Pub Date : 2025-12-31DOI: 10.1016/j.chroma.2025.466668
Deyun Li , Fangjie Shi , Huayi Chen , Jianjun Zhang , Yusong Dai , Yonglin Liu , Wenyan Li , Hui-juan Xu , Jinjin Wang , Yulong Zhang
Heavy metal contamination in water and soil can be remediated using biochar, however, the limited adsorption capacity and difficult separation of raw biochar restrict its practical application. To address these challenges, this study developed a recyclable magnesium-doped keratin-based biochar@hydrogel composite (MBC@HG) via a facile one-pot synthesis method. The composite features a three-dimensional network structure that ensures excellent mechanical strength and environmental stability. The specific surface area, Mg content, total basic metal content, and adsorption capacities for Cd2+ and Pb2+ all increased proportionally with the mass ratio of Mg-doped keratin-based biochar (MBC) within the MBC@HG composite. Adsorption kinetics for MHG (the best mass ratio of biochar/acrylamide) followed the pseudo-second-order kinetic model. Notably, the adsorption capacity achieved 80% of the equilibrium adsorption capacity within the first hour. The Cd2+ and Pb2+ maximum adsorption capacities of MHG in isotherm experiments were 141 mg g–1 and 291 mg g–1, respectively. The primary adsorption mechanisms were identified as surface complexation, ion exchange, and precipitation. This work presents a novel and sustainable strategy that simultaneously enables keratin waste valorization and production of an efficient, easily separable adsorbent for heavy metal removal.
{"title":"Mg-doped keratin-based biochar@hydrogel composite: An efficient cadmium and lead adsorbent","authors":"Deyun Li , Fangjie Shi , Huayi Chen , Jianjun Zhang , Yusong Dai , Yonglin Liu , Wenyan Li , Hui-juan Xu , Jinjin Wang , Yulong Zhang","doi":"10.1016/j.chroma.2025.466668","DOIUrl":"10.1016/j.chroma.2025.466668","url":null,"abstract":"<div><div>Heavy metal contamination in water and soil can be remediated using biochar, however, the limited adsorption capacity and difficult separation of raw biochar restrict its practical application. To address these challenges, this study developed a recyclable magnesium-doped keratin-based biochar@hydrogel composite (MBC@HG) via a facile one-pot synthesis method. The composite features a three-dimensional network structure that ensures excellent mechanical strength and environmental stability. The specific surface area, Mg content, total basic metal content, and adsorption capacities for Cd<sup>2+</sup> and Pb<sup>2+</sup> all increased proportionally with the mass ratio of Mg-doped keratin-based biochar (MBC) within the MBC@HG composite. Adsorption kinetics for MHG (the best mass ratio of biochar/acrylamide) followed the pseudo-second-order kinetic model. Notably, the adsorption capacity achieved 80% of the equilibrium adsorption capacity within the first hour. The Cd<sup>2+</sup> and Pb<sup>2+</sup> maximum adsorption capacities of MHG in isotherm experiments were 141 mg g<sup>–1</sup> and 291 mg g<sup>–1</sup>, respectively. The primary adsorption mechanisms were identified as surface complexation, ion exchange, and precipitation. This work presents a novel and sustainable strategy that simultaneously enables keratin waste valorization and production of an efficient, easily separable adsorbent for heavy metal removal.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1768 ","pages":"Article 466668"},"PeriodicalIF":4.0,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145916484","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 : 2025-12-30DOI: 10.1016/j.chroma.2025.466664
Miao Jing , Juntao Wang , Ruiyang Ma , Yaxing Guo , Zichen Zhao , Qiuhua Wu , Zhi Wang
A porous hyper-crosslinked polymer (OPS/BCM-HCP) was synthesized for the first time using cage-shaped octaphenyl POSS as the monomer and biphenyl-p-dichlorobenzene as the cross-linker for the efficient enrichment of phenylurea herbicides (chlorotoluron, isoproturon, monolinuron and buturon). High performance extraction for the phenylureas was realized by using the OPS/BCM-HCP as the SPE adsorbent from water, cabbage and white radish samples. Under the optimized conditions, the newly established method by coupling the SPE with HPLC-UV had a good linear response for phenylureas in the range of 0.06–100.0 ng mL⁻¹ for water, 2.10–200.0 ng g⁻¹ for cabbage, and 1.20–200.0 ng g⁻¹ for white radish samples, with the determination coefficient larger than 0.9912. The limits of detection (LODs, S/N = 3) and limits of quantification (LOQs, S/N = 9) were 0.02–0.03 and 0.06–0.09 ng mL⁻¹ for water, 0.70–0.95 and 2.10–2.85 ng g⁻¹ for cabbage, and 0.40–0.85 and 1.20–2.55 ng g⁻¹ for white radish, respectively. The method recoveries were 80.0 %-116 % with the RSDs from 3.6 % to 8.9 %. The experimental results showed that OPS/BCM-HCP had an excellent adsorption effect on phenylurea herbicides, and the method provided an alternative way for the effective quantification of the herbicides in vegetable samples.
