Triphenylmethane dyes (TPMs) were widely used in aquaculture due to their antibacterial properties; however, their high toxicity, carcinogenicity, and environmental persistence have led to their prohibition in many countries. Nevertheless, their residues continue to be detected in various environmental media. Accurate detection remains challenging due to complex matrix interference and trace-level analysis difficulties, highlighting the urgent need for efficient, sensitive pretreatment techniques and rapid, precise detection methods. This review summarizes recent advances in the analysis of TPMs in environmental samples. It focuses on emerging advanced pretreatment methods-such as liquid-phase microextraction based on deep eutectic solvents and ionic liquids, as well as solid-phase microextraction utilizing metal-organic frameworks and molecularly imprinted polymers-alongside detection techniques including liquid chromatography-mass spectrometry and sensor technology. The review systematically evaluates the advantages of these approaches in improving selectivity, sensitivity, and environmental sustainability, while also discussing current technical limitations and future research directions.
{"title":"A review of pretreatment and analytical methods for triphenylmethane dyes in environmental samples.","authors":"Yan-Jie Wei, Yuan Zhang, Yu-Peng Zhang, Chong Liu, Yue-Xi Shao, Yi Zhai, Xiu Wang, Xue-Song Feng","doi":"10.1016/j.chroma.2026.466901","DOIUrl":"https://doi.org/10.1016/j.chroma.2026.466901","url":null,"abstract":"<p><p>Triphenylmethane dyes (TPMs) were widely used in aquaculture due to their antibacterial properties; however, their high toxicity, carcinogenicity, and environmental persistence have led to their prohibition in many countries. Nevertheless, their residues continue to be detected in various environmental media. Accurate detection remains challenging due to complex matrix interference and trace-level analysis difficulties, highlighting the urgent need for efficient, sensitive pretreatment techniques and rapid, precise detection methods. This review summarizes recent advances in the analysis of TPMs in environmental samples. It focuses on emerging advanced pretreatment methods-such as liquid-phase microextraction based on deep eutectic solvents and ionic liquids, as well as solid-phase microextraction utilizing metal-organic frameworks and molecularly imprinted polymers-alongside detection techniques including liquid chromatography-mass spectrometry and sensor technology. The review systematically evaluates the advantages of these approaches in improving selectivity, sensitivity, and environmental sustainability, while also discussing current technical limitations and future research directions.</p>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1774 ","pages":"466901"},"PeriodicalIF":4.0,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147490327","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}
Dendrobii Officinalis Flos (DOF) is the flower of Dendrobium officinale Kimura et Migo (Fam. Orchidaceae), distinguished by its uniquely shaped and elegantly pale blossoms. In recent years, this flower has attracted considerable attention in the food industry due to its pleasant flavor and rich nutritional profile. The present study investigated the effects of different drying methods-microwave drying (MD), vacuum drying (VD), hot-air drying (HAD), and vacuum freeze-drying (VFD)-on the appearance, volatile organic compounds (VOCs), and antioxidant capacity of DOF. Analysis via gas chromatography-ion mobility spectrometry (GC-IMS) identified a total of 52 VOCs across the five sample groups, including 16 alcohols, 18 aldehydes, 10 ketones, 4 esters, 1 carboxylic acid, 2 heterocyclic compounds, and 1 disulfide. The findings revealed that fresh flowers contained higher levels of VOCs such as 2-octanone and 3-methyl-1-butanol. VFD-treated flowers showed higher levels of key flavor markers (e.g., (E)-2-butenal, (E)-2-heptenal, (E)-2-pentenal), suggesting their potential as flavor enhancers. VD-treated samples retained more tea-like aromatics (e.g., (Z)-2-penten-1-ol), making them suitable for enhancing premium tea beverages. In contrast, MD and HAD resulted in noticeable color darkening and a significant loss of volatile constituents. The antioxidant activity was evaluated using two complementary assays: the 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radical cation scavenging assay and the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging assay. Fresh samples showed the strongest bioactivity, followed by VFD-treated ones. VFD was optimal for preserving morphology, flavor, and antioxidant capacity. This study provides a basis for optimizing DOF processing, with drying methods selected for specific applications.
