Journal of Chromatography A最新文献_第10页

Rational design of a mesoporous COF with tailored porosity for synergistic extraction and analysis of organic ultraviolet stabilizers 为有机紫外稳定剂的协同萃取和分析，合理设计具有定制孔隙率的介孔COF。

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-12-02 DOI: 10.1016/j.chroma.2025.466603

Shuang Li , Yiling Zhu , Zhen Ren , Chunying Zheng , Jinhua Li , Xiaoyan Wang , Jiping Ma , Lingxin Chen

Organic ultraviolet stabilizers (OUVSs) have raised significant concerns due to their widespread occurrence and potential endocrine-disrupting effects. Herein, a kind of novel mesoporous covalent organic frameworks (COF), i.e., Fe₃O₄@TFPB-BD, was rationally designed and fabricated for the vortex-assisted magnetic solid-phase extraction (MSPE) of seven kinds of OUVSs from water samples prior to ultra-high performance liquid chromatography–tandem mass spectrometry (UHPLC–MS/MS) analysis. The pore size (42.1 Å) of the material was pre-designed using density functional theory (DFT) to match the molecular dimensions of the OUVSs (10.6–12.5 Å), facilitating rapid mass transfer. The adsorption mechanism was elucidated to involve synergistic π-π conjugation and hydrogen bonding interactions. Under optimized MSPE conditions, the developed method demonstrated exceptional performance with a remarkably short pretreatment time of only 8 min, excellent precision (intra-day RSDs of 4.2–14.4 %; inter-day RSDs of 1.8–14.8 %), and ultra-low detection limits between 0.23 and 0.35 ng/L. The method was successfully applied to the analysis of coastal seawater and swimming pool water, achieving satisfactory spiked recoveries ranging from 83.66 % to 118.48 %. This study presents a rapid, sensitive, and robust approach for monitoring trace-level OUVSs in complex aquatic environments.

有机紫外线稳定剂（OUVSs）由于其广泛存在和潜在的内分泌干扰作用而引起了人们的极大关注。本文合理设计并制备了一种新型介孔共价有机骨架（COF） Fe3O4@TFPB-BD，用于涡旋辅助磁固相萃取（MSPE）提取水样中7种ouvs，并进行超高效液相色谱-串联质谱（UHPLC-MS/MS）分析。利用密度泛函理论（DFT）预先设计了材料的孔径（42.1 Å），以匹配OUVSs的分子尺寸（10.6-12.5 Å），从而促进快速传质。吸附机理涉及协同π-π共轭和氢键相互作用。在优化的MSPE条件下，该方法预处理时间短，仅为8 min，精密度高（日内rsd为4.2 ~ 14.4%，日内rsd为1.8 ~ 14.8%），检出限在0.23 ~ 0.35 ng/L之间。该方法成功地应用于沿海海水和游泳池水的分析，加标回收率为83.66% ~ 118.48%。本研究提出了一种快速、灵敏、可靠的方法来监测复杂水生环境中痕量OUVSs。

{"title":"Rational design of a mesoporous COF with tailored porosity for synergistic extraction and analysis of organic ultraviolet stabilizers","authors":"Shuang Li , Yiling Zhu , Zhen Ren , Chunying Zheng , Jinhua Li , Xiaoyan Wang , Jiping Ma , Lingxin Chen","doi":"10.1016/j.chroma.2025.466603","DOIUrl":"10.1016/j.chroma.2025.466603","url":null,"abstract":"<div><div>Organic ultraviolet stabilizers (OUVSs) have raised significant concerns due to their widespread occurrence and potential endocrine-disrupting effects. Herein, a kind of novel mesoporous covalent organic frameworks (COF), i.e., Fe<sub>3</sub>O<sub>4</sub>@TFPB-BD, was rationally designed and fabricated for the vortex-assisted magnetic solid-phase extraction (MSPE) of seven kinds of OUVSs from water samples prior to ultra-high performance liquid chromatography–tandem mass spectrometry (UHPLC–MS/MS) analysis. The pore size (42.1 Å) of the material was pre-designed using density functional theory (DFT) to match the molecular dimensions of the OUVSs (10.6–12.5 Å), facilitating rapid mass transfer. The adsorption mechanism was elucidated to involve synergistic π-π conjugation and hydrogen bonding interactions. Under optimized MSPE conditions, the developed method demonstrated exceptional performance with a remarkably short pretreatment time of only 8 min, excellent precision (intra-day RSDs of 4.2–14.4 %; inter-day RSDs of 1.8–14.8 %), and ultra-low detection limits between 0.23 and 0.35 ng/L. The method was successfully applied to the analysis of coastal seawater and swimming pool water, achieving satisfactory spiked recoveries ranging from 83.66 % to 118.48 %. This study presents a rapid, sensitive, and robust approach for monitoring trace-level OUVSs in complex aquatic environments.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1766 ","pages":"Article 466603"},"PeriodicalIF":4.0,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145720176","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}

引用次数: 0

Analysis of N-methyl-2-pyrrolidone and its hydroxy metabolite at low concentration level in water samples using liquid chromatography tandem mass spectrometry 液相色谱串联质谱法分析水样中低浓度n -甲基-2-吡咯烷酮及其羟基代谢物。

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-12-01 DOI: 10.1016/j.chroma.2025.466599

Ádám Tölgyesi , Carlos Gonçalves , Eszter Benes , Andrea Simon , Virender K. Sharma

N-methyl-2-pyrrolidone (NMP) is a synthetic organic compound used as a solvent in several industrial processes such as battery and cosmetics production. There are growing concerns regarding the toxicity of NMP in the environment. We present for the first time a liquid chromatography tandem mass spectrometric (LC-MS/MS) method for the determination of NMP and its hydroxy metabolite (5‑hydroxy-N-methyl-2-pyrrolidone, 5-OHNMP) in water at trace concentration (< 1.0 ng/mL). The HPLC separation was carried out on an aqueous mixed-mode column packed with C18 and anion exchange particles that enabled appropriate retention for both compounds. Quick sample preparation was performed by mixing isotopically labelled internal standards with the samples, followed by extraction with ethyl acetate in the presence of a QuEChERS salt mixture. After eliminating the use of plasticware from the entire sample treatment process, the target analytes could be detected at the 0.1 ng/mL level. The further reducing of the limit of quantification (LOQ) in real samples was limited by the cross contamination of NMP originating from the equipment used for the analysis. The method was validated between the 0.1 ng/mL and 10 ng/mL levels and the recovery ranged from 101 % to 109 % with high precision (RSD = 1.69 % - 7.34 %), with the exception for NMP at 0.10 ng/mL (RSD% = 24.7 %). The method was applied to the analysis of NMP in thirty-five surface and groundwater samples.

