Pub Date : 2026-05-10Epub Date: 2026-02-27DOI: 10.1016/j.chroma.2026.466847
Haile Kassahun , Ann Van Schepdael , Erwin Adams
Reversed-phase liquid chromatography (RP-LC) is widely used in pharmaceutical analysis, often relying on traditional organic solvents which present significant environmental and health risks. As a result, the growing demand for sustainable analytical practices has led to the development of eco-friendly solvents for RP-LC. This review discusses recent developments in the application of greener alternative solvents, such as ethanol, glycerol, dimethyl carbonate, cyrene, acetone, propylene carbonate, ionic liquids, propylene glycol, deep eutectic solvents, and surfactants, in pharmaceutical analysis using RP-LC. The review also highlights the potential of these greener solvents to replace conventional ones in the analysis of pharmaceuticals. Overall, green solvents can achieve analytical performance comparable to traditional methods while significantly reducing environmental burden and health risks. The limitations and practical strategies to overcome the challenges are also discussed.
{"title":"Recent advances in greener alternative solvents for reversed-phase liquid chromatography in pharmaceutical analysis","authors":"Haile Kassahun , Ann Van Schepdael , Erwin Adams","doi":"10.1016/j.chroma.2026.466847","DOIUrl":"10.1016/j.chroma.2026.466847","url":null,"abstract":"<div><div>Reversed-phase liquid chromatography (RP-LC) is widely used in pharmaceutical analysis, often relying on traditional organic solvents which present significant environmental and health risks. As a result, the growing demand for sustainable analytical practices has led to the development of eco-friendly solvents for RP-LC. This review discusses recent developments in the application of greener alternative solvents, such as ethanol, glycerol, dimethyl carbonate, cyrene, acetone, propylene carbonate, ionic liquids, propylene glycol, deep eutectic solvents, and surfactants, in pharmaceutical analysis using RP-LC. The review also highlights the potential of these greener solvents to replace conventional ones in the analysis of pharmaceuticals. Overall, green solvents can achieve analytical performance comparable to traditional methods while significantly reducing environmental burden and health risks. The limitations and practical strategies to overcome the challenges are also discussed.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1774 ","pages":"Article 466847"},"PeriodicalIF":4.0,"publicationDate":"2026-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147387930","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-05-10Epub Date: 2026-02-23DOI: 10.1016/j.chroma.2026.466839
Sina Mohammad Mehri , Mohammad Reza Afshar Mogaddam , Mir Ali Farajzadeh , Mahboob Nemati
For the first time, a new magnetic core-shell adsorbent (synthesized from Fe₃O₄, mercaptoacetic acid, and hexamethylene diamine) was introduced for the effective extraction of pesticide residues from agricultural products, including cucumber, tomato, and zucchini. The structural and magnetic characteristics of the synthesized adsorbent were fully confirmed through a series of instrumental techniques such as Fourier transform infrared spectrometry, scanning electron microscopy, Brunauer-Emmett-Teller, thermogravimetric analysis, X-ray diffraction, transmission electron microscopy, energy dispersive X-ray, vibrating sample magnetometer, and zeta-potential analysis. The combination of dispersive micro solid phase extraction with dispersive liquid–liquid microextraction enabled a highly efficient two-step sample preparation protocol with minimal solvent consumption and rapid operation. Due to the magnetic nature of the adsorbent, phase separation was rapidly achieved using an external magnet, eliminating the need for repeated centrifugation and significantly reducing extraction time. The optimized procedure utilized only 3 mg of the sorbent and μL volumes of environmentally benign organic solvents, making the method green and cost-effective. Under the optimized conditions, the method achieved excellent analytical performance, including low detection limits (0.31–2.65 µg L⁻¹), wide linear ranges, good repeatability (relative standard deviations of 1.1–6.3%), high enrichment factors (225–480), and acceptable extraction recoveries (45–96%). The method was successfully applied to real agricultural matrices, and relative recoveries within the 80–120% range confirmed the absence of significant matrix effects. Altogether, this study highlighted a powerful and innovative analytical platform that offered high sensitivity, selectivity, and operational simplicity for the determination of pesticide residues in complex food samples.