铁皮石斛（DOF）是木村石斛（Kimura et Migo）的花。兰科植物，以其独特的形状和优雅的苍白花朵而闻名。近年来，由于其令人愉悦的风味和丰富的营养成分，这种花在食品工业中引起了相当大的关注。研究了微波干燥（MD）、真空干燥（VD）、热风干燥（HAD）和真空冷冻干燥（VFD）等不同干燥方式对DOF外观、挥发性有机化合物（VOCs）和抗氧化能力的影响。通过气相色谱离子迁移谱（GC-IMS）分析，在5个样品组中共鉴定出52种挥发性有机化合物，包括16种醇类、18种醛类、10种酮类、4种酯类、1种羧酸、2种杂环化合物和1种二硫化物。研究结果显示，鲜花含有较高水平的挥发性有机化合物，如2-辛酮和3-甲基-1-丁醇。vfd处理的花显示出更高水平的关键风味标志物(如(E)-2-丁烯醛，（E)-2-庚烯醛，(E)-2-戊烯醛），表明它们具有增强风味的潜力。vd处理的样品保留了更多的茶类芳香物质（例如，(Z)-2-戊烯-1-醇），使其适合用于增强优质茶饮料。相反，MD和HAD导致明显的颜色变暗和挥发性成分的显著损失。用2,2'-氮基-双（3-乙基苯并噻唑-6-磺酸）（ABTS）自由基清除试验和2,2-二苯基-1-吡啶肼（DPPH）自由基清除试验来评价其抗氧化活性。新鲜样品的生物活性最强，其次是vfd处理过的样品。VFD在保存形态、风味和抗氧化能力方面是最佳的。该研究为优化自由度加工提供了基础，并针对具体应用选择了干燥方法。
{"title":"Comparison of volatile organic compounds and antioxidant activity in Dendrobii Officinalis Flos under different drying methods.","authors":"Yanxin Dai, Ziran Yu, Junmei Huang, Shijia Zhang, Yuqing Liu, Shunxiang Li, Dan Huang","doi":"10.1016/j.chroma.2026.466898","DOIUrl":"https://doi.org/10.1016/j.chroma.2026.466898","url":null,"abstract":"<p><p>Dendrobii Officinalis Flos (DOF) is the flower of Dendrobium officinale Kimura et Migo (Fam. Orchidaceae), distinguished by its uniquely shaped and elegantly pale blossoms. In recent years, this flower has attracted considerable attention in the food industry due to its pleasant flavor and rich nutritional profile. The present study investigated the effects of different drying methods-microwave drying (MD), vacuum drying (VD), hot-air drying (HAD), and vacuum freeze-drying (VFD)-on the appearance, volatile organic compounds (VOCs), and antioxidant capacity of DOF. Analysis via gas chromatography-ion mobility spectrometry (GC-IMS) identified a total of 52 VOCs across the five sample groups, including 16 alcohols, 18 aldehydes, 10 ketones, 4 esters, 1 carboxylic acid, 2 heterocyclic compounds, and 1 disulfide. The findings revealed that fresh flowers contained higher levels of VOCs such as 2-octanone and 3-methyl-1-butanol. VFD-treated flowers showed higher levels of key flavor markers (e.g., (E)-2-butenal, (E)-2-heptenal, (E)-2-pentenal), suggesting their potential as flavor enhancers. VD-treated samples retained more tea-like aromatics (e.g., (Z)-2-penten-1-ol), making them suitable for enhancing premium tea beverages. In contrast, MD and HAD resulted in noticeable color darkening and a significant loss of volatile constituents. The antioxidant activity was evaluated using two complementary assays: the 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radical cation scavenging assay and the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging assay. Fresh samples showed the strongest bioactivity, followed by VFD-treated ones. VFD was optimal for preserving morphology, flavor, and antioxidant capacity. This study provides a basis for optimizing DOF processing, with drying methods selected for specific applications.</p>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1774 ","pages":"466898"},"PeriodicalIF":4.0,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147484187","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-15Epub Date: 2026-01-23DOI: 10.1016/j.chroma.2026.466737
Weiman Zhao, Longchan Liu, Wenxiang Fan, Ziwei Li, Haizhen Zhang, Linnan Li, Zhengtao Wang, Li Yang
Ginsenosides are a class of natural glycosidic compounds characterized by structural diversity and significant bioactivities, mainly derived from Panax genus plants. However, there are still challenges in achieving efficient and green separation of ginsenosides from complex plant matrices. Traditional methods often suffer from high consumption of organic solvents, poor selectivity, and complex purification processes. In this study, a boronic acid-functionalized dendritic mesoporous silica nanomaterial was constructed based on the reversible covalent interaction between boronic acid ligands and the cis-diol motifs in ginsenosides. It was used as the solid phase extraction adsorbent for the separation and purification of ginsenosides. Taking the decoction of Panax notoginseng stems and leaves as an example, the adsorption performance and impurity removal efficiency of this strategy were systematically