以笼形八苯基POSS为单体，联苯-对二氯苯为交联剂，首次合成了多孔超交联聚合物OPS/BCM-HCP，用于高效富集苯脲类除草剂（氯脲、异丙脲、单脲和布脲）。采用OPS/BCM-HCP作为固相萃取剂，从水、白菜和白萝卜样品中高效提取苯脲类化合物。在优化的条件下，建立的固相萃取-高效液相色谱-紫外耦合法对苯脲的测定结果在0.06 ~ 100.0 ng mL毒葫芦、2.10 ~ 200.0 ng g毒葫芦、1.20 ~ 200.0 ng g毒葫芦范围内有良好的线性反应，且测定系数大于0.9912。对水的检测限（S/N = 3）和定量限（S/N = 9）分别为0.02-0.03和0.06-0.09 ng g⁻，对白菜的检测限为0.70-0.95和2.10-2.85 ng g⁻，对白萝卜的检测限为0.40-0.85和1.20-2.55 ng g⁻。方法加样回收率为80.0% ~ 116%，rsd为3.6% ~ 8.9%。实验结果表明，OPS/BCM-HCP对苯脲类除草剂具有良好的吸附效果，为蔬菜样品中苯脲类除草剂的有效定量提供了一种替代方法。
{"title":"Synthesis of modified siloxane-based three-dimensional porous polymer as adsorbent for high-efficiency enrichment of phenyl urea herbicides from vegetables","authors":"Miao Jing , Juntao Wang , Ruiyang Ma , Yaxing Guo , Zichen Zhao , Qiuhua Wu , Zhi Wang","doi":"10.1016/j.chroma.2025.466664","DOIUrl":"10.1016/j.chroma.2025.466664","url":null,"abstract":"<div><div>A porous hyper-crosslinked polymer (OPS/BCM-HCP) was synthesized for the first time using cage-shaped octaphenyl POSS as the monomer and biphenyl-p-dichlorobenzene as the cross-linker for the efficient enrichment of phenylurea herbicides (chlorotoluron, isoproturon, monolinuron and buturon). High performance extraction for the phenylureas was realized by using the OPS/BCM-HCP as the SPE adsorbent from water, cabbage and white radish samples. Under the optimized conditions, the newly established method by coupling the SPE with HPLC-UV had a good linear response for phenylureas in the range of 0.06–100.0 ng mL⁻¹ for water, 2.10–200.0 ng g⁻¹ for cabbage, and 1.20–200.0 ng g⁻¹ for white radish samples, with the determination coefficient larger than 0.9912. The limits of detection (LODs, S/<em>N</em> = 3) and limits of quantification (LOQs, S/<em>N</em> = 9) were 0.02–0.03 and 0.06–0.09 ng mL⁻¹ for water, 0.70–0.95 and 2.10–2.85 ng g⁻¹ for cabbage, and 0.40–0.85 and 1.20–2.55 ng g⁻¹ for white radish, respectively. The method recoveries were 80.0 %-116 % with the RSDs from 3.6 % to 8.9 %. The experimental results showed that OPS/BCM-HCP had an excellent adsorption effect on phenylurea herbicides, and the method provided an alternative way for the effective quantification of the herbicides in vegetable samples.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1769 ","pages":"Article 466664"},"PeriodicalIF":4.0,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145883754","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 : 2025-12-30DOI: 10.1016/j.chroma.2025.466667
Hai-Long Jiang , Hong-Yan Liu , Xiao-Li Wang , Da-Feng Jiang , Dong-Mei Liu , Jin-Peng Yuan , Xia Wang , Ru-Song Zhao
In this study, a coral like structure conjugated microporous polymer with abundant N/O functional groups was synthesized using a one-step method. The synthesized material was assembled into a solid-phase extraction (SPE) column, and it showed efficient extraction performance for paraben-based preservatives. Under optimized SPE conditions, a high performance liquid chromatographic (HPLC) method with good linear (r≥0.998), low detection limit (0.07-0.19 ng/mL) and high precision (1.8-6.7%, n=6) was developed. The applicability of this method was evaluated by analyzing real samples (milk and water), with spiked recovery rates ranging from 82.8% to 106%, further confirming the accuracy and reliability of the method. The adsorption mechanism was also discussed by simulation calculations, and it was mainly dominated by hydrogen bonding, π-π interactions and van der Waals forces.