{"title":"Development of a magnetic core–shell adsorbent-based microextraction method for the determination of pesticide residues in edible vegetables","authors":"Sina Mohammad Mehri , Mohammad Reza Afshar Mogaddam , Mir Ali Farajzadeh , Mahboob Nemati","doi":"10.1016/j.chroma.2026.466839","DOIUrl":"10.1016/j.chroma.2026.466839","url":null,"abstract":"<div><div>For the first time, a new magnetic core-shell adsorbent (synthesized from Fe₃O₄, mercaptoacetic acid, and hexamethylene diamine) was introduced for the effective extraction of pesticide residues from agricultural products, including cucumber, tomato, and zucchini. The structural and magnetic characteristics of the synthesized adsorbent were fully confirmed through a series of instrumental techniques such as Fourier transform infrared spectrometry, scanning electron microscopy, Brunauer-Emmett-Teller, thermogravimetric analysis, X-ray diffraction, transmission electron microscopy, energy dispersive X-ray, vibrating sample magnetometer, and zeta-potential analysis. The combination of dispersive micro solid phase extraction with dispersive liquid–liquid microextraction enabled a highly efficient two-step sample preparation protocol with minimal solvent consumption and rapid operation. Due to the magnetic nature of the adsorbent, phase separation was rapidly achieved using an external magnet, eliminating the need for repeated centrifugation and significantly reducing extraction time. The optimized procedure utilized only 3 mg of the sorbent and μL volumes of environmentally benign organic solvents, making the method green and cost-effective. Under the optimized conditions, the method achieved excellent analytical performance, including low detection limits (0.31–2.65 µg L⁻¹), wide linear ranges, good repeatability (relative standard deviations of 1.1–6.3%), high enrichment factors (225–480), and acceptable extraction recoveries (45–96%). The method was successfully applied to real agricultural matrices, and relative recoveries within the 80–120% range confirmed the absence of significant matrix effects. Altogether, this study highlighted a powerful and innovative analytical platform that offered high sensitivity, selectivity, and operational simplicity for the determination of pesticide residues in complex food samples.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1774 ","pages":"Article 466839"},"PeriodicalIF":4.0,"publicationDate":"2026-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147353255","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-05-10Epub Date: 2026-03-07DOI: 10.1016/j.chroma.2026.466887
Daniel Foshag , Stephan Buckenmaier , Patrik Petersson
Strong sample solvents and lipidic excipients hamper reversed‑phase (RP) liquid chromatography (LC) analysis of lipid‑based pharmaceutical formulations by causing solvent mismatch, resulting in peak distortion and restricting the applicable injection volume, which ultimately reduces the sensitivity to detect impurities. In this work, we evaluated feed injection (FI) under gradient conditions for the analysis of sesame oil-based formulations dissolved in ethyl acetate (EtOAc) and integrated FI with two‑dimensional LC coupled to mass spectrometry (2D‑LC/MS) for impurity profiling. Findings were compared to conventional flow‑through injection (FTI) and sandwich injection, across injection volumes of 1–40 µL. FI at low feed flow fractions (≤ 5 % of mobile phase flow rate) provided ≥ 1:20 online dilution, sustaining column head focusing, and preserving peak shape and linearity across the full injection range. In contrast, higher feed flow fractions (≥ 20 % of the mobile phase flow rate, ≤ 1:5 dilution) resulted in severe fronting peaks and non-linear ultraviolet (UV) detector response. Finally, the 2D transfers resolved matrix‑ and Active Pharmaceutical Ingredient (API)‑related impurities without laborious offline reconstitution or dilution. This work extends the application field of FI from analyte diluents to complex lipid matrices, offering a robust, scalable workflow for pharmaceutical formulation analysis.
