume of 1.26 cm3/g. The rich pore structure and high specific surface area confer multiple size-exclusion effects. By virtue of these structural merits， an ET-COF-bonded capillary chromatographic column was further prepared via a facile in-situ growth method， which enables stable and uniform strong chemical bonding of the COF layer to the inner wall of a fused-silica capillary. Finally， the chromatographic performance of this column was systematically evaluated. The heteroporous ET-COF column demonstrated excellent separation performance across a wide range of test analytes. Baseline separation was successfully achieved for diverse mixtures， including homologous n-alkanes （C5-C10）， alkylbenzenes （from benzene to butylbenzene）， n-straight-chain fatty acid esters， and critically a set of C9 aromatic hydrocarbon isomers （n-propylbenzene， isopropylbenzene， and mesitylene）， with resolution values ranging from 2.0 to 15.3， suggesting outstanding separation efficiency. The improved chromatographic behavior can be rationalized by the uniquely hierarchical pore structure originating from rational topological design. The triangular micropores afford a confined microenvironment that imposes prominent size- and shape-selectivity， enabling discrimination of isomers with subtle differences in molecular configuration. Meanwhile， the hexagonal mesopores act as rapid transport pathways to promote fast mass transfer and avoid pore blocking. Such a synergistic effect of selective micropores and high-flux mesopores within one crystalline framework represents a distinct merit of the heteroporous topology. In summary， this work establishes a feasible topological strategy for constructing high-performance COF-based stationary phases and investigates the impact of hierarchical pore structures （synergistic effects of microporous shape selectivity and mesoporous mass transfer） on separation performance. By rational topological assembly， precise pore engineering and integration of hierarchical channels are readily realized， which greatly boost the separation selectivity toward challenging isomers. This study not only develops a promising heteroporous COF stationary phase for gas chromatography， but also provides a new design paradigm for extending the application of COFs in analytical separation science.

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Preparation and chiral separation performance evaluation of a high performance liquid chromatography stationary phase based on a ［2+4］-type chiral porous organic cage Pim CHEN Chun, GONG Yanan, WANG Bangjin, XIE Shengming, ZHANG Junhui, YUAN Liming 2026, 44 (10):  1212-1222.  DOI: 10.3724/SP.J.1123.2026.01017 Abstract ( 82 )   HTML ( 2 )   PDF (1938KB) ( 22 )   Supporting Information Porous organic cages （POCs） represent a class of emerging porous materials assembled from discrete three-dimensional cage-like molecules via intermolecular interactions. Owing to their good solubility and unique pore structures， they show great potential in gas adsorption， molecular recognition， separation， catalysis， and sensing. In this study， a phenolphthalein-based tetraaldehyde compound was synthesized via the Duff reaction using phenolphthalein as the substrate and trifluoroacetic acid （TFA） combined with hexamethylenetetramine （HMTA） as the formylation reagent. Subsequently， a ［2+4］-type chiral imine POC， Pim （C72H68N8O8）， was constructed by reacting the tetraaldehyde precursor with （1R，2R）-（-）-1，2-diaminocyclohexane via imine condensation. The synthesized Pim was functionalized with alkenyl groups using 5-bromo-1-pentene and then immobilized onto thiol-modified silica via thiol-ene click chemistry to afford a novel chiral stationary phase （CSP） for high performance liquid chromatography （HPLC）. The successful syntheses of tetraaldehyde compound， Pim， and CSP were characterized by nuclear magnetic resonance （NMR）， fourier transform infrared spectroscopy （FT-IR）， electrospray ionization mass spectrometry （ESI-MS）， thermogravimetric analysis （TGA）， and elemental analysis （EA）. The chiral separation performance of this CSP was evaluated under both normal-phase （NP） and reversed-phase （RP） HPLC separation modes. The results demonstrated that the CSP exhibits excellent chiral separation capabilities in both two separation modes. Under NP-HPLC conditions， ten racemates were resolved， including five with baseline separation. Under RP-HPLC conditions， nine racemates were resolved， of which eight achieved baseline separation. Furthermore， this CSP exhibits good chiral separation complementarity with two widely used commercial columns， Chiralpak AD-H and Chiralcel OD-H， showing the ability to resolve some chiral compounds that cannot be resolved or are poorly resolved by the two commercial columns. The effects of analyte injection mass and column temperature on chiral separation performance of the column were also investigated. Additionally， the prepared HPLC column exhibits good repeatability and stability. After hundreds of injections， no significant changes were observed in the retention times and resolutions compared to its initial performance， with relative standard deviations （RSDs， n=5） of ≤1.50% and ≤1.92%， respectively. Meanwhile， after the column was placed and stored for one month， its separation performance showed no significant change compared with that at the initial stage of column use， and the RSDs （n=3） of retention time and resolution were ≤1.88% and ≤2.26%， respectively. This study confirms that the chiral POC Pim is a promising material for HPLC chiral separation， providing significant theoretical and experimental support for the development of novel POC-based CSPs and holding great significance for expanding the POC-based CSPs.