n -甲基-2-吡咯烷酮（NMP）是一种合成有机化合物，在电池和化妆品生产等多种工业过程中用作溶剂。人们越来越关注NMP在环境中的毒性。本文首次建立了液相色谱串联质谱（LC-MS/MS）测定水中微量浓度（< 1.0 ng/mL） NMP及其羟基代谢物（5 -羟基- n -甲基-2-吡罗烷酮，5- ohnmp）的方法。高效液相色谱分离是在水混合模式柱上进行的，柱上填充了C18和阴离子交换颗粒，使两种化合物都能适当保留。通过将同位素标记的内标物与样品混合进行快速样品制备，然后在QuEChERS盐混合物存在下用乙酸乙酯萃取。在整个样品处理过程中消除塑料制品的使用后，目标分析物可以在0.1 ng/mL的水平上检测到。进一步降低实际样品的定量限（LOQ）受到来自分析所用设备的NMP交叉污染的限制。该方法在0.1 ng/mL ~ 10 ng/mL范围内有效，加样回收率为101% ~ 109%，精密度（RSD = 1.69% ~ 7.34%），除NMP为0.10 ng/mL （RSD% = 24.7%）外。将该方法应用于35个地表水和地下水样品的NMP分析。

{"title":"Analysis of N-methyl-2-pyrrolidone and its hydroxy metabolite at low concentration level in water samples using liquid chromatography tandem mass spectrometry","authors":"Ádám Tölgyesi , Carlos Gonçalves , Eszter Benes , Andrea Simon , Virender K. Sharma","doi":"10.1016/j.chroma.2025.466599","DOIUrl":"10.1016/j.chroma.2025.466599","url":null,"abstract":"<div><div><em>N</em>-methyl-2-pyrrolidone (NMP) is a synthetic organic compound used as a solvent in several industrial processes such as battery and cosmetics production. There are growing concerns regarding the toxicity of NMP in the environment. We present for the first time a liquid chromatography tandem mass spectrometric (LC-MS/MS) method for the determination of NMP and its hydroxy metabolite (5‑hydroxy-<em>N</em>-methyl-2-pyrrolidone, 5-OH<img>NMP) in water at trace concentration (< 1.0 ng/mL). The HPLC separation was carried out on an aqueous mixed-mode column packed with C18 and anion exchange particles that enabled appropriate retention for both compounds. Quick sample preparation was performed by mixing isotopically labelled internal standards with the samples, followed by extraction with ethyl acetate in the presence of a QuEChERS salt mixture. After eliminating the use of plasticware from the entire sample treatment process, the target analytes could be detected at the 0.1 ng/mL level. The further reducing of the limit of quantification (LOQ) in real samples was limited by the cross contamination of NMP originating from the equipment used for the analysis. The method was validated between the 0.1 ng/mL and 10 ng/mL levels and the recovery ranged from 101 % to 109 % with high precision (RSD = 1.69 % - 7.34 %), with the exception for NMP at 0.10 ng/mL (RSD% = 24.7 %). The method was applied to the analysis of NMP in thirty-five surface and groundwater samples.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1766 ","pages":"Article 466599"},"PeriodicalIF":4.0,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145676073","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}

引用次数: 0

Theoretical and experimental evaluation of biosolvents with different degrees of hydrophobicity for the extraction of safranal and crocins from saffron 不同疏水度的生物溶剂提取藏红花中的藏红花醛和藏红花素的理论和实验评价

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-12-01 DOI: 10.1016/j.chroma.2025.466597

Marta Rivas-Piña , Adal Mena-García , Ana Isabel Ruiz-Matute , Rosa Lebrón-Aguilar , María Luz , Jesús Eduardo Quintanilla-López

Saffron (Crocus sativus) is a rich source of safranal and crocins, compounds responsible for its organoleptic and bioactive properties. Currently, there is a growing interest in obtaining saffron-based bioactive ingredients using sustainable technologies to develop functional products.

This study explores the use of green biosolvents, including natural deep eutectic solvents (NADESs), for the extraction of safranal and crocins. Solvent selection was guided by COSMO-RS (COnductor-like Screening MOdel for Real Solvents) predictions, also considering solvent polarity, toxicity level, and commercial availability. These predictions were also validated through σ-profile analysis and molecular dynamics simulations. Selected solvents, namely verbenone, carvacrol, and NADESs based on thymol and choline chloride, were evaluated against conventional solvents (H₂O and MeOH:H₂O). Saffron extracts were analysed using HPLC-DAD-MS, with choline chloride:ethylene glycol emerging as the most effective extractant for safranal (2.55 mg g⁻¹), comparable to MeOH:H₂O (2.56 mg g⁻¹), and superior to H₂O (1.29 mg g⁻¹). These solvents also provided the highest crocin recoveries (114.76-117.16 mg g⁻¹). Among the terpenoid-based solvents, carvacrol exhibited a higher selectivity for safranal (1.04 mg g⁻¹), with only 0.91 mg g⁻¹ for crocins.

Overall, the hydrophilic solvents were more efficient than the hydrophobic ones, finding a clear relationship between polarity and extraction capacity. These findings suggest the potential application of choline chloride:ethylene glycol NADES in the food industry for the extraction of bioactives from saffron, providing ecological benefits with low health risks and environmental impact.

藏红花（藏红花）是藏红花醛和藏红花素的丰富来源，这些化合物负责其感官和生物活性特性。目前，人们对利用可持续技术获得藏红花基生物活性成分以开发功能性产品的兴趣日益浓厚。本研究探索了绿色生物溶剂的使用，包括天然深共晶溶剂（NADESs），用于提取藏红花和藏红花。溶剂选择以cosmos - rs（真实溶剂类导体筛选模型）预测为指导，同时考虑溶剂极性、毒性水平和商业可用性。这些预测也通过σ-剖面分析和分子动力学模拟得到了验证。选择溶剂，即马鞭草酮，香芹酚，以及基于百里酚和氯化胆碱的NADESs，对传统溶剂（h2o和MeOH: h2o）进行了评价。用高效液相色谱-双相质谱法分析藏红花提取物，氯化胆碱：乙二醇是藏红花最有效的萃取剂（2.55 mg g⁻¹），与MeOH:H₂O （2.56 mg g⁻¹）相当，优于H₂O （1.29 mg⁻¹）。这些溶剂也提供了最高的藏红花素回收率（114.76-117.16 mg g⁻）。在萜类溶剂中，香芹酚对沙弗兰（1.04 mg g⁻）有较高的选择性，而对藏红花（0.91 mg g⁻）有较高的选择性。总的来说，亲水溶剂比疏水溶剂更有效，极性和萃取量之间存在明确的关系。这些发现表明氯化胆碱：乙二醇NADES在食品工业中的潜在应用，用于从藏红花中提取生物活性物质，提供低健康风险和环境影响的生态效益。