{"title":"Feed injection–enabled reversed phase liquid chromatography for simplified analysis of lipophilic drugs and formulations","authors":"Daniel Foshag , Stephan Buckenmaier , Patrik Petersson","doi":"10.1016/j.chroma.2026.466887","DOIUrl":"10.1016/j.chroma.2026.466887","url":null,"abstract":"<div><div>Strong sample solvents and lipidic excipients hamper reversed‑phase (RP) liquid chromatography (LC) analysis of lipid‑based pharmaceutical formulations by causing solvent mismatch, resulting in peak distortion and restricting the applicable injection volume, which ultimately reduces the sensitivity to detect impurities. In this work, we evaluated feed injection (FI) under gradient conditions for the analysis of sesame oil-based formulations dissolved in ethyl acetate (EtOAc) and integrated FI with two‑dimensional LC coupled to mass spectrometry (2D‑LC/MS) for impurity profiling. Findings were compared to conventional flow‑through injection (FTI) and sandwich injection, across injection volumes of 1–40 µL. FI at low feed flow fractions (≤ 5 % of mobile phase flow rate) provided ≥ 1:20 online dilution, sustaining column head focusing, and preserving peak shape and linearity across the full injection range. In contrast, higher feed flow fractions (≥ 20 % of the mobile phase flow rate, ≤ 1:5 dilution) resulted in severe fronting peaks and non-linear ultraviolet (UV) detector response. Finally, the <sup>2</sup>D transfers resolved matrix‑ and Active Pharmaceutical Ingredient (API)‑related impurities without laborious offline reconstitution or dilution. This work extends the application field of FI from analyte diluents to complex lipid matrices, offering a robust, scalable workflow for pharmaceutical formulation analysis.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1774 ","pages":"Article 466887"},"PeriodicalIF":4.0,"publicationDate":"2026-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147387950","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Understanding bio-nano interactions and protein corona formation is critical for advancing nanomedicines towards clinical translation. However, conventional methods for nanoparticle analysis have limited utility for in situ analysis due to interference from unbound proteins present in bulk biological media. Electrical asymmetric flow field-flow fractionation (EAF4), which integrates AF4 with an applied electrical field, enables size and surface charge-based separation, and when coupled with online detectors, provides simultaneous measurement of particle size, electrophoretic mobility, and zeta potential, key parameters governing bio-nano interactions. Here, we report the first application of multiplexed EAF4 with online detection for evaluating biophysical changes occurring in polystyrene latex and silk nanoparticles, used as model nanomedicine systems, following exposure to serum under conditions that mimic the protein composition of cell culture media. Our findings reveal significant alterations in particle physical attributes, including particle size, shape factor, zeta potential, and electrophoretic mobility following exposure to protein-containing media. Furthermore, we demonstrate that EAF4 enables gentle fractionation of complex biological samples, providing comprehensive physicochemical profiling of diverse particulate and macromolecular species within nanoparticle–protein complexes. This work establishes EAF4 as a powerful analytical platform for resolving nano–bio interactions and guiding the rational design of next-generation nanomedicines.
{"title":"Analysis of bio-nano interactions by electrical asymmetric flow field-flow fractionation with multiple online detectors","authors":"Panida Punnabhum , Karim Daramy , Napaporn Roamcharern , Caterina Minelli , Yiwen Pei , Nelli Chourmouziadi Laleni , Yvonne Perrie , Zahra Rattray","doi":"10.1016/j.chroma.2026.466879","DOIUrl":"10.1016/j.chroma.2026.466879","url":null,"abstract":"<div><div>Understanding bio-nano interactions and protein corona formation is critical for advancing nanomedicines towards clinical translation. However, conventional methods for nanoparticle analysis have limited utility for <em>in situ</em> analysis due to interference from unbound proteins present in bulk biological media. Electrical asymmetric flow field-flow fractionation (EAF4), which integrates AF4 with an applied electrical field, enables size and surface charge-based separation, and when coupled with online detectors, provides simultaneous measurement of particle size, electrophoretic mobility, and zeta potential, key parameters governing bio-nano interactions. Here, we report the first application of multiplexed EAF4 with online detection for evaluating biophysical changes occurring in polystyrene latex and silk nanoparticles, used as model nanomedicine systems, following exposure to serum under conditions that mimic the protein composition of cell culture media. Our findings reveal significant alterations in particle physical attributes, including particle size, shape factor, zeta potential, and electrophoretic mobility following exposure to protein-containing media. Furthermore, we demonstrate that EAF4 enables gentle fractionation of complex biological samples, providing comprehensive physicochemical profiling of diverse particulate and macromolecular species within nanoparticle–protein complexes. This work establishes EAF4 as a powerful analytical platform for resolving nano–bio interactions and guiding the rational design of next-generation nanomedicines.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1774 ","pages":"Article 466879"},"PeriodicalIF":4.0,"publicationDate":"2026-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147387953","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-05-10Epub Date: 2026-02-28DOI: 10.1016/j.chroma.2026.466852
Listya Eka Anggraini , Muhammad Naeem Younis , Mohammed A. Abdalmwla , Ghadeer Ghannam Alharbi , Khaoula El Yanboui , Abdulaziz A. Al-Saadi , Chanbasha Basheer
The emergence of advanced, innovative microfluidic devices has reshaped analytical separation methodologies and biomolecular diagnostics by introducing highly integrated, miniaturized systems that enable next-generation fluid manipulation, enhanced automation, precision, cost efficiency, and high-throughput capabilities. Advances in fabrication methods, such as soft lithography, photolithography, and 3D printing, have enabled the production of customizable microfluidic platforms from materials such as PDMS, glass, and thermoplastics. These microfluidic systems support a range of analytical functionalities of the technologies, including gas chromatography (GC), high-performance liquid chromatography (HPLC), and electrophoresis, delivering rapid, high-resolution analyses with minimal sample and reagent requirements, quicker analysis, and enhanced uniformity and stability, facilitating high productivity screening, improved sensitivity and portability. Integration of micro-GC systems enables rapid, portable detection of volatile compounds, while microfluidic HPLC and electrophoresis provide precise biomolecular separations and real-time diagnostics. Recent advancements in artificial intelligence (AI) have now brought significant innovations in microfluidic devices, resulting in a new era of intelligent analytical separations, where machine learning algorithms and neural networks are applicable not only for data processing and pattern recognition but also for real-time optimization, anomaly detection, innovative read-out systems, and autonomous system control. The fusion of AI and microfluidics has enabled new approaches to dynamic experimentation, reshaping traditional microfluidics and personalized diagnostics and health care systems, where rapid, reliable analysis is paramount. In this review article, we comprehensively explain the progressive convergence of microfluidics and AI across various electrophoretic and chromatographic analytical separation techniques, elaborating on the latest technological innovations, fundamental fabrication strategies, and emergent applications. The article also presents a forward-looking perspective on how AI-enabled microfluidics enhances automation, scalability, and application-specific customization, which could shape the future of intelligent analytical separation systems.