{"title":"Solid phase extraction based on a coral like structure conjugated microporous polymer for the detection of preservatives in milk and water","authors":"Hai-Long Jiang , Hong-Yan Liu , Xiao-Li Wang , Da-Feng Jiang , Dong-Mei Liu , Jin-Peng Yuan , Xia Wang , Ru-Song Zhao","doi":"10.1016/j.chroma.2025.466667","DOIUrl":"10.1016/j.chroma.2025.466667","url":null,"abstract":"<div><div>In this study, a coral like structure conjugated microporous polymer with abundant N/O functional groups was synthesized using a one-step method. The synthesized material was assembled into a solid-phase extraction (SPE) column, and it showed efficient extraction performance for paraben-based preservatives. Under optimized SPE conditions, a high performance liquid chromatographic (HPLC) method with good linear (r≥0.998), low detection limit (0.07-0.19 ng/mL) and high precision (1.8-6.7%, n=6) was developed. The applicability of this method was evaluated by analyzing real samples (milk and water), with spiked recovery rates ranging from 82.8% to 106%, further confirming the accuracy and reliability of the method. The adsorption mechanism was also discussed by simulation calculations, and it was mainly dominated by hydrogen bonding, π-π interactions and van der Waals forces.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1769 ","pages":"Article 466667"},"PeriodicalIF":4.0,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145883756","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}
In order to study the adsorption interaction and behavior of organophosphate pesticides (OPPs) on the surface of different microplastics, a Zr-covalent organic framework (COF)-based magnetic solid-phase extraction (MSPE) was established. Due to various interactions (π-π interaction, hydrogen bonding and Zr-O-P coordination interactions), Zr-COF exhibited higher adsorption capacities towards five OPPs than COF without Zr through the theoretical calculation and analysis. The established MSPE-HPLC method showed the detection limit of 0.011–0.019 mg L−1 for OPPs. It was used to determine the adsorption performance of four microplastics towards OPPs. Small sized and aging microplastics showed more adsorption capacities than the large sized and original microplastics. Polylactic acid exhibited higher adsorption capacities than most OPPs, especially with the N element, -NO2, and P=O groups, due to the presence of hydrogen bonding. Besides, the method matrix effect was between 2.90%-17.84% in real samples, and the adsorption capacity in juice was significantly higher than that in aquatic samples because of the acidic environment.
为了研究有机磷农药（OPPs）在不同微塑料表面的吸附相互作用及其行为，建立了一种基于zr共价有机骨架（COF）的磁固相萃取（MSPE）方法。通过理论计算和分析，由于π-π相互作用、氢键相互作用和Zr- o - p配位相互作用，Zr-COF对5种OPPs的吸附能力高于不含Zr的COF。建立的MSPE-HPLC法对OPPs的检出限为0.011 ~ 0.019 mg L−1。测定了四种微塑料对OPPs的吸附性能。小尺寸和老化的微塑料比大尺寸和原始微塑料具有更高的吸附能力。由于氢键的存在，聚乳酸表现出比大多数OPPs更高的吸附能力，特别是对N元素、-NO2和P=O基团。实际样品的方法基质效应在2.90% ~ 17.84%之间，且由于环境酸性，果汁中的吸附量明显高于水生样品。
{"title":"The adsorption determination of organophosphate pesticides on microplastics in aquatic and juice samples using a Zr-COF-based magnetic solid-phase extraction","authors":"Yufei Liu, Sitian Gu, Wenli Zhu, Man Gong, Qingli Yang, Xiudan Hou","doi":"10.1016/j.chroma.2025.466666","DOIUrl":"10.1016/j.chroma.2025.466666","url":null,"abstract":"<div><div>In order to study the adsorption interaction and behavior of organophosphate pesticides (OPPs) on the surface of different microplastics, a Zr-covalent organic framework (COF)-based magnetic solid-phase extraction (MSPE) was established. Due to various interactions (π-π interaction, hydrogen bonding and Zr-O-P coordination interactions), Zr-COF exhibited higher adsorption capacities towards five OPPs than COF without Zr through the theoretical calculation and analysis. The established MSPE-HPLC method showed the detection limit of 0.011–0.019 mg L<sup>−1</sup> for OPPs. It was used to determine the adsorption performance of four microplastics towards OPPs. Small sized and aging microplastics showed more adsorption capacities than the large sized and original microplastics. Polylactic acid exhibited higher adsorption capacities than most OPPs, especially with the N element, -NO<sub>2</sub>, and P=O groups, due to the presence of hydrogen bonding. Besides, the method matrix effect was between 2.90%-17.84% in real samples, and the adsorption capacity in juice was significantly higher than that in aquatic samples because of the acidic environment.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1767 ","pages":"Article 466666"},"PeriodicalIF":4.0,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880741","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 : 2025-12-29DOI: 10.1016/j.chroma.2025.466665
Shuning Li , Xiaojing Liang , Yong Guo , Xiaofeng Lu , Licheng Wang