evaluated. The key extraction parameters were optimized by single-factor experiments and Box-Behnken response surface methodology. Quantitative analysis of nine major ginsenosides using HPLC-CAD demonstrated that the developed strategy outperformed traditional macroporous resin, achieving enrichment fold of 3.4-4.0, which were nearly 2.0 times higher than those of the resin, along with adsorption recoveries of 93.5-98.7% and desorption recoveries of 88.9–97.9%. The extracted sample was further analyzed by UPLC-Q-TOF-MS. 127 ginsenosides were successfully identified, and the interference signals of non-ginsenosides were markedly reduced. The greenness evaluation by Analytical GREEnness metric and Green Analytical Procedure Index indicated that the boron affinity strategy had significant advantages in terms of environmental friendliness and process sustainability. The solid phase extraction technique based on boron-affinity materials provides a promising approach for the efficient, large-scale and green preparation of ginsenosides and other cis-diol natural products.
{"title":"A green and efficient boronate affinity solid-phase extraction strategy for ginsenosides enrichment based on dendritic mesoporous silica","authors":"Weiman Zhao, Longchan Liu, Wenxiang Fan, Ziwei Li, Haizhen Zhang, Linnan Li, Zhengtao Wang, Li Yang","doi":"10.1016/j.chroma.2026.466737","DOIUrl":"10.1016/j.chroma.2026.466737","url":null,"abstract":"<div><div>Ginsenosides are a class of natural glycosidic compounds characterized by structural diversity and significant bioactivities, mainly derived from <em>Panax</em> genus plants. However, there are still challenges in achieving efficient and green separation of ginsenosides from complex plant matrices. Traditional methods often suffer from high consumption of organic solvents, poor selectivity, and complex purification processes. In this study, a boronic acid-functionalized dendritic mesoporous silica nanomaterial was constructed based on the reversible covalent interaction between boronic acid ligands and the cis-diol motifs in ginsenosides. It was used as the solid phase extraction adsorbent for the separation and purification of ginsenosides. Taking the decoction of <em>Panax notoginseng</em> stems and leaves as an example, the adsorption performance and impurity removal efficiency of this strategy were systematically evaluated. The key extraction parameters were optimized by single-factor experiments and Box-Behnken response surface methodology. Quantitative analysis of nine major ginsenosides using HPLC-CAD demonstrated that the developed strategy outperformed traditional macroporous resin, achieving enrichment fold of 3.4-4.0, which were nearly 2.0 times higher than those of the resin, along with adsorption recoveries of 93.5-98.7% and desorption recoveries of 88.9–97.9%. The extracted sample was further analyzed by UPLC-Q-TOF-MS. 127 ginsenosides were successfully identified, and the interference signals of non-ginsenosides were markedly reduced. The greenness evaluation by Analytical GREEnness metric and Green Analytical Procedure Index indicated that the boron affinity strategy had significant advantages in terms of environmental friendliness and process sustainability. The solid phase extraction technique based on boron-affinity materials provides a promising approach for the efficient, large-scale and green preparation of ginsenosides and other cis-diol natural products.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1770 ","pages":"Article 466737"},"PeriodicalIF":4.0,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146083672","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-15Epub Date: 2026-01-26DOI: 10.1016/j.chroma.2026.466749
Yaming Sun , Shiqi Chai , Junnan Li , Chenchen Song , Hailiang Zhao , Lijun He , Dongmei Liu