{"title":"Theoretical and experimental evaluation of biosolvents with different degrees of hydrophobicity for the extraction of safranal and crocins from saffron","authors":"Marta Rivas-Piña , Adal Mena-García , Ana Isabel Ruiz-Matute , Rosa Lebrón-Aguilar , María Luz , Jesús Eduardo Quintanilla-López","doi":"10.1016/j.chroma.2025.466597","DOIUrl":"10.1016/j.chroma.2025.466597","url":null,"abstract":"<div><div>Saffron (<em>Crocus sativus</em>) is a rich source of safranal and crocins, compounds responsible for its organoleptic and bioactive properties. Currently, there is a growing interest in obtaining saffron-based bioactive ingredients using sustainable technologies to develop functional products.</div><div>This study explores the use of green biosolvents, including natural deep eutectic solvents (NADESs), for the extraction of safranal and crocins. Solvent selection was guided by COSMO-RS (COnductor-like Screening MOdel for Real Solvents) predictions, also considering solvent polarity, toxicity level, and commercial availability. These predictions were also validated through σ-profile analysis and molecular dynamics simulations. Selected solvents, namely verbenone, carvacrol, and NADESs based on thymol and choline chloride, were evaluated against conventional solvents (H₂O and MeOH:H₂O). Saffron extracts were analysed using HPLC-DAD-MS, with choline chloride:ethylene glycol emerging as the most effective extractant for safranal (2.55 mg g⁻¹), comparable to MeOH:H₂O (2.56 mg g⁻¹), and superior to H₂O (1.29 mg g⁻¹). These solvents also provided the highest crocin recoveries (114.76-117.16 mg g⁻¹). Among the terpenoid-based solvents, carvacrol exhibited a higher selectivity for safranal (1.04 mg g⁻¹), with only 0.91 mg g⁻¹ for crocins.</div><div>Overall, the hydrophilic solvents were more efficient than the hydrophobic ones, finding a clear relationship between polarity and extraction capacity. These findings suggest the potential application of choline chloride:ethylene glycol NADES in the food industry for the extraction of bioactives from saffron, providing ecological benefits with low health risks and environmental impact.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1767 ","pages":"Article 466597"},"PeriodicalIF":4.0,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145665536","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}

引用次数: 0

Purification-free immobilization of dopamine D2 receptor and glucocorticoid receptor by alkyne–azide cycloaddition for affinity chromatography-based drug screening 烷基叠氮环加成法无纯化固定多巴胺D2受体和糖皮质激素受体的亲和层析药物筛选

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-12-01 DOI: 10.1016/j.chroma.2025.466596

Ruoxue Bai, Manling Li, Yingyi Zhang, Jiangwei He, Yujin Lin, Haoran Zhang, Ping Shu, Xiaojing Yan, Bo Wang, Tingting Huang, Xue Zhao, Xinfeng Zhao

Immobilized protein-based affinity chromatography offers a promising alternative for high-throughput drug screening, yet its effectiveness is often hampered by conventional immobilization techniques as they result in functional loss of the protein due to random orientation and multi-step purification. Herein, we developed a universal strategy for fabricating highly efficient chromatographic methods by integrating genetic code expansion with alkyne-azide click cycloaddition in the immobilization of dopamine D2 receptor (DRD2) and glucocorticoid receptor (GR) strain-promoted alkyne-azide cycloaddition (SPAAC). The site-specific incorporation of p-azidophenylalanine (pAzF) into the two receptors using an engineered E. coli C321.ΔA strain enabled direct, oriented, and covalent immobilization of them onto dibenzocyclooctyne (DBCO)-functionalized silica by a copper-free click reaction without the need for prior purification. The resulting immobilized DRD2_p_AzF and GR_p_AzF stationary phases were thoroughly characterized by XPS, SEM/EDS, and immunofluorescence, confirming successful immobilization and preserved receptor activity. These exhibited exceptional specificity, stability (>30 days), and reproducibility (RSD<1 %). Applications immobilized DRD2 and GR in analyzing Wendan Decoction identified liquiritigenin, neohesperidin, and naringin as active components of the prescription. Among them, liquiritigenin, neohesperidin were characterized as dual-target ligands. Determination of their binding affinities to the receptors by frontal analysis enables calculation of drug-like efficiency indices (SEI, BEI, LLE). Cellular assays in HT22 cells further confirmed their bioactivities and target specificity to the receptors. This work is possible to advance the discovery of potential leads from natural products as it has the properties of streamlining the construction of reliable receptor chromatography methods, integrating the screening with binding affinity measurement, and preliminary drug-likeness evaluation.

基于固定蛋白的亲和层析为高通量药物筛选提供了一种很有前途的选择，但其有效性经常受到传统固定技术的阻碍，因为它们会导致蛋白质因随机取向和多步骤纯化而失去功能。在此，我们开发了一种通用策略，通过整合遗传密码扩展和炔-叠氮化物点击环加成来固定多巴胺D2受体（DRD2）和糖皮质激素受体（GR）株促进的炔-叠氮化物环加成（SPAAC），以构建高效的色谱方法。利用工程化大肠杆菌C321将对叠氮苯丙氨酸（pAzF）特异地结合到这两种受体中。ΔA菌株通过无铜点击反应将它们直接、定向和共价固定在二苯并环环泰（DBCO）功能化二氧化硅上，而无需事先纯化。通过XPS、SEM/EDS和免疫荧光对固定化后的DRD2pAzF和GRpAzF固定相进行了全面的表征，证实了固定化成功并保留了受体活性。这些方法具有特殊的特异性、稳定性（30天）和重复性（rsd1 %）。应用固定化DRD2和GR对温胆汤进行分析，确定其有效成分为清肾素、新橙皮苷和柚皮苷。其中，利尿原素、新橙皮苷为双靶配体。通过正面分析确定它们与受体的结合亲和力，可以计算药物样效率指数（SEI， BEI， LLE）。HT22细胞实验进一步证实了它们的生物活性和对受体的靶向特异性。该方法简化了可靠的受体层析方法的构建，将筛选与结合亲和性测量相结合，并进行了初步的药物相似性评估，因此有可能促进从天然产物中发现潜在的线索。