Hydrophilic chromatography (HILIC) serves as an effective means of separating different polar compounds. Several studies have indicated the ability of HILIC to distinguish between structurally similar compounds. Hence, the development and study of HILIC stationary phases with superior separation capabilities hold substantial practical importance. In this work, a three-dimensional hydrogel network was synthesized using polyvinyl alcohol (PVA) and polyacrylic acid (PAA). This was further developed into a nanocomposite hydrogel by incorporating carbon dots (CDs) produced from citric acid and ethylenediamine. A new stationary phase (Sil@PVA/PAA/CDs) was synthesized by coating the nanocomposite hydrogel onto the surface of bare silica. Compared to traditional hydrogel, nanocomposite hydrogel not only significantly improve the swelling behavior, mechanical properties, and adsorption capacity of hydrogel, but also synergistically enhance and precisely modulate the network structure and interactions within the hydrogel, ultimately enabling successful separation of target analytes. The separation mechanism revealed that Sil@PVA/PAA/CDs demonstrated good HILIC separation ability. A variety of polar compounds achieved effective separation, encompassing ten types of nucleosides/bases, seven types of antibiotics, and six types of organic acids. Notably, the column efficiency for guanosine separation reached an impressive 90,977.3 N/m. Furthermore, three structurally similar uridine nucleotides and four fluoroquinolone antibiotics (FQs) were separated successfully on Sil@PVA/PAA/CDs. Given the limited reports on HPLC separation of FQs, this offered a valuable reference. The integration of CDs with hydrogel has effectively addressed the limitations of conventional hydrogel, including their poor mechanical properties and limited functions.
{"title":"Nanocomposite hydrogel functionalized silica stationary phase for the separation of polar compounds and fluoroquinolone antibiotics","authors":"Shuning Li , Xiaojing Liang , Yong Guo , Xiaofeng Lu , Licheng Wang","doi":"10.1016/j.chroma.2025.466665","DOIUrl":"10.1016/j.chroma.2025.466665","url":null,"abstract":"<div><div>Hydrophilic chromatography (HILIC) serves as an effective means of separating different polar compounds. Several studies have indicated the ability of HILIC to distinguish between structurally similar compounds. Hence, the development and study of HILIC stationary phases with superior separation capabilities hold substantial practical importance. In this work, a three-dimensional hydrogel network was synthesized using polyvinyl alcohol (PVA) and polyacrylic acid (PAA). This was further developed into a nanocomposite hydrogel by incorporating carbon dots (CDs) produced from citric acid and ethylenediamine. A new stationary phase (Sil@PVA/PAA/CDs) was synthesized by coating the nanocomposite hydrogel onto the surface of bare silica. Compared to traditional hydrogel, nanocomposite hydrogel not only significantly improve the swelling behavior, mechanical properties, and adsorption capacity of hydrogel, but also synergistically enhance and precisely modulate the network structure and interactions within the hydrogel, ultimately enabling successful separation of target analytes. The separation mechanism revealed that Sil@PVA/PAA/CDs demonstrated good HILIC separation ability. A variety of polar compounds achieved effective separation, encompassing ten types of nucleosides/bases, seven types of antibiotics, and six types of organic acids. Notably, the column efficiency for guanosine separation reached an impressive 90,977.3 N/m. Furthermore, three structurally similar uridine nucleotides and four fluoroquinolone antibiotics (FQs) were separated successfully on Sil@PVA/PAA/CDs. Given the limited reports on HPLC separation of FQs, this offered a valuable reference. The integration of CDs with hydrogel has effectively addressed the limitations of conventional hydrogel, including their poor mechanical properties and limited functions.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1767 ","pages":"Article 466665"},"PeriodicalIF":4.0,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880676","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 : 2025-12-28DOI: 10.1016/j.chroma.2025.466663
Jingyi Yan , Siyuan Peng , Jingying Huang , Zhihua Song , Dani Sun , Yongfei Ming , Lingxin Chen , Jinhua Li , Huaying Fan
Antibiotics have received wide concerns especially in coastal-zone waters, necessitating their sensitive determination. Metal-organic frameworks (MOFs) based molecularly imprinted polymers (MIPs) composites have demonstrated excellent versatility, recognition properties, and practical applicability in the sample preparation. Herein, zeolitic imidazolate frameworks (ZIFs)-8 (ZIF-8) as a kind of typical MOF material, was employed as the support of MIPs and the resultant ZIF-8-MIPs were used for solid-phase extraction (SPE) of fluoroquinolones (FQs) in coastal-zone environmental water samples followed by high-performance liquid chromatography (HPLC) determination. The composites were facilely prepared via precipitation polymerization combined with surface imprinting, using enrofloxacin (ENR) as template molecule. The composition, structure and morphology of ZIF-8@MIPs were well characterized, and the adsorption followed pseudo-second-order kinetic and Langmuir isotherm models. Rapid adsorption equilibrium can be reached within 30 min, with a maximum adsorption capacity of 79.97 mg/g. Then, key parameters of SPE packed with ZIF-8@MIPs were systematically investigated. Under the optimal conditions, a sensitive SPE-HPLC method was developed towards four FQs, offering high enrichment factors of 82–153. Excellent linearity was attained in the wide range of 0.1–200 μg/L, and the limits of detection were as low as 0.024–0.034 μg/L together with limits of quantitation within 0.081–0.113 μg/L. The matrix effect values in the tested coastal waters including seawater, aquaculture wastewater, lake water, and river water, were from –6.69% to 5.47%, indicating the ZIF-8@MIPs-SPE efficiently eliminated matrix interference and ensured accurate reliable quantification. Consequently, in all the four water samples, high recoveries ranged from 91.4 to 105.2%, with low relative standard deviations of 1.8–8.7%. This study can enrich the research connotation of MOF@MIPs composites based sample preparation and provide an alternative detection scheme for the monitoring of trace antibiotics in complicated matrices.