{"title":"Microfluidics in separation science: Fabrication, applications and intelligent systems","authors":"Listya Eka Anggraini , Muhammad Naeem Younis , Mohammed A. Abdalmwla , Ghadeer Ghannam Alharbi , Khaoula El Yanboui , Abdulaziz A. Al-Saadi , Chanbasha Basheer","doi":"10.1016/j.chroma.2026.466852","DOIUrl":"10.1016/j.chroma.2026.466852","url":null,"abstract":"<div><div>The emergence of advanced, innovative microfluidic devices has reshaped analytical separation methodologies and biomolecular diagnostics by introducing highly integrated, miniaturized systems that enable next-generation fluid manipulation, enhanced automation, precision, cost efficiency, and high-throughput capabilities. Advances in fabrication methods, such as soft lithography, photolithography, and 3D printing, have enabled the production of customizable microfluidic platforms from materials such as PDMS, glass, and thermoplastics. These microfluidic systems support a range of analytical functionalities of the technologies, including gas chromatography (GC), high-performance liquid chromatography (HPLC), and electrophoresis, delivering rapid, high-resolution analyses with minimal sample and reagent requirements, quicker analysis, and enhanced uniformity and stability, facilitating high productivity screening, improved sensitivity and portability. Integration of micro-GC systems enables rapid, portable detection of volatile compounds, while microfluidic HPLC and electrophoresis provide precise biomolecular separations and real-time diagnostics. Recent advancements in artificial intelligence (AI) have now brought significant innovations in microfluidic devices, resulting in a new era of intelligent analytical separations, where machine learning algorithms and neural networks are applicable not only for data processing and pattern recognition but also for real-time optimization, anomaly detection, innovative read-out systems, and autonomous system control. The fusion of AI and microfluidics has enabled new approaches to dynamic experimentation, reshaping traditional microfluidics and personalized diagnostics and health care systems, where rapid, reliable analysis is paramount. In this review article, we comprehensively explain the progressive convergence of microfluidics and AI across various electrophoretic and chromatographic analytical separation techniques, elaborating on the latest technological innovations, fundamental fabrication strategies, and emergent applications. The article also presents a forward-looking perspective on how AI-enabled microfluidics enhances automation, scalability, and application-specific customization, which could shape the future of intelligent analytical separation systems.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1774 ","pages":"Article 466852"},"PeriodicalIF":4.0,"publicationDate":"2026-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147353232","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-04-26Epub Date: 2026-02-08DOI: 10.1016/j.chroma.2026.466784
Xiao Wang , Hongle Wan , Xinhua Li , Ruya Wang , Boyu Hao , Wenchong Tang , Mengyuan Zhang , Wenbin Liu , Mingyuan Gao , Weidong Zhang
A core–shell magnetic surface molecularly imprinted polymer (MIP) was synthesized using chitosan-modified Fe3O4 nanoparticles (Fe3O4@CS) as the support and Schisandrol A as the template for selective recognition. After optimization of adsorption conditions, static and dynamic binding experiments demonstrated high selectivity toward Schisandrol A, with an imprinting factor of 4.556. Based on this material, a magnetic solid-phase extraction coupled with high-performance liquid chromatography (MSPE–HPLC) method was established for the enrichment and quantitative determination of Schisandrol A in Schisandra chinensis, achieving a limit of detection of 0.59 ng/mL and a limit of quantification of 2.47 ng/mL. The practical applicability of the MIP was further evaluated by selectively depleting Schisandrol A from the herbal extract, followed by assessment of hepatoprotective activity using an ethanol-induced fatty liver zebrafish larva model. Comparative analysis of hepatic lipid accumulation and biochemical markers (AST, ALT, and SOD) revealed that removal of Schisandrol A significantly reduced the hepatoprotective efficacy of the extract, confirming its functional contribution. These results demonstrate that the proposed MIP-based MSPE–HPLC strategy provides a robust analytical tool for selective lignan analysis and enables component-specific functional evaluation in complex herbal systems.