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Trifluoroacetic acid-modulated synthesis of defective UiO-66 for highly efficient removal of sodium p-perfluorous nonenoxybenzenesulfonate WANG Xuan, WANG Chunxiao, XIA Yan 2026, 44 (10):  1223-1232.  DOI: 10.3724/SP.J.1123.2026.01019 Abstract ( 161 )   HTML ( 2 )   PDF (1891KB) ( 21 )   Per- and polyfluoroalkyl substances （PFAS）， widely known as “forever chemicals”， present a severe and escalating global threat to ecological systems and human health. Their extreme persistence originates from remarkably strong carbon-fluorine bonds， while their amphiphilic nature facilitates widespread environmental dispersal and bioaccumulation. Among them， sodium p-perfluorous nonenoxybenzenesulfonate （OBS） has been extensively used as a commercial alternative to perfluorooctanesulfonic acid （PFOS）， which is under strict global regulation. However， mounting evidence has revealed that OBS exhibits higher bioaccumulation， higher environmental persistence， and significant cytotoxicity， raising urgent environmental concerns and creating an urgent demand for efficient remediation technologies. To tackle this challenge， this study proposes a defect-engineering strategy for the design of advanced adsorbent materials. Specifically， a series of trifluoroacetic acid （TFA）-modulated UiO-66-type metal-organic frameworks （MOFs）， denoted as U-TFA-10 M， UN-TFA-10 M etc.， were successfully synthesized via a solvothermal method. The intentional introduction of structural defects was designed to increase the density of active sites and tailor surface properties， thereby achieving enhanced pollutant capture performance. Comprehensive characterization confirmed the successful material synthesis and modification. Scanning electron microscopy （SEM） and transmission electron microscopy （TEM） images revealed that U-TFA-10 M and UN-TFA-10 M particles exhibited irregular， fragmented morphologies， a stark contrast to the regular octahedral shape of pristine UiO-66， visually indicating abundant structural defects. X-ray diffraction （XRD） patterns displayed a new broad peak in the 2θ range of 3°-5°， further confirming defect formation. Fourier-transform infrared spectroscopy （FT-IR） identified characteristic vibrations： peaks at 556 cm–1 and 482 cm–1 corresponded to Zr-O coordination， while a distinct peak at 1 212 cm–1 confirmed the presence of -CF3 groups. X-ray photoelectron spectroscopy （XPS） provided definitive evidence， with a clear F 1s signal verifying the successful incorporation of trifluoromethyl moieties into the MOF framework—a critical modification for enabling specific interactions with the target pollutant. Systematic adsorption evaluation and optimization were conducted. The optimal synthesis condition was identified as using 10 mol/L TFA as the modulator. The pH of the solution profoundly influenced adsorption， with maximum OBS removal achieved at pH 3， where the protonated adsorbent surface exerted strong electrostatic attraction towards anionic OBS molecules. Notably， adsorption efficiency remained stable across a range of ionic strengths （Cl– mass concentration 0-100 mg/L）， indicating strong resistance to interference from common salts， a vital advantage for practical application. Adsorption equilibrium data fitted the Langmuir isotherm model （R2 of 0.999 9 for U-TFA-10 M and 0.999 5 for UN-TFA-10 M）， suggesting monolayer adsorption on homogeneous active sites. The maximum adsorption capacities were 684.9 mg/g for U-TFA-10 M and 602.4 mg/g for UN-TFA-10 M. Kinetic analysis followed the pseudo-second-order model （R2 of 0.999 9 for U-TFA-10 M and 0.998 8 for UN-TFA-10 M）， implying chemisorption as the rate-limiting step. The materials also exhibited excellent regenerability and reusability， maintaining high efficiency after repeated adsorption-desorption cycles. Mechanistic studies revealed that the superior performance stems from a synergistic combination of multiple interactions： （1） pore-size matching for physical entrapment； （2） electrostatic attraction between the protonated surface and the OBS sulfonate group； （3） acid-base interaction between unsaturated metal sites （Lewis acids） and the sulfonate group； （4） specific fluorine-fluorine （F-F） interaction between the -CF3 groups and the OBS perfluorinated chain， enhancing selectivity； and （5） hydrophobic interaction promoting partitioning from the aqueous phase. Compared with other reported OBS adsorbents， U-TFA-10 M and UN-TFA-10 M combined ultrahigh capacity and fast kinetics， with a simple and scalable synthesis route， showing great practical potential. In summary， this work successfully developed U-TFA-10 M and UN-TFA-10 M as efficient， stable， and easily prepared adsorbents for OBS removal. It also validated defect engineering coupled with -CF3 functionalization as a powerful material design strategy. The mechanistic insights provide a valuable theoretical foundation for developing next-generation materials for the separation and remediation of persistent aquatic pollutants.

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Fluorine-functionalized zirconium-based metal-organic framework immobilized thin film microextraction array for high-throughput analysis of glyphosate residues LI Sainan, YIN Xiaoju, LIU Jiawei, YANG Yang, BAI Quan 2026, 44 (10):  1233-1242.  DOI: 10.3724/SP.J.1123.2026.01034 Abstract ( 109 )   HTML ( 3 )   PDF (1360KB) ( 13 )   Supporting Information The development of high-throughput sample pretreatment methods is essential for the rapid screening and accurate analysis of contaminants in food and environmental matrices. In this study， we established a novel high-throughput sample pretreatment approach for glyphosate using a 96-blade thin-film microextraction （TFME） device. The blade surface was coated with a functionalized metal-organic framework （MOF） as the extractive phase. Specifically， a fluorinated zirconium-based MOF （UiO-66-F4） was synthesized via a hydrothermal method. Various characterization techniques， including scanning electron microscopy （SEM）， transmission electron microscopy （TEM）， Fourier-transform infrared spectroscopy （FT-IR）， X-ray diffraction （XRD）， and nitrogen adsorption-desorption isotherms， were employed to confirm the successful synthesis of UiO-66-F4 crystals. The results demonstrated that the synthesized crystals possessed a high specific surface area （559.5 m2/g） and an irregularly stacked porous structure. The prepared UiO-66-F4 was subsequently homogenized with a polyacrylonitrile （PAN） solution to form a slurry. This slurry was solidified onto 96 stainless-steel blades using an improved laboratory-developed spraying technique. As a result， an array of 96 UiO-66-F4/PAN extraction coatings was obtained. Each coating in the array was fabricated with uniform dimensions of 2 cm in length， 0.2 cm in width， and approximately 100 μm in thickness. The relative standard deviations （RSDs， n=8） for the length， width， and thickness of the coatings measured were 0.29%， 0.48%， and 4.64%， respectively. The UiO-66-F4 adsorbent offers multiple interaction forces with glyphosate， including metal coordination， hydrogen bonding， and electrostatic interactions. Therefore， the adsorption of glyphosate onto UiO-66-F4 occurred rapidly， reaching equilibrium within 5 min. The pseudo-second-order kinetic model provides a superior fit for the adsorption kinetics behavior of glyphosate on the surface of UiO-66-F4， suggesting that the adsorption process is predominantly controlled by chemisorption. Furthermore， the glyphosate adsorption isotherms indicate that its adsorption behavior closely conforms to the Langmuir isotherm model （R2>0.97）. This finding suggests that glyphosate is adsorbed as a monolayer on the adsorbent surface， giving rise to a maximum adsorption capacity of 239.4 mg/g. The developed TFME method efficiently enriches glyphosate from aqueous solutions at pH 5–7 within 30 min and allows for analyte desorption using an aqueous solution containing 5% （V/V） triethylamine. The UiO-66-F4/PAN coatings displayed high repeatability and reproducibility， as evidenced by the RSD values below 2.3% （n=5）. In addition， the coatings exhibited remarkable robustness， maintaining a recovery of 98.2% after nine consecutive TFME processing cycles. Furthermore， coupling this TFME method with ultra performance liquid chromatography-tandem mass spectrometry （UPLC-MS/MS） enabled high-throughput analysis of glyphosate. The