{"title":"Metal-organic framework-based molecularly imprinted polymers for solid-phase extraction of fluoroquinolones in coastal-zone water samples","authors":"Jingyi Yan , Siyuan Peng , Jingying Huang , Zhihua Song , Dani Sun , Yongfei Ming , Lingxin Chen , Jinhua Li , Huaying Fan","doi":"10.1016/j.chroma.2025.466663","DOIUrl":"10.1016/j.chroma.2025.466663","url":null,"abstract":"<div><div>Antibiotics have received wide concerns especially in coastal-zone waters, necessitating their sensitive determination. Metal-organic frameworks (MOFs) based molecularly imprinted polymers (MIPs) composites have demonstrated excellent versatility, recognition properties, and practical applicability in the sample preparation. Herein, zeolitic imidazolate frameworks (ZIFs)-8 (ZIF-8) as a kind of typical MOF material, was employed as the support of MIPs and the resultant ZIF-8-MIPs were used for solid-phase extraction (SPE) of fluoroquinolones (FQs) in coastal-zone environmental water samples followed by high-performance liquid chromatography (HPLC) determination. The composites were facilely prepared via precipitation polymerization combined with surface imprinting, using enrofloxacin (ENR) as template molecule. The composition, structure and morphology of ZIF-8@MIPs were well characterized, and the adsorption followed pseudo-second-order kinetic and Langmuir isotherm models. Rapid adsorption equilibrium can be reached within 30 min, with a maximum adsorption capacity of 79.97 mg/g. Then, key parameters of SPE packed with ZIF-8@MIPs were systematically investigated. Under the optimal conditions, a sensitive SPE-HPLC method was developed towards four FQs, offering high enrichment factors of 82–153. Excellent linearity was attained in the wide range of 0.1–200 μg/L, and the limits of detection were as low as 0.024–0.034 μg/L together with limits of quantitation within 0.081–0.113 μg/L. The matrix effect values in the tested coastal waters including seawater, aquaculture wastewater, lake water, and river water, were from –6.69% to 5.47%, indicating the ZIF-8@MIPs-SPE efficiently eliminated matrix interference and ensured accurate reliable quantification. Consequently, in all the four water samples, high recoveries ranged from 91.4 to 105.2%, with low relative standard deviations of 1.8–8.7%. This study can enrich the research connotation of MOF@MIPs composites based sample preparation and provide an alternative detection scheme for the monitoring of trace antibiotics in complicated matrices.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1767 ","pages":"Article 466663"},"PeriodicalIF":4.0,"publicationDate":"2025-12-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880675","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}
To address the growing demand for enhanced chromatographic resolution of diverse analytes, the development of novel stationary phases exhibiting superior selectivity and broader applicability is imperative. Poly(ionic liquid)s and polymer hydrogels, recognize as versatile functional materials, can be combined into novel poly(ionic liquid) hydrogels to enhance the performance of silica-based stationary phase through tailored functionalization and multi-mode interactions, demonstrating advantageous potential for advanced chromatographic separations. Herein, employing 3-hexadecyl-1-vinylimidazolium bromide ([HDVIM]Br) and acrylic acid (AA) as monomers, a novel poly([HDVIM]Br-co-AA) hydrogel-modified stationary phase (Sil-PHA) was synthesized via thiol-ene click polymerization, and its applicability in chromatographic separation was systematically evaluated. Benefitting from the synergistic effect of poly(ionic liquid)s and hydrogels, the Sil-PHA effectively produces multiple interactions with the analytes and achieves a hydrophobicity/hydrophilicity balance, resulting in excellent separation ability for various compounds. The Sil-PHA column demonstrates effective separation capabilities for hydrophilic nucleosides and diverse hydrophobic aromatic compounds (alkylphenols, alkylbenzenes, phthalates, polycyclic aromatic hydrocarbons, bisphenols and aromatic ketones). This study establishes poly(ionic liquid) hydrogels as a transformative class of separation materials with demonstrated core functionality in chromatographic science. This not only delivers a new material platform for achieving high-performance separation of diverse samples but also pioneers an innovative approach for constructing multifunctional separation system.