{"title":"Core-shell magnetic molecularly imprinted microspheres for selective extraction and determination of Schisandrol A with hepatoprotective evaluation in zebrafish larvae","authors":"Xiao Wang , Hongle Wan , Xinhua Li , Ruya Wang , Boyu Hao , Wenchong Tang , Mengyuan Zhang , Wenbin Liu , Mingyuan Gao , Weidong Zhang","doi":"10.1016/j.chroma.2026.466784","DOIUrl":"10.1016/j.chroma.2026.466784","url":null,"abstract":"<div><div>A core–shell magnetic surface molecularly imprinted polymer (MIP) was synthesized using chitosan-modified Fe<sub>3</sub>O<sub>4</sub> nanoparticles (Fe<sub>3</sub>O<sub>4</sub>@CS) as the support and Schisandrol A as the template for selective recognition. After optimization of adsorption conditions, static and dynamic binding experiments demonstrated high selectivity toward Schisandrol A, with an imprinting factor of 4.556. Based on this material, a magnetic solid-phase extraction coupled with high-performance liquid chromatography (MSPE–HPLC) method was established for the enrichment and quantitative determination of Schisandrol A in <em>Schisandra chinensis</em>, achieving a limit of detection of 0.59 ng/mL and a limit of quantification of 2.47 ng/mL. The practical applicability of the MIP was further evaluated by selectively depleting Schisandrol A from the herbal extract, followed by assessment of hepatoprotective activity using an ethanol-induced fatty liver zebrafish larva model. Comparative analysis of hepatic lipid accumulation and biochemical markers (AST, ALT, and SOD) revealed that removal of Schisandrol A significantly reduced the hepatoprotective efficacy of the extract, confirming its functional contribution. These results demonstrate that the proposed MIP-based MSPE–HPLC strategy provides a robust analytical tool for selective lignan analysis and enables component-specific functional evaluation in complex herbal systems.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1773 ","pages":"Article 466784"},"PeriodicalIF":4.0,"publicationDate":"2026-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146172724","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-04-26Epub Date: 2026-02-07DOI: 10.1016/j.chroma.2026.466782
Wentao Xu , Huizhen Ni , Linna Xu , Jiajun Gong , Dongping Cheng , Huawei Lv , Xianchao Hu , Chu Chu , Xingnuo Li , Shengqiang Tong
Chiral covalent organic frameworks (CCOFs) have attracted considerable attention as promising materials for enantioseparation. In this work, a series of β-cyclodextrin-bridged chiral COFs with precisely tunable chiral-site densities were synthesized via a bottom-up strategy using the 1,3,5-tris(4-aminophenyl)benzene (TPB) linkers and newly designed BPTA-CD monomers. The BPTA-CD unit was synthesized by grafting mercapto-β-cyclodextrin (SH-β-CD) onto 2,5-bis(prop‑2-yn-1-yloxy) terephthalaldehyde (BPTA) via a thiol–alkyne “click” reaction. By adjusting the BPTA-CD/BPTA ratio, the density of chiral recognition sites within the COF framework could be finely regulated. The resulting CCOFs were covalently grafted onto silica microspheres to yield COF-grafted silica stationary phases for HPLC enantioseparation. Under optimized conditions, these stationary phases successfully separated 14 out of 19 dansylated amino acids (DNS-AAs) and exhibited high thermal stability and good reproducibility. Increasing the chiral-site density led to markedly enhanced enantioresolution, demonstrating the pivotal role of tunable chiral environments in recognition performance. This work provides an effective strategy for constructing chiral-site-controllable COFs for high-performance liquid chromatographic enantioseparation.