{"title":"Purification-free immobilization of dopamine D2 receptor and glucocorticoid receptor by alkyne–azide cycloaddition for affinity chromatography-based drug screening","authors":"Ruoxue Bai, Manling Li, Yingyi Zhang, Jiangwei He, Yujin Lin, Haoran Zhang, Ping Shu, Xiaojing Yan, Bo Wang, Tingting Huang, Xue Zhao, Xinfeng Zhao","doi":"10.1016/j.chroma.2025.466596","DOIUrl":"10.1016/j.chroma.2025.466596","url":null,"abstract":"<div><div>Immobilized protein-based affinity chromatography offers a promising alternative for high-throughput drug screening, yet its effectiveness is often hampered by conventional immobilization techniques as they result in functional loss of the protein due to random orientation and multi-step purification. Herein, we developed a universal strategy for fabricating highly efficient chromatographic methods by integrating genetic code expansion with alkyne-azide click cycloaddition in the immobilization of dopamine D2 receptor (DRD2) and glucocorticoid receptor (GR) strain-promoted alkyne-azide cycloaddition (SPAAC). The site-specific incorporation of <em>p</em>-azidophenylalanine (<em>p</em>AzF) into the two receptors using an engineered <em>E. coli</em> C321.ΔA strain enabled direct, oriented, and covalent immobilization of them onto dibenzocyclooctyne (DBCO)-functionalized silica by a copper-free click reaction without the need for prior purification. The resulting immobilized DRD2<em><sub>p</sub></em><sub>AzF</sub> and GR<em><sub>p</sub></em><sub>AzF</sub> stationary phases were thoroughly characterized by XPS, SEM/EDS, and immunofluorescence, confirming successful immobilization and preserved receptor activity. These exhibited exceptional specificity, stability (>30 days), and reproducibility (RSD<1 %). Applications immobilized DRD2 and GR in analyzing Wendan Decoction identified liquiritigenin, neohesperidin, and naringin as active components of the prescription. Among them, liquiritigenin, neohesperidin were characterized as dual-target ligands. Determination of their binding affinities to the receptors by frontal analysis enables calculation of drug-like efficiency indices (SEI, BEI, LLE). Cellular assays in HT22 cells further confirmed their bioactivities and target specificity to the receptors. This work is possible to advance the discovery of potential leads from natural products as it has the properties of streamlining the construction of reliable receptor chromatography methods, integrating the screening with binding affinity measurement, and preliminary drug-likeness evaluation.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1766 ","pages":"Article 466596"},"PeriodicalIF":4.0,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145681974","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}

引用次数: 0

Systematic assessment of column selectivity for the isolation of subcordatine and other flavonoid glycosides from Strychnos subcordata spruce ex Benth using off-line single heart-cutting two-dimensional liquid chromatography 离线单心切割二维液相色谱法分离马钱子中马钱子碱及其他类黄酮苷的选择性评价

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-12-01 DOI: 10.1016/j.chroma.2025.466598

Rebeca dos S. França , Giovana A. Bataglion , Ana Paula A. Castro , Brenda L.C. Leocadio , Kidney de Oliveira G. Neves , Francinaldo Araujo da Silva Filho , Bruna R. Lima , Fernando Cassas , Hector H.F. Koolen , Afonso Duarte L. de Souza , Maria Lúcia B. Pinheiro , Quezia B. Cass , Felipe Moura A. da Silva

The genus Strychnos has gained worldwide recognition due to its role in the preparation of curare, a traditional arrow poison used by Indigenous peoples in South America, and its potential as a promising source of bioactive natural products. Although the phytochemical content of several Strychnos species has been extensively investigated, others, such as S. subcordata, remain largely unexplored. In this study, we describe for the first time the systematic screening of the selectivity of selected columns (C18, C8, PFP, phenyl-hexyl, CN and biphenyl) for the isolation of target compounds from the methanol fraction of S. subcordata leaves based on the off-line single heart-cutting two-dimensional liquid chromatography (2D-LC) approach. Among these compounds, an unknown isoflavone, herein named subcordatine, and two rare flavonoid glycosides containing a terminal apiosyl unit were isolated and elucidated using 1D and 2D NMR analyses, as well as MS. Among the tested configurations, the combination of a C18 column in the first dimension (¹D) and a biphenyl column in the second dimension (²D) proved particularly effective for isolating the target compounds in higher yields. Subcordatine, in particular, exhibited stronger retention on phenyl-type columns, especially the biphenyl column, likely due to conformational similarities between isoflavones and the biphenyl moieties in the stationary phase. These findings underscore the importance of specific molecular interactions in chromatographic selectivity and highlight the potential of off-line heart-cutting 2D-LC methodologies for isolating structurally complex natural products.

马钱子属因其在南美土著人民使用的传统箭毒curare的制备中所起的作用以及其作为生物活性天然产物的潜力而获得了全世界的认可。虽然几种马钱子属植物的化学成分已被广泛研究，但其他种类，如S. subcordata，仍未被广泛研究。在这项研究中，我们首次描述了基于离线单心切割二维液相色谱（2D-LC）方法，系统筛选了所选色谱柱（C18, C8， PFP，苯基己基，CN和联苯）从荆芥叶片甲醇部分分离目标化合物的选择性。在这些化合物中，分离出一种未知的异黄酮（本文命名为subcordatine）和两种罕见的含有末端apiosyl单元的黄酮类苷，并通过1D和2D NMR分析以及ms进行了鉴定。在测试的构型中，一维C18柱和二维联苯柱的组合被证明特别有效，可以分离出更高收率的目标化合物。尤其是亚cordatine，在苯基柱，特别是联苯柱上表现出更强的保留，这可能是由于异黄酮与固定相中联苯部分的构象相似。这些发现强调了特定分子相互作用在色谱选择性中的重要性，并强调了离线心脏切割2D-LC方法在分离结构复杂的天然产物方面的潜力。