method demonstrated excellent linearity over a range of 0.5–500 ng/mL （R2=0.999 9）. The limits of detection （LOD） and quantification （LOQ） were 0.12 ng/mL and 0.5 ng/mL， respectively. Intra-day （n=3） and inter-day （n=5） precisions， expressed as RSDs， were 3.6% and 1.6%， respectively. The method was successfully applied to real-world environmental water and fruit samples， detecting glyphosate residues of （1.7±0.7） ng/g in orange peel and （1.2±0.5） ng/mL in irrigation river water. Spiked recoveries in real samples ranged from 88.1% to 107.1%， with precisions （RSDs， n=3） below 8.1%. This method is accurate， reliable， and reproducible， enabling parallel processing of 96 samples， which are well-suited for rapid screening and precise quantification of glyphosate contamination in large-scale sample analyses.

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Irreversible azo covalent organic framework for adsorption of 2，5-dichloro-1，4-benzoquinone from water RAN Xuqin, YANG Xu, LONG Chaoyi, QIAN Hailong, YAN Xiuping 2026, 44 (10):  1243-1250.  DOI: 10.3724/SP.J.1123.2026.01012 Abstract ( 84 )   HTML ( 3 )   PDF (1353KB) ( 16 )   The disinfection of water is a fundamental and indispensable process in modern public health infrastructure. It plays a pivotal role in safeguarding drinking water safety by inactivating pathogenic microorganisms such as bacteria and viruses， thereby preventing waterborne disease outbreaks. However， a significant and well-documented drawback of chemical disinfection， particularly with chlorine-based agents， is the formation of disinfection byproducts （DBPs）. These DBPs are generated through complex reactions between disinfectants and natural organic matter present in source water. Among the vast array of identified DBPs， halogenated compounds are of particular concern due to their enhanced toxicity and persistence. 2，5-Dichloro-1，4-benzoquinone （2，5-DCBQ） is a prominent representative of these toxic halogenated DBPs. Toxicological studies have conclusively demonstrated that 2，5-DCBQ can induce pronounced oxidative stress in mammalian cells. This leads to a cascade of detrimental effects including a marked increase in intracellular reactive oxygen species. Subsequently， the detrimental effects may cause DNA single-strand breaks， oxidative base damage， and chromosomal aberrations. Consequently， developing effective technologies for the targeted removal of 2，5-DCBQ from aqueous environments is of paramount importance for mitigating its associated health risks. Current removal strategies， including adsorption using solid-phase materials， often suffer from several limitations. These include reliance on a single interaction mechanism， modest adsorption capacities， or slow kinetics. This hinders their practical application for efficient 2，5-DCBQ control. To address these challenges， this study presents the design， synthesis， and application of a novel porous organic adsorbent. Termed Tp-Azo， this adsorbent is specifically engineered for the rapid and efficient removal of 2，5-DCBQ. Tp-Azo was synthesized via a condensation reaction and possesses an exceptionally high specific surface area of 824.5 m2/g. It incorporates a high density of electron-rich azo （-N=N-） functional groups within its framework. These groups act as strong electron donors， enabling potent electron donor-acceptor interactions with the electron-deficient quinone ring of 2，5-DCBQ. Furthermore， the predominantly aromatic backbone of Tp-Azo facilitates strong π-π stacking interactions with the aromatic structure of 2，5-DCBQ. The inherent hydrophobicity of Tp-Azo promotes additional adsorption via hydrophobic effects. Critically， the material possesses an average pore diameter of approximately 2.0 nm. It is substantially larger than the estimated molecular kinetic diameter of 2，5-DCBQ. This suitable pore size ensures minimal diffusion resistance， allowing 2，5-DCBQ to rapidly access the internal adsorption sites.The adsorption performance of Tp-Azo was systematically evaluated under various conditions. Under pH 2-3， the adsorption efficiency was reduced. This is attributed to the protonation of 2，5-DCBQ， which diminishes its hydrophobicity. The shielding effect of high H⁺ concentration can also