手性共价有机框架（CCOFs）作为一种很有前途的对映体分离材料受到了广泛的关注。在这项工作中，利用1,3,5-三（4-氨基苯基）苯（TPB）连接剂和新设计的BPTA-CD单体，通过自下而上的策略合成了一系列具有精确可调手性位点密度的β-环糊精桥接手性COFs。以巯基-炔“咔嗒”反应将巯基-β-环糊精（SH-β-CD）接枝到2,5-双（prop - 2-yn-1-yloxy）对苯二甲酸（BPTA）上，合成了BPTA- cd单元。通过调整BPTA- cd /BPTA的比例，可以很好地调节COF框架内手性识别位点的密度。将得到的CCOFs共价接枝到二氧化硅微球上，得到了用于HPLC对映体分离的CCOFs接枝二氧化硅固定相。在优化的条件下，这些固定相成功地分离了19种丹基化氨基酸（DNS-AAs）中的14种，具有较高的热稳定性和良好的重现性。增加手性位点密度导致对映体分辨率显著提高，表明可调手性环境在识别性能中的关键作用。本研究为高效液相色谱对映体分离构建手性位点可控COFs提供了有效的策略。
{"title":"Bottom-up synthesis of bridged Bis(β-cyclodextrin)-functionalized chiral COFs@SiO2 for enantioseparation in liquid chromatography","authors":"Wentao Xu , Huizhen Ni , Linna Xu , Jiajun Gong , Dongping Cheng , Huawei Lv , Xianchao Hu , Chu Chu , Xingnuo Li , Shengqiang Tong","doi":"10.1016/j.chroma.2026.466782","DOIUrl":"10.1016/j.chroma.2026.466782","url":null,"abstract":"<div><div>Chiral covalent organic frameworks (CCOFs) have attracted considerable attention as promising materials for enantioseparation. In this work, a series of <em>β</em>-cyclodextrin-bridged chiral COFs with precisely tunable chiral-site densities were synthesized via a bottom-up strategy using the 1,3,5-tris(4-aminophenyl)benzene (TPB) linkers and newly designed BPTA-CD monomers. The BPTA-CD unit was synthesized by grafting mercapto-<em>β</em>-cyclodextrin (SH-<em>β</em>-CD) onto 2,5-bis(prop‑2-yn-1-yloxy) terephthalaldehyde (BPTA) via a thiol–alkyne “click” reaction. By adjusting the BPTA-CD/BPTA ratio, the density of chiral recognition sites within the COF framework could be finely regulated. The resulting CCOFs were covalently grafted onto silica microspheres to yield COF-grafted silica stationary phases for HPLC enantioseparation. Under optimized conditions, these stationary phases successfully separated 14 out of 19 dansylated amino acids (DNS-AAs) and exhibited high thermal stability and good reproducibility. Increasing the chiral-site density led to markedly enhanced enantioresolution, demonstrating the pivotal role of tunable chiral environments in recognition performance. This work provides an effective strategy for constructing chiral-site-controllable COFs for high-performance liquid chromatographic enantioseparation.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1773 ","pages":"Article 466782"},"PeriodicalIF":4.0,"publicationDate":"2026-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146172726","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-04-26Epub Date: 2026-02-11DOI: 10.1016/j.chroma.2026.466798
Selen Al , Demet Dincel , Aykut Kul , Olcay Sagirli
Immunosuppressive drugs play a critical role in preventing organ rejection following transplantation and require close monitoring due to their narrow therapeutic ranges and interindividual pharmacokinetic variability. This review provides an overview of the pharmacokinetic properties, mechanisms of action, and clinical applications of drugs such as cyclosporine A, tacrolimus, sirolimus, everolimus, mycophenolate mofetil, and azathioprine. Within this clinical context, therapeutic drug monitoring (TDM) represents a cornerstone of individualized immunosuppressive therapy, directly linking drug exposure to efficacy and safety outcomes. Analytical approaches commonly used in the therapeutic monitoring of these agents—high-performance liquid chromatography (HPLC), liquid chromatography-tandem mass spectrometry (LC-MS/MS)—are described, with particular emphasis on LC-MS/MS as the primary analytical platform due to its superior selectivity, sensitivity, and multi-analyte capability. Recent advancements in sample preparation techniques are discussed in relation to their role in minimizing matrix effects and meeting the stringent analytical requirements of TDM. Tabulated data are presented on instrumentation, sample matrices, sample preparation techniques, calibration ranges, lower limits of quantification (LLOQ), analysis times, mobile phase compositions, and chromatographic columns for each analytical method. By critically integrating analytical methodology with clinical TDM needs, this review is intended to provide researchers and clinicians with a useful reference that supports the advancement of more effective and dependable strategies for therapeutic drug monitoring in clinical settings.