{"title":"Efficient construction of superior poly(ionic liquid) hydrogels for promising application in HPLC analysis","authors":"Linjun Zuo, Qian Zhao, Hongjie Wang, Yixuan Xie, Wei Chen, Sheng Tang","doi":"10.1016/j.chroma.2025.466662","DOIUrl":"10.1016/j.chroma.2025.466662","url":null,"abstract":"<div><div>To address the growing demand for enhanced chromatographic resolution of diverse analytes, the development of novel stationary phases exhibiting superior selectivity and broader applicability is imperative. Poly(ionic liquid)s and polymer hydrogels, recognize as versatile functional materials, can be combined into novel poly(ionic liquid) hydrogels to enhance the performance of silica-based stationary phase through tailored functionalization and multi-mode interactions, demonstrating advantageous potential for advanced chromatographic separations. Herein, employing 3-hexadecyl-1-vinylimidazolium bromide ([HDVIM]Br) and acrylic acid (AA) as monomers, a novel poly([HDVIM]Br-<em>co</em>-AA) hydrogel-modified stationary phase (Sil-PHA) was synthesized <em>via</em> thiol-ene click polymerization, and its applicability in chromatographic separation was systematically evaluated. Benefitting from the synergistic effect of poly(ionic liquid)s and hydrogels, the Sil-PHA effectively produces multiple interactions with the analytes and achieves a hydrophobicity/hydrophilicity balance, resulting in excellent separation ability for various compounds. The Sil-PHA column demonstrates effective separation capabilities for hydrophilic nucleosides and diverse hydrophobic aromatic compounds (alkylphenols, alkylbenzenes, phthalates, polycyclic aromatic hydrocarbons, bisphenols and aromatic ketones). This study establishes poly(ionic liquid) hydrogels as a transformative class of separation materials with demonstrated core functionality in chromatographic science. This not only delivers a new material platform for achieving high-performance separation of diverse samples but also pioneers an innovative approach for constructing multifunctional separation system.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1767 ","pages":"Article 466662"},"PeriodicalIF":4.0,"publicationDate":"2025-12-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880739","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 : 2025-12-27DOI: 10.1016/j.chroma.2025.466660
Alper Şahin , Yeliz Akpinar , Erol Yildirim , Ahmet E Eroğlu , Ezel Boyaci
Molecularly imprinted polymers (MIPs) have been extensively used as selective extractive phases for sample preparation because of their analyte-selective binding sites. However, MIP preparation requires optimized monomer-template interactions and long polymerization reactions.
In this study, a novel and simple method of MIP preparation was proposed based on electrospinning. Instead of preparing analyte-monomer complexes before polymerization, model analytes (trifluralin and carbaryl) were directly dissolved in a polyacrylonitrile (PAN) solution, then electrospun into nanofibrous mats. This allowed for a means of preparation of highly crystalline, template-imprinted nanostructures with minimal synthetic complexity.
Following the characterization studies for the new material, the extraction properties of the imprinted and nonimprinted electrospun mats were investigated in thin film microextraction (TFME) studies by extracting trifluralin and carbaryl from water samples, followed by gas chromatography-mass spectrometry (GC–MS) analysis. The optimization results showed that samplers containing 10.0 mg of MIP sorbents made by electrospinning of a solution containing 5.0 mg of template in 1.0 mL of PAN solution resulted in approximately 4 and 7 times enhanced extraction recoveries for carbaryl and trifluralin compared to samplers made of non-imprinted bulk PAN. Moreover, the cross-reactivity testing performed with non-template analytes (malathion and diazinon) suggested a more specific extraction towards trifluralin compared to carbaryl. The proposed new technique was also validated using computational methodology, which supported the experimental finding about higher selectivity towards trifluralin. This may signify a probability for structural orientation of partially charged trifluralin under an electrical field in electrospun PAN creating favorable extraction sites.