weaken electrostatic interactions. In contrast， within pH 4-6， Tp-Azo exhibited consistently high removal rates. Therefore， pH 5 was selected as the optimal condition for subsequent experiments to simulate typical water treatment scenarios. The adsorption kinetics were remarkably fast within the first 3 min and complete equilibrium was reached within 20 min. The kinetics were best described by the pseudo-second-order model， indicating that the adsorption process is primarily governed by chemisorption. Isotherm studies revealed that the adsorption capacity increased with the initial 2，5-DCBQ concentration. They were accurately modeled by the Langmuir isotherm， suggesting a homogeneous adsorption surface and monolayer coverage. The calculated maximum adsorption capacity was significantly higher than that reported for many conventional adsorbents.Swimming pool water and tap water were spiked with 2，5-DCBQ at 5 mg/L and 50 mg/L. Impressively， Tp-Azo achieved removal efficiencies of 96.2% and 96.6% at 5 mg/L， 87.9% and 88.7% at 50 mg/L， respectively. Given that realistic environmental concentrations of halogenated DBPs like 2，5-DCBQ are typically in the μg/L range， this suggests that Tp-Azo is highly capable of achieving virtually complete removal in real-world applications. The study provides a novel and highly effective material enabling targeted removal of halogenated DBPs. It also offers a strategic design principle for developing advanced adsorbents for DBPs in water treatment.

Teaching Research

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A comprehensive undergraduate experiment： development of a dispersive solid-phase extraction method based on halogen-bonded organic frameworks and its application to the analysis of brominated flame retardants WANG Dandan, HU Jiaqi, QIN Cui, WANG Mingyue, KE Famin, NIU Hong, YANG Xilin, GAO Die 2026, 44 (10):  1251-1261.  DOI: 10.3724/SP.J.1123.2026.04016 Abstract ( 92 )   HTML ( 5 )   PDF (2342KB) ( 23 )   To address the evolving demands for innovation and practical competencies in pharmaceutical education， and in alignment with the “student-centered， outcome-driven” pedagogical approach， our teaching team has undertaken a comprehensive reform of the Pharmaceutical Analysis curriculum. We designed and implemented an integrative， research-based laboratory experiment for undergraduate students. Centered on the design and application of functional materials， the experiment guides students through the independent synthesis of a halogen-bonded organic framework， designated as XOF-1， followed by systematic structural characterization， performance evaluation， and analytical application. The experiment is grounded in real-world environmental analysis challenges， requiring students to employ the synthesized material as a dispersive solid-phase extraction （DSPE） adsorbent for the selective enrichment of typical brominated flame retardants， including tetrabromobisphenol A （TBBPA）， tetrachlorobisphenol A （TCBPA）， and hexabromobenzene （HBB）， and to achieve the removal of TBBPA from actual water samples. The instructional process fully encompasses the workflow from material preparation and structural characterization to method development and performance assessment， enabling students to experience a complete research pathway from material design to practical application. This approach immerses them in the scientific inquiry cycle of theory-design-experiment-analysis. Through this experiment， students gain solid proficiency in synthesizing and characterizing functional materials and applying them to sample pretreatment. By engaging in experimental design， condition optimization， and data interpretation， they develop critical thinking， problem-solving skills， and capacity for independent inquiry. The exercise fosters deep integration of theoretical knowledge and practical skills， stimulates research interest， strengthens innovative and applied mindsets， and cultivates a sense of professional responsibility in environmental and public health. Ultimately， it achieves a cohesive blend of knowledge acquisition， competency development， and value cultivation， fulfilling the overarching goal of holistic education through experimental learning.