{"title":"Systematic assessment of column selectivity for the isolation of subcordatine and other flavonoid glycosides from Strychnos subcordata spruce ex Benth using off-line single heart-cutting two-dimensional liquid chromatography","authors":"Rebeca dos S. França , Giovana A. Bataglion , Ana Paula A. Castro , Brenda L.C. Leocadio , Kidney de Oliveira G. Neves , Francinaldo Araujo da Silva Filho , Bruna R. Lima , Fernando Cassas , Hector H.F. Koolen , Afonso Duarte L. de Souza , Maria Lúcia B. Pinheiro , Quezia B. Cass , Felipe Moura A. da Silva","doi":"10.1016/j.chroma.2025.466598","DOIUrl":"10.1016/j.chroma.2025.466598","url":null,"abstract":"<div><div>The genus <em>Strychnos</em> has gained worldwide recognition due to its role in the preparation of curare, a traditional arrow poison used by Indigenous peoples in South America, and its potential as a promising source of bioactive natural products. Although the phytochemical content of several <em>Strychnos</em> species has been extensively investigated, others, such as <em>S. subcordata</em>, remain largely unexplored. In this study, we describe for the first time the systematic screening of the selectivity of selected columns (C18, C8, PFP, phenyl-hexyl, CN and biphenyl) for the isolation of target compounds from the methanol fraction of <em>S. subcordata</em> leaves based on the off-line single heart-cutting two-dimensional liquid chromatography (2D-LC) approach. Among these compounds, an unknown isoflavone, herein named subcordatine, and two rare flavonoid glycosides containing a terminal apiosyl unit were isolated and elucidated using 1D and 2D NMR analyses, as well as MS. Among the tested configurations, the combination of a C18 column in the first dimension (<sup>1</sup>D) and a biphenyl column in the second dimension (<sup>2</sup>D) proved particularly effective for isolating the target compounds in higher yields. Subcordatine, in particular, exhibited stronger retention on phenyl-type columns, especially the biphenyl column, likely due to conformational similarities between isoflavones and the biphenyl moieties in the stationary phase. These findings underscore the importance of specific molecular interactions in chromatographic selectivity and highlight the potential of off-line heart-cutting 2D-LC methodologies for isolating structurally complex natural products.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1766 ","pages":"Article 466598"},"PeriodicalIF":4.0,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145733284","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}

引用次数: 0

Magnetic surface molecularly imprinted polymer for selective enrichment and detection of nitrofuran metabolite residues in water 磁性表面分子印迹聚合物在水中硝基呋喃代谢物残留的选择性富集和检测。

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-11-30 DOI: 10.1016/j.chroma.2025.466593

Xiao Wang, Xinhua Li, Ruya Wang, Boyu Hao, Mengyuan Zhang, Wenchong Tang, Mingyuan Gao, Weidong Zhang

Nitrofuran metabolites are of regulatory concern due to their persistence and health risks, yet their simultaneous detection in water remains challenging. In this study, a magnetic surface molecularly imprinted polymer (MIP) was developed for the selective enrichment of four nitrofuran metabolites. A dual-template strategy using 1-aminohydantoin (AHD) and 3-amino-5-morpholinomethyl-2-oxazolidinone (AMOZ) was employed, with methacrylic acid as the functional monomer and a choline chloride–p-coumaric acid deep eutectic solvent as an auxiliary monomer. Chitosan-modified magnetic halloysite nanotubes (CS-Fe₃O₄@HNT) served as carriers, and surface imprinting polymerization was applied. The material was characterized by scanning electron microscopy, transmission electron microscopy, Fourier-transform infrared spectroscopy, and thermogravimetric analysis, confirming successful imprinting.

The adsorption conditions were optimized using single-factor and orthogonal experiments. Coupled with high-performance liquid chromatography with ultraviolet detection, a highly linear analytical method was established. Spiked recoveries from water samples (lake, aquaculture tank, and tap water) ranged from 70.83 % to 96.39 %, with relative standard deviations (RSDs) of 0.11–9.8 %. The limits of detection (LODs) and quantification (LOQs) were 0.25–0.93 ng/mL and 0.84–3.11 ng/mL, respectively. Zebrafish embryo assays confirmed that the imprinted material was non-toxic (p > 0.05), whereas nitrofuran metabolites caused developmental malformations, edema, and mortality. In co-exposure experiments, the material significantly reduced both mortality and malformation rates (p < 0.05), demonstrating excellent environmental compatibility.

This work represents the first report of a molecularly imprinted material capable of simultaneously recognizing four nitrofuran metabolites. The developed approach offers a sensitive and reliable platform for monitoring nitrofuran residues in water with potential for environmentally safe remediation.

硝基呋喃代谢物因其持久性和健康风险而受到监管关注，但在水中同时检测它们仍然具有挑战性。本研究开发了一种磁性表面分子印迹聚合物（MIP），用于选择性富集四种硝基呋喃代谢物。以甲基丙烯酸为功能单体，氯化胆碱-对香豆酸深度共熔溶剂为辅助单体，采用1-氨基酰乙酮（AHD）和3-氨基-5-氨基-甲基-2-恶唑烷酮（AMOZ）为双模板策略。以壳聚糖修饰磁性高岭土纳米管（CS-Fe3O4@HNT）为载体，采用表面印迹聚合技术。通过扫描电子显微镜、透射电子显微镜、傅里叶变换红外光谱和热重分析对材料进行了表征，证实了印迹成功。采用单因素试验和正交试验对吸附条件进行优化。结合紫外检测的高效液相色谱法，建立了高度线性的分析方法。水体样品（湖泊、养殖池和自来水）加标回收率为70.83% ~ 96.39%，相对标准偏差（rsd）为0.11 ~ 9.8%。检测限（lod）为0.25 ~ 0.93 ng/mL，定量限（loq）为0.84 ~ 3.11 ng/mL。斑马鱼胚胎试验证实，印迹物质是无毒的（p > 0.05），而硝基呋喃代谢物会导致发育畸形、水肿和死亡。在共暴露实验中，该材料显著降低了死亡率和畸形率（p < 0.05），表现出良好的环境相容性。这项工作代表了能够同时识别四种硝基呋喃代谢物的分子印迹材料的第一份报告。所开发的方法为监测水中硝基呋喃残留提供了一个敏感可靠的平台，具有环境安全修复的潜力。

{"title":"Magnetic surface molecularly imprinted polymer for selective enrichment and detection of nitrofuran metabolite residues in water","authors":"Xiao Wang, Xinhua Li, Ruya Wang, Boyu Hao, Mengyuan Zhang, Wenchong Tang, Mingyuan Gao, Weidong Zhang","doi":"10.1016/j.chroma.2025.466593","DOIUrl":"10.1016/j.chroma.2025.466593","url":null,"abstract":"<div><div>Nitrofuran metabolites are of regulatory concern due to their persistence and health risks, yet their simultaneous detection in water remains challenging. In this study, a magnetic surface molecularly imprinted polymer (MIP) was developed for the selective enrichment of four nitrofuran metabolites. A dual-template strategy using 1-aminohydantoin (AHD) and 3-amino-5-morpholinomethyl-2-oxazolidinone (AMOZ) was employed, with methacrylic acid as the functional monomer and a choline chloride–p-coumaric acid deep eutectic solvent as an auxiliary monomer. Chitosan-modified magnetic halloysite nanotubes (CS-Fe<sub>3</sub>O<sub>4</sub>@HNT) served as carriers, and surface imprinting polymerization was applied. The material was characterized by scanning electron microscopy, transmission electron microscopy, Fourier-transform infrared spectroscopy, and thermogravimetric analysis, confirming successful imprinting.</div><div>The adsorption conditions were optimized using single-factor and orthogonal experiments. Coupled with high-performance liquid chromatography with ultraviolet detection, a highly linear analytical method was established. Spiked recoveries from water samples (lake, aquaculture tank, and tap water) ranged from 70.83 % to 96.39 %, with relative standard deviations (RSDs) of 0.11–9.8 %. The limits of detection (LODs) and quantification (LOQs) were 0.25–0.93 ng/mL and 0.84–3.11 ng/mL, respectively. Zebrafish embryo assays confirmed that the imprinted material was non-toxic (<em>p</em> > 0.05), whereas nitrofuran metabolites caused developmental malformations, edema, and mortality. In co-exposure experiments, the material significantly reduced both mortality and malformation rates (<em>p</em> < 0.05), demonstrating excellent environmental compatibility.</div><div>This work represents the first report of a molecularly imprinted material capable of simultaneously recognizing four nitrofuran metabolites. The developed approach offers a sensitive and reliable platform for monitoring nitrofuran residues in water with potential for environmentally safe remediation.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1766 ","pages":"Article 466593"},"PeriodicalIF":4.0,"publicationDate":"2025-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145766536","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}