{"title":"Advances in LC–MS/MS methods and sample preparation strategies for therapeutic drug monitoring of immunosuppressive drugs","authors":"Selen Al , Demet Dincel , Aykut Kul , Olcay Sagirli","doi":"10.1016/j.chroma.2026.466798","DOIUrl":"10.1016/j.chroma.2026.466798","url":null,"abstract":"<div><div>Immunosuppressive drugs play a critical role in preventing organ rejection following transplantation and require close monitoring due to their narrow therapeutic ranges and interindividual pharmacokinetic variability. This review provides an overview of the pharmacokinetic properties, mechanisms of action, and clinical applications of drugs such as cyclosporine A, tacrolimus, sirolimus, everolimus, mycophenolate mofetil, and azathioprine. Within this clinical context, therapeutic drug monitoring (TDM) represents a cornerstone of individualized immunosuppressive therapy, directly linking drug exposure to efficacy and safety outcomes. Analytical approaches commonly used in the therapeutic monitoring of these agents—high-performance liquid chromatography (HPLC), liquid chromatography-tandem mass spectrometry (LC-MS/MS)—are described, with particular emphasis on LC-MS/MS as the primary analytical platform due to its superior selectivity, sensitivity, and multi-analyte capability. Recent advancements in sample preparation techniques are discussed in relation to their role in minimizing matrix effects and meeting the stringent analytical requirements of TDM. Tabulated data are presented on instrumentation, sample matrices, sample preparation techniques, calibration ranges, lower limits of quantification (LLOQ), analysis times, mobile phase compositions, and chromatographic columns for each analytical method. By critically integrating analytical methodology with clinical TDM needs, this review is intended to provide researchers and clinicians with a useful reference that supports the advancement of more effective and dependable strategies for therapeutic drug monitoring in clinical settings.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1773 ","pages":"Article 466798"},"PeriodicalIF":4.0,"publicationDate":"2026-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146172763","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Water resources are increasingly contaminated by industrial and agricultural pollutants, with pesticide residues posing a persistent challenge. Most existing methods were designed for a single purpose of either measuring or eliminating water pollutants, while integrated strategies containing both functions remain scarce. Here we reported a novel semi-automatic silicone rubber (SR) based multi-vial microextraction technique for the simultaneous determination and removal of fifteen pesticides from aqueous matrices. An integrated adsorption-desorption platform enabled effective in-situ extraction of the target pesticides via hydrophobic effects. Key parameters including ultrasonication extraction for 45 min and two sequential 5-min desorption with 5 mL of hexane/ethyl acetate (1:1, v/v) were employed. The quantitative analysis was validated in real waters of the Nanfei River, Chao Lake, and tap water with good recoveries (72.8–112.6 %) and relative standard deviations (0.1–7.5 %), superior limits of detection (0.0020–0.20 μg/L) and quantification (0.006 to 0.50 µg/L), and free matrix effects (87.5–102.1 %) by gas chromatography equipped with electron capture detector. Focusing on its selectivity and recyclability, the proposed approach was further applied to purifying green tea and chrysanthmum tea infusions, achieving over 90 % removal efficiency for most pesticides. These results demonstrated that the semi-automatic SR-based multi-vial microextraction is a robust and effective method for both quantifying and eliminating target pesticides from waters and tea infusions. The high throughput and low cost encourage its potential for customized commercial application in monitoring and remediating emerging pesticides in environment and food fields.