分子印迹聚合物（MIPs）由于其具有分析选择性结合位点而被广泛用作样品制备的选择性萃取相。然而，MIP的制备需要优化单体-模板相互作用和长时间的聚合反应。本研究提出了一种基于静电纺丝的新型、简单的MIP制备方法。模型分析物（三氟拉林和西威因）直接溶解在聚丙烯腈（PAN）溶液中，然后电纺成纳米纤维垫，而不是在聚合前制备分析物-单体复合物。这使得以最小的合成复杂性制备高度结晶的模板印迹纳米结构成为可能。在对新材料进行表征研究之后，采用薄膜微萃取法（TFME）研究了印迹和非印迹电纺丝毡的提取性能，分别从水样中提取三氟拉灵和西威尼，然后进行气相色谱-质谱（GC-MS）分析。优化结果表明，在含有5.0 mg模板的1.0 mL PAN溶液中，静电纺丝制备含有10.0 mg MIP吸附剂的样品，与未印迹的大体积PAN样品相比，提取西威因和氟拉林的回收率提高了约4倍和7倍。此外，与非模板分析物（马拉硫磷和二嗪农）进行的交叉反应性测试表明，与西威因相比，对三氟拉林的提取更具特异性。提出的新技术也使用计算方法进行了验证，这支持了对氟拉林有更高选择性的实验发现。这可能表明在静电纺PAN中的电场作用下，部分带电的氟虫灵有可能形成结构取向，从而产生有利的提取位点。
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A green and efficient analytical method was developed for the simultaneous determination of triazole fungicides using sodium alginate/supramolecular solvent composite beads (SA-SUPRAS beads) as an adsorbent in dispersive solid-phase extraction (dSPE), followed by ultra-performance liquid chromatography (UPLC). The supramolecular solvent was synthesized by the aggregation of 1-dodecanol and tetrahydrofuran in a molar ratio of 1:5 and incorporated into the alginate solution before a one-step formation process. Although THF is not an ideal green solvent, its use was minimized and handled under fume hood conditions. The nanoscale micelle-bead interactions enhanced the adsorption performance. The structural and physicochemical characteristics of the SA-SUPRAS beads were evaluated by FTIR, TGA, BET, XRD, 1H-NMR, SEM, and the adsorption kinetics, and the impact of salt concentration was also investigated. Additionally, the parameters influencing the desorption process, such as the sorbent amount, type, and volume of the desorption solvent, sample concentration and volume, and extraction time, were optimized. The method demonstrated excellent linearity within a concentration range of 9–500 μg L-1, with a correlation coefficient (R²) of 0.99. Detection and quantification limits ranged from 3.00 to 10.00 μg L⁻¹ and 9.00 to 30.00 μg L⁻¹, respectively. The precision of the method, expressed as relative standard deviation, was <7 %. Furthermore, enrichment factors ranged from 48.40 to 53.13, and extraction recoveries were between 96.00 and 106.25 %. However, the SA-SUPRAS beads exhibited limited reusability, and substantial matrix effects originating from UV-absorbing co-extractives in chili and tea necessitated matrix-matched calibration for reliable quantification. These findings highlight that the SA-SUPRAS beads-dSPE procedure is a rapid, sensitive, and reduced-solvent alternative to conventional sample preparation methods for the reliable determination of triazole fungicides in dried chili and tea leaves.