引用次数: 0

Development and application of automatic magnetic solid phase extraction assisted High-resolution mass spectrometry for sensitive and rapid determination of 26 fentanyl and metabolites in urine samples 全自动磁固相萃取辅助高分辨率质谱法快速灵敏测定尿液中26种芬太尼及其代谢物

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-11-30 DOI: 10.1016/j.chroma.2025.466594

Wanli Li , Yang Wang , Meixiang Yu , Hai Zhang , Xiaojun Deng

Over the past three decades, numerous deaths caused by the illicit use of fentanyl analogues have drawn worldwide concern. However, the detection of trace levels of fentanyl compounds remains challenging due to labor-intensive sample pretreatment, low sensitivity, and limited screening efficiency. In this study, we developed and validated a rapid and sensitive method based on high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC–MS/MS) for the simultaneous determination of 26 fentanyl analogues and metabolites in urine samples. After automated magnetic solid-phase extraction (auto-MSPE), analytes were separated on a C18 column and detected using MRM HR mode. The limits of detection (LOD) and limits of quantification (LOQ) ranged from 0.01 to 0.05 ng/mL and 0.04 to 0.1 ng/mL, respectively. This approach required only 30 min for the pretreatment of 32 urine samples, meeting routine detection requirements while achieving a green and economical workflow. Within the concentration range of 0.1–100 ng/mL (0.5–100 ng/mL for two compounds), all analytes exhibited good linearity with correlation coefficients (R² > 0.99). Accuracy ranged from 75.1 % to 117.0 %, extraction recoveries from 72.1 % to 100 %, and matrix effects from 64.2 % to 111.7 %. The method was successfully applied to the detection and quantification of fentanyl and its major metabolite norfentanyl in authentic urine samples. These results demonstrate the potential of this method for the reliable detection of fentanyl analogues in forensic and clinical toxicology.

在过去三十年中，非法使用芬太尼类似物造成的大量死亡引起了全世界的关注。然而，痕量芬太尼化合物的检测仍然具有挑战性，由于劳动密集型的样品预处理，低灵敏度和有限的筛选效率。在本研究中，我们建立并验证了一种基于高效液相色谱-串联质谱（HPLC-MS /MS）同时测定尿液样品中26种芬太尼类似物和代谢物的快速灵敏方法。自动磁固相萃取（auto-MSPE）后，分析物在C18柱上分离，用MRM HR模式检测。检测限（LOD）为0.01 ~ 0.05 ng/mL，定量限（LOQ）为0.04 ~ 0.1 ng/mL。该方法预处理32份尿样仅需30分钟，既满足常规检测要求，又实现了绿色经济的工作流程。在0.1 ~ 100 ng/mL（两种化合物为0.5 ~ 100 ng/mL）的浓度范围内，所有分析物均具有良好的线性关系，相关系数为R²>； 0.99。精密度为75.1% ~ 117.0%，萃取回收率为72.1% ~ 100%，基质效应为64.2% ~ 111.7%。该方法成功地应用于真实尿液样品中芬太尼及其主要代谢物去芬太尼的检测和定量。这些结果证明了这种方法在法医和临床毒理学中可靠检测芬太尼类似物的潜力。

{"title":"Development and application of automatic magnetic solid phase extraction assisted High-resolution mass spectrometry for sensitive and rapid determination of 26 fentanyl and metabolites in urine samples","authors":"Wanli Li , Yang Wang , Meixiang Yu , Hai Zhang , Xiaojun Deng","doi":"10.1016/j.chroma.2025.466594","DOIUrl":"10.1016/j.chroma.2025.466594","url":null,"abstract":"<div><div>Over the past three decades, numerous deaths caused by the illicit use of fentanyl analogues have drawn worldwide concern. However, the detection of trace levels of fentanyl compounds remains challenging due to labor-intensive sample pretreatment, low sensitivity, and limited screening efficiency. In this study, we developed and validated a rapid and sensitive method based on high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC–MS/MS) for the simultaneous determination of 26 fentanyl analogues and metabolites in urine samples. After automated magnetic solid-phase extraction (auto-MSPE), analytes were separated on a C18 column and detected using MRM HR mode. The limits of detection (LOD) and limits of quantification (LOQ) ranged from 0.01 to 0.05 ng/mL and 0.04 to 0.1 ng/mL, respectively. This approach required only 30 min for the pretreatment of 32 urine samples, meeting routine detection requirements while achieving a green and economical workflow. Within the concentration range of 0.1–100 ng/mL (0.5–100 ng/mL for two compounds), all analytes exhibited good linearity with correlation coefficients (R² > 0.99). Accuracy ranged from 75.1 % to 117.0 %, extraction recoveries from 72.1 % to 100 %, and matrix effects from 64.2 % to 111.7 %. The method was successfully applied to the detection and quantification of fentanyl and its major metabolite norfentanyl in authentic urine samples. These results demonstrate the potential of this method for the reliable detection of fentanyl analogues in forensic and clinical toxicology.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1766 ","pages":"Article 466594"},"PeriodicalIF":4.0,"publicationDate":"2025-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145681975","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}

引用次数: 0

PDE-5 inhibitors in complex matrices: Recent updates on pretreatment and detection methods 复杂基质中的PDE-5抑制剂：预处理和检测方法的最新进展。

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-11-29 DOI: 10.1016/j.chroma.2025.466581

Xiang-yu Tian , Miao-miao Zhang , Fu-rong Sun

Phosphodiesterase-5 (PDE-5) inhibitors are a class of drugs primarily used to treat male erectile dysfunction. Common medications include sildenafil, tadalafil, and vardenafil. However, issues such as their illegal adulteration pose significant public health concerns. Furthermore, the structural ambiguity and unknown toxicity of analogues illicitly added to health products further increase the risks associated with their use. This review summarizes sample pretreatment methods and detection techniques. Pretreatment methods include common techniques such as dissolution, dilution, protein precipitation, and liquid-liquid extraction, as well as emerging methods like magnetic solid-phase extraction, dispersive liquid-liquid microextraction, and solid-phase microextraction. The application of novel materials, such as covalent organic frameworks, multi-walled carbon nanotubes, and molecularly imprinted polymers, represents a major development direction in the evolution of pretreatment methodologies. Detection methods encompass liquid chromatography-tandem mass spectrometry, gas chromatography-mass spectrometry, and high-performance thin-layer chromatography, among others. Among these, the use of high-resolution mass spectrometry is a current research hotspot. The review critically evaluates the advantages and limitations of existing methodologies, identifies future development directions, and supports the selection of efficient analytical strategies for specific sample matrices and research purposes.