{"title":"Semi-automatic silicon rubber based multi-vial microextraction for determination and removal of pesticides from waters and tea","authors":"Huiru Xu, Yuqing Zong, Kehan Yin, Rimao Hua, Xiangwei Wu, Jiaying Xue","doi":"10.1016/j.chroma.2026.466796","DOIUrl":"10.1016/j.chroma.2026.466796","url":null,"abstract":"<div><div>Water resources are increasingly contaminated by industrial and agricultural pollutants, with pesticide residues posing a persistent challenge. Most existing methods were designed for a single purpose of either measuring or eliminating water pollutants, while integrated strategies containing both functions remain scarce. Here we reported a novel semi-automatic silicone rubber (SR) based multi-vial microextraction technique for the simultaneous determination and removal of fifteen pesticides from aqueous matrices. An integrated adsorption-desorption platform enabled effective in-situ extraction of the target pesticides via hydrophobic effects. Key parameters including ultrasonication extraction for 45 min and two sequential 5-min desorption with 5 mL of hexane/ethyl acetate (1:1, v/v) were employed. The quantitative analysis was validated in real waters of the Nanfei River, Chao Lake, and tap water with good recoveries (72.8–112.6 %) and relative standard deviations (0.1–7.5 %), superior limits of detection (0.0020–0.20 μg/L) and quantification (0.006 to 0.50 µg/L), and free matrix effects (87.5–102.1 %) by gas chromatography equipped with electron capture detector. Focusing on its selectivity and recyclability, the proposed approach was further applied to purifying green tea and chrysanthmum tea infusions, achieving over 90 % removal efficiency for most pesticides. These results demonstrated that the semi-automatic SR-based multi-vial microextraction is a robust and effective method for both quantifying and eliminating target pesticides from waters and tea infusions. The high throughput and low cost encourage its potential for customized commercial application in monitoring and remediating emerging pesticides in environment and food fields.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1773 ","pages":"Article 466796"},"PeriodicalIF":4.0,"publicationDate":"2026-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146161726","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-04-26Epub Date: 2026-02-10DOI: 10.1016/j.chroma.2026.466794
Shijie Xing , Zhikun Li , Jiaxiang Liu , Wei Zhang , Fuqiang Sun , Shu-Xuan Liang
To address the ongoing issue of quinolones (QNs) residues in aquatic products, accurate and sensitive detection of trace QNs has always been necessary and urgent. In this work, a composite material of NH2−MIL-125(Ti)@TpBD(SO3H)2 consisting of metal organic frameworks and based on bisulfonic acid-based covalent organic frameworks was synthesized and applied as a dispersive solid-phase extraction (dSPE) adsorbent. Combining with liquid chromatography-tandem mass spectrometry, a simple and effective method for simultaneous detection of 18 QNs in aquatic products was established. Meanwhile, the selective adsorption mechanism was thoroughly investigated through material characterization combined with density functional theory calculations. The results showed that the method had a good linear relationship (r ≥ 0.9981), low limits of detection of 0.0019–0.0641 μg kg⁻¹, along with high recovery rates in the range of 80.6–113.2 %, and good precision with relative standard deviations less than 8.8 %. The selective adsorption mechanism revealed the synergistic adsorption mechanism of electrostatic interactions, hydrogen bonding, and π-π interactions. The material had good reusability and excellent stability. In summary, the dSPE method based on NH2−MIL-125(Ti)@TpBD(SO3H)2 composites provided a practical sample pretreatment solution for the determination of trace QNs in complex matrixes.
{"title":"Fabrication of NH2-MIL-125(Ti)@TpBD(SO3H)2 selective adsorption material for dispersive solid-phase extraction of quinolone antibiotics in fish and shrimp combined with liquid chromatography-tandem mass spectrometric analysis","authors":"Shijie Xing , Zhikun Li , Jiaxiang Liu , Wei Zhang , Fuqiang Sun , Shu-Xuan Liang","doi":"10.1016/j.chroma.2026.466794","DOIUrl":"10.1016/j.chroma.2026.466794","url":null,"abstract":"<div><div>To address the ongoing issue of quinolones (QNs) residues in aquatic products, accurate and sensitive detection of trace QNs has always been necessary and urgent. In this work, a composite material of NH<sub>2</sub>−MIL-125(Ti)@TpBD(SO<sub>3</sub>H)<sub>2</sub> consisting of metal organic frameworks and based on bisulfonic acid-based covalent organic frameworks was synthesized and applied as a dispersive solid-phase extraction (dSPE) adsorbent. Combining with liquid chromatography-tandem mass spectrometry, a simple and effective method for simultaneous detection of 18 QNs in aquatic products was established. Meanwhile, the selective adsorption mechanism was thoroughly investigated through material characterization combined with density functional theory calculations. The results showed that the method had a good linear relationship (<em>r</em> ≥ 0.9981), low limits of detection of 0.0019–0.0641 μg kg⁻¹, along with high recovery rates in the range of 80.6–113.2 %, and good precision with relative standard deviations less than 8.8 %. The selective adsorption mechanism revealed the synergistic adsorption mechanism of electrostatic interactions, hydrogen bonding, and π-π interactions. The material had good reusability and excellent stability. In summary, the dSPE method based on NH<sub>2</sub>−MIL-125(Ti)@TpBD(SO<sub>3</sub>H)<sub>2</sub> composites provided a practical sample pretreatment solution for the determination of trace QNs in complex matrixes.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1773 ","pages":"Article 466794"},"PeriodicalIF":4.0,"publicationDate":"2026-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146172725","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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