{"title":"Sodium alginate-supramolecular solvent composite beads for green extraction of triazole fungicides in dried chili and tea leaves followed by ultra-performance liquid chromatography","authors":"Rawikan Kachangoon , Yanawath Santaladchaiyakit , Jitlada Vichapong","doi":"10.1016/j.chroma.2025.466659","DOIUrl":"10.1016/j.chroma.2025.466659","url":null,"abstract":"<div><div>A green and efficient analytical method was developed for the simultaneous determination of triazole fungicides using sodium alginate/supramolecular solvent composite beads (SA-SUPRAS beads) as an adsorbent in dispersive solid-phase extraction (dSPE), followed by ultra-performance liquid chromatography (UPLC). The supramolecular solvent was synthesized by the aggregation of 1-dodecanol and tetrahydrofuran in a molar ratio of 1:5 and incorporated into the alginate solution before a one-step formation process. Although THF is not an ideal green solvent, its use was minimized and handled under fume hood conditions. The nanoscale micelle-bead interactions enhanced the adsorption performance. The structural and physicochemical characteristics of the SA-SUPRAS beads were evaluated by FTIR, TGA, BET, XRD, <sup>1</sup>H-NMR, SEM, and the adsorption kinetics, and the impact of salt concentration was also investigated. Additionally, the parameters influencing the desorption process, such as the sorbent amount, type, and volume of the desorption solvent, sample concentration and volume, and extraction time, were optimized. The method demonstrated excellent linearity within a concentration range of 9–500 μg L<sup>-1</sup>, with a correlation coefficient (R²) of 0.99. Detection and quantification limits ranged from 3.00 to 10.00 μg L⁻¹ and 9.00 to 30.00 μg L⁻¹, respectively. The precision of the method, expressed as relative standard deviation, was <7 %. Furthermore, enrichment factors ranged from 48.40 to 53.13, and extraction recoveries were between 96.00 and 106.25 %. However, the SA-SUPRAS beads exhibited limited reusability, and substantial matrix effects originating from UV-absorbing co-extractives in chili and tea necessitated matrix-matched calibration for reliable quantification. These findings highlight that the SA-SUPRAS beads-dSPE procedure is a rapid, sensitive, and reduced-solvent alternative to conventional sample preparation methods for the reliable determination of triazole fungicides in dried chili and tea leaves.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1767 ","pages":"Article 466659"},"PeriodicalIF":4.0,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145877400","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 : 2025-12-27DOI: 10.1016/j.chroma.2025.466658
Hung-Wei Tsui
The determination of total adsorption isotherms in liquid chromatography is fundamentally sensitive to the definition of the hold-up volume (), which implicitly fixes the Gibbs-like dividing plane between the mobile and stationary phases. Conventional approaches often rely on arbitrary dead-time markers, leading to inconsistencies between excess and total adsorption quantities and potentially inducing artificial saturation artifacts in model fitting. To resolve this ambiguity, this study establishes a self-consistent dividing-plane framework coupled with affinity energy distribution analysis. Using minor disturbance method data for homologous alcohols (ethanol to butanol) on a cyano-silica column, we propose an iterative approach that adjusts the dividing plane until the model-derived isotherm slope reconciles with experimental perturbation times. This approach robustly deconvolutes the adsorption landscape into two distinct contributions: a high-affinity family (sites B) governing specific hydrogen-bonding interactions at the ligand surface, and a low-affinity family (sites A) representing non-specific solute accumulation within the diffuse interfacial region. Thermodynamic analysis further validates this mechanism, revealing that sites B exhibit a strongly exothermic enthalpy of adsorption (-35 kJ/mol for 2-propanol), whereas sites A are energetically weaker and geometrically sensitive to the choice of the dividing plane. By strictly defining the reference state, this framework offers a rigorous route to separate specific binding from interfacial accumulation, yielding adsorption parameters that are physically interpretable and thermodynamically consistent.
{"title":"Self-consistent determination of hold-up volume in normal-phase liquid chromatography: A dividing-plane framework for adsorption isotherm interpretation","authors":"Hung-Wei Tsui","doi":"10.1016/j.chroma.2025.466658","DOIUrl":"10.1016/j.chroma.2025.466658","url":null,"abstract":"<div><div>The determination of total adsorption isotherms in liquid chromatography is fundamentally sensitive to the definition of the hold-up volume (<span><math><msubsup><mi>V</mi><mrow><mi>L</mi></mrow><mo>′</mo></msubsup></math></span>), which implicitly fixes the Gibbs-like dividing plane between the mobile and stationary phases. Conventional approaches often rely on arbitrary dead-time markers, leading to inconsistencies between excess and total adsorption quantities and potentially inducing artificial saturation artifacts in model fitting. To resolve this ambiguity, this study establishes a self-consistent dividing-plane framework coupled with affinity energy distribution analysis. Using minor disturbance method data for homologous alcohols (ethanol to butanol) on a cyano-silica column, we propose an iterative approach that adjusts the dividing plane until the model-derived isotherm slope reconciles with experimental perturbation times. This approach robustly deconvolutes the adsorption landscape into two distinct contributions: a high-affinity family (sites B) governing specific hydrogen-bonding interactions at the ligand surface, and a low-affinity family (sites A) representing non-specific solute accumulation within the diffuse interfacial region. Thermodynamic analysis further validates this mechanism, revealing that sites B exhibit a strongly exothermic enthalpy of adsorption (<span><math><mrow><mstyle><mi>Δ</mi></mstyle><msup><mrow><mi>H</mi></mrow><mn>0</mn></msup><mo>≈</mo></mrow></math></span>-35 kJ/mol for 2-propanol), whereas sites A are energetically weaker and geometrically sensitive to the choice of the dividing plane. By strictly defining the reference state, this framework offers a rigorous route to separate specific binding from interfacial accumulation, yielding adsorption parameters that are physically interpretable and thermodynamically consistent.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1767 ","pages":"Article 466658"},"PeriodicalIF":4.0,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145877402","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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