磷酸二酯酶5 （PDE-5）抑制剂是一类主要用于治疗男性勃起功能障碍的药物。常用的药物包括西地那非、他达拉非和伐地那非。然而，非法掺假等问题构成了重大的公共卫生问题。此外，非法添加到保健品中的类似物的结构不明确和毒性未知，进一步增加了与使用相关的风险。本文综述了样品的前处理方法和检测技术。预处理方法包括溶解、稀释、蛋白质沉淀、液液萃取等常用技术，以及磁固相萃取、分散液液微萃取、固相微萃取等新兴技术。新型材料的应用，如共价有机框架、多壁碳纳米管和分子印迹聚合物，代表了预处理方法发展的一个主要方向。检测方法包括液相色谱-串联质谱法、气相色谱-质谱法、高效薄层色谱法等。其中，高分辨率质谱的使用是当前的研究热点。该综述批判性地评估了现有方法的优点和局限性，确定了未来的发展方向，并支持为特定样本矩阵和研究目的选择有效的分析策略。

{"title":"PDE-5 inhibitors in complex matrices: Recent updates on pretreatment and detection methods","authors":"Xiang-yu Tian , Miao-miao Zhang , Fu-rong Sun","doi":"10.1016/j.chroma.2025.466581","DOIUrl":"10.1016/j.chroma.2025.466581","url":null,"abstract":"<div><div>Phosphodiesterase-5 (PDE-5) inhibitors are a class of drugs primarily used to treat male erectile dysfunction. Common medications include sildenafil, tadalafil, and vardenafil. However, issues such as their illegal adulteration pose significant public health concerns. Furthermore, the structural ambiguity and unknown toxicity of analogues illicitly added to health products further increase the risks associated with their use. This review summarizes sample pretreatment methods and detection techniques. Pretreatment methods include common techniques such as dissolution, dilution, protein precipitation, and liquid-liquid extraction, as well as emerging methods like magnetic solid-phase extraction, dispersive liquid-liquid microextraction, and solid-phase microextraction. The application of novel materials, such as covalent organic frameworks, multi-walled carbon nanotubes, and molecularly imprinted polymers, represents a major development direction in the evolution of pretreatment methodologies. Detection methods encompass liquid chromatography-tandem mass spectrometry, gas chromatography-mass spectrometry, and high-performance thin-layer chromatography, among others. Among these, the use of high-resolution mass spectrometry is a current research hotspot. The review critically evaluates the advantages and limitations of existing methodologies, identifies future development directions, and supports the selection of efficient analytical strategies for specific sample matrices and research purposes.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1766 ","pages":"Article 466581"},"PeriodicalIF":4.0,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145676112","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}

引用次数: 0

Hollow zeolitic imidazolate framework-8 anchored on reduced graphene oxide aerogel as adsorbent of solid-phase extraction coupled with high-performance liquid chromatography for determination of ciprofloxacin in egg 固相萃取-高效液相色谱法测定鸡蛋中环丙沙星。

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-11-29 DOI: 10.1016/j.chroma.2025.466579

Chunhua Li , Liuxin Xue , Mengyao Cui , Yimin An , Xieyang Zhang , Chao Li

The development of adsorbents in sample pretreatment technologies for detecting fluoroquinolone antibiotic residues remains a critical challenge in ensuring food safety. A hollow ZIF-8/reduced graphene oxide aerogel (HRA) is developed as an adsorbent of solid-phase extraction (SPE) in combination with high performance liquid chromatography (HPLC) to realize the efficient enrichment and trace detection of ciprofloxacin (CIP) in egg. Etched hollow ZIF-8 provides unsaturated Zn metal sites and abundant functional groups to specifically recognize CIP. Hollow ZIF-8 loaded onto reduced graphene oxide aerogel displays favorable formability and hierarchical structure, effectively improving the mass transfer effect. An exceptional adsorption capacity of CIP up to 893.1 mg·g⁻¹ realizes the effective pre-enrichment of CIP, with a low limit of detection (LOD) and limit of quantification (LOQ) are 0.042 μg·L⁻¹ and 0.14 μg·L⁻¹, respectively. Satisfactory recovery rates of 90.7 %-108.9 % with RSD<3.4 % are obtained in detecting CIP residues in egg samples. This study provides a promising approach for detecting antibiotic residues in eggs to ensure food safety.

在检测氟喹诺酮类抗生素残留的样品前处理技术中吸附剂的开发仍然是确保食品安全的关键挑战。采用空心ZIF-8/还原氧化石墨烯气凝胶（HRA）作为固相萃取（SPE）吸附剂，结合高效液相色谱（HPLC）实现鸡蛋中环丙沙星（CIP）的高效富集和痕量检测。蚀刻空心ZIF-8提供不饱和锌金属位和丰富的官能团特异性识别CIP。负载在还原氧化石墨烯气凝胶上的中空ZIF-8具有良好的成形性和层次化结构，有效地提高了传质效果。CIP的吸附量高达893.1 mg·g-1，实现了CIP的有效预富集，低检出限（LOD）为0.042 μg·L-1，定量限（LOQ）为0.14 μg·L-1。回收率为90.7% ~ 108.9%，RSD满意