Phthalate acid esters (PAEs) are ubiquitous pollutants in food, necessitating accurate detection to ensure food quality and safety. Herein, a novel MOF-199/graphene aerogel composite-derived porous carbon material (MGC) was successfully fabricated and applied as a solid-phase microextraction (SPME) coating for the efficient extraction and enrichment of trace PAEs from condiment. The MGC coating exhibits high enrichment capacity for PAEs, attributed to its hydrophobic carbon skeleton and abundant mesoporous structure. A sensitive analytical method based on headspace SPME coupled with gas chromatography-flame ionization detection was established using the MGC coated fiber. The method achieved a good linear response, low limits of detection (0.005–0.1 μg L−1), satisfactory recoveries (71.9 %-122.6 %). The intra-fiber relative standard deviations are between 0.1 % and 7.9 %, and those for inter-fiber are from 4.8 % to 11.2 %. The successful determination of PAEs in soy sauce and monosodium glutamate confirms the feasibility and practicality of the method. This work offers a novel analytical method with exceptional sensitivity and reliability, while also expanding the application of porous carbon in SPME.
{"title":"MOF-199/graphene aerogel-derived porous carbon as solid-phase microextraction coating for the highly sensitive determination of phthalate acid esters in condiments","authors":"Yaming Sun , Shiqi Chai , Junnan Li , Chenchen Song , Hailiang Zhao , Lijun He , Dongmei Liu","doi":"10.1016/j.chroma.2026.466749","DOIUrl":"10.1016/j.chroma.2026.466749","url":null,"abstract":"<div><div>Phthalate acid esters (PAEs) are ubiquitous pollutants in food, necessitating accurate detection to ensure food quality and safety. Herein, a novel MOF-199/graphene aerogel composite-derived porous carbon material (MGC) was successfully fabricated and applied as a solid-phase microextraction (SPME) coating for the efficient extraction and enrichment of trace PAEs from condiment. The MGC coating exhibits high enrichment capacity for PAEs, attributed to its hydrophobic carbon skeleton and abundant mesoporous structure. A sensitive analytical method based on headspace SPME coupled with gas chromatography-flame ionization detection was established using the MGC coated fiber. The method achieved a good linear response, low limits of detection (0.005–0.1 μg L<sup>−1</sup>), satisfactory recoveries (71.9 %-122.6 %). The intra-fiber relative standard deviations are between 0.1 % and 7.9 %, and those for inter-fiber are from 4.8 % to 11.2 %. The successful determination of PAEs in soy sauce and monosodium glutamate confirms the feasibility and practicality of the method. This work offers a novel analytical method with exceptional sensitivity and reliability, while also expanding the application of porous carbon in SPME.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1770 ","pages":"Article 466749"},"PeriodicalIF":4.0,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146090512","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-15DOI: 10.1016/j.chroma.2026.466902
Rumen Denev, Strahil Berkov
Background: Galanthamine, an AChE inhibitor marketed for symptomatic treatment of mild to moderate Alzheimer's disease, is produced by both chemical synthesis and extraction from plant of the Amaryllidoideae subfamily. There are a few validated GC-MS and HPLC-MS methods for its quantification in plant material. All of these methods apply multi-step sample preparation procedures including toxic solvents. The assessment of plant material and development of extraction methodologies from new plant sources (e.g. Hippeastrum papilio) requires validation of quantitative analytical methods considering the species alkaloid pattern.
Results: The extraction of galanthamine from H. papilio raw material was optimized selecting 0.072% of HCl water solution as the most effective extractant. An aliquot (1 µL) of the total extract (1 mL) was directly injected into the GC-MS system avoiding any purification steps with toxic solvents. Selectivity, linearity, sensitivity, precision, accuracy, stability and robustness were determined. The LLOQ and LLOD in SIM mode were found at a concentration of 10 ng/mL and 2 ng/mL, respectively. The method was used for assessment of plant raw material, alkaloid fractions and extraction effectiveness.
Significance: The method describes