{"title":"Hollow zeolitic imidazolate framework-8 anchored on reduced graphene oxide aerogel as adsorbent of solid-phase extraction coupled with high-performance liquid chromatography for determination of ciprofloxacin in egg","authors":"Chunhua Li , Liuxin Xue , Mengyao Cui , Yimin An , Xieyang Zhang , Chao Li","doi":"10.1016/j.chroma.2025.466579","DOIUrl":"10.1016/j.chroma.2025.466579","url":null,"abstract":"<div><div>The development of adsorbents in sample pretreatment technologies for detecting fluoroquinolone antibiotic residues remains a critical challenge in ensuring food safety. A hollow ZIF-8/reduced graphene oxide aerogel (HRA) is developed as an adsorbent of solid-phase extraction (SPE) in combination with high performance liquid chromatography (HPLC) to realize the efficient enrichment and trace detection of ciprofloxacin (CIP) in egg. Etched hollow ZIF-8 provides unsaturated Zn metal sites and abundant functional groups to specifically recognize CIP. Hollow ZIF-8 loaded onto reduced graphene oxide aerogel displays favorable formability and hierarchical structure, effectively improving the mass transfer effect. An exceptional adsorption capacity of CIP up to 893.1 mg·g<sup>−1</sup> realizes the effective pre-enrichment of CIP, with a low limit of detection (LOD) and limit of quantification (LOQ) are 0.042 μg·L<sup>−1</sup> and 0.14 μg·L<sup>−1</sup>, respectively. Satisfactory recovery rates of 90.7 %-108.9 % with RSD<3.4 % are obtained in detecting CIP residues in egg samples. This study provides a promising approach for detecting antibiotic residues in eggs to ensure food safety.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1766 ","pages":"Article 466579"},"PeriodicalIF":4.0,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145676157","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}

引用次数: 0

A rapid and environmental-friendly method for characterization and determination of the major sesquiterpenoid constituents in the essential oil of Nardostachys jatamansi DC. 一种快速、环境友好的方法表征和测定野檀挥发油中主要倍半萜类成分。

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-11-28 DOI: 10.1016/j.chroma.2025.466573

Ruirui Wang , Heng Zhong , Jingyun Shi , Jiaxin Lai , Wenzhi Yang , Xin Chai , Yuefei Wang , Lihua Zhang , Honghua Wu

Essential oil is a key quality marker of Nardostachys jatamansi DC. (NJ), and is one of the main application forms of NJ alone or in a prescription with efficacies such as sedative and antiarrhythmic activities. Herein, GC/EI-MS and UPC²-QTOF-MS were simultaneously applied to characterize the chemical profile of the essential oil of N. jatamansi (EONJ), and a UPC²-PDA method was further established to determine the contents of the major sesquiterpenones in EONJ. As a result, a total of 81 and 35 constituents were tentatively identified by GC/EI-MS and UPC²-QTOF-MS, respectively. Among them, there were three major sesquiterpenones, 1,8,9,10-tetradehydroaristolan-2-one, aristolone, and kanshone H were accurately identified from EONJ. Then, the modifying agent, column temperature, backpressure, flow rate, wavelength, and injection volume were optimized for a UPC²-PDA method, whose linearity, precision, repeatability, stability, and recovery were further evaluated to make sure it was accurate and feasible for quantitative determination of the 1,8,9,10-tetradehydroaristolan-2-one, aristolone, and kanshone H in 38 batches of EONJ. Their contents fell into the ranges of 0.0804–0.4876 %, 0.0201–0.0870 %, and 0.0083–0.0444 %, respectively. This study supplies a simple, rapid, and environmental-friendly UPC²-PDA method dedicated to the content determination of sesquiterpenone isomers in EONJ, with a new reference for global quality control of N. jatamansi.

精油是野藿香的重要品质标志。（NJ），是NJ单独或在处方中具有镇静和抗心律失常等功效的主要应用形式之一。本文采用GC/EI-MS和UPC2-QTOF-MS同时对野檀挥发油（EONJ）的化学成分进行了表征，并建立了UPC2-PDA方法对野檀挥发油中主要倍半萜类化合物的含量进行了测定。结果，GC/EI-MS和UPC2-QTOF-MS分别初步鉴定了81个和35个成分。其中，从EONJ中准确鉴定出1、8、9、10- tetradehydro马兜铃-2-one、马兜铃酮和kanshone H三个主要倍半萜类化合物。然后，对UPC2-PDA法的改性剂、柱温、背压、流量、波长、进样量进行优化，并对其线性度、精密度、重复性、稳定性、回收率进行评价，确保该方法准确、可行地定量测定38批EONJ中1,8,9,10-十烷基氢马兜铃酮-2- 1、马兜铃酮和康舒尼H。其含量分别为0.0804 ~ 0.4876%、0.0201 ~ 0.0870%和0.0083 ~ 0.0444%。本研究提供了一种简便、快速、环保的UPC2-PDA方法，专门用于测定白参药材中倍半萜类异构体的含量，为白参药材的全球质量控制提供新的参考依据。

{"title":"A rapid and environmental-friendly method for characterization and determination of the major sesquiterpenoid constituents in the essential oil of Nardostachys jatamansi DC.","authors":"Ruirui Wang , Heng Zhong , Jingyun Shi , Jiaxin Lai , Wenzhi Yang , Xin Chai , Yuefei Wang , Lihua Zhang , Honghua Wu","doi":"10.1016/j.chroma.2025.466573","DOIUrl":"10.1016/j.chroma.2025.466573","url":null,"abstract":"<div><div>Essential oil is a key quality marker of <em>Nardostachys jatamansi</em> DC. (NJ), and is one of the main application forms of NJ alone or in a prescription with efficacies such as sedative and antiarrhythmic activities. Herein, GC/EI-MS and UPC<sup>2</sup>-QTOF-MS were simultaneously applied to characterize the chemical profile of the essential oil of <em>N. jatamansi</em> (EONJ), and a UPC<sup>2</sup>-PDA method was further established to determine the contents of the major sesquiterpenones in EONJ. As a result, a total of 81 and 35 constituents were tentatively identified by GC/EI-MS and UPC<sup>2</sup>-QTOF-MS, respectively. Among them, there were three major sesquiterpenones, 1,8,9,10-tetradehydroaristolan-2-one, aristolone, and kanshone H were accurately identified from EONJ. Then, the modifying agent, column temperature, backpressure, flow rate, wavelength, and injection volume were optimized for a UPC<sup>2</sup>-PDA method, whose linearity, precision, repeatability, stability, and recovery were further evaluated to make sure it was accurate and feasible for quantitative determination of the 1,8,9,10-tetradehydroaristolan-2-one, aristolone, and kanshone H in 38 batches of EONJ. Their contents fell into the ranges of 0.0804–0.4876 %, 0.0201–0.0870 %, and 0.0083–0.0444 %, respectively. This study supplies a simple, rapid, and environmental-friendly UPC<sup>2</sup>-PDA method dedicated to the content determination of sesquiterpenone isomers in EONJ, with a new reference for global quality control of <em>N. jatamansi</em>.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1766 ","pages":"Article 466573"},"PeriodicalIF":4.0,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145681967","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}

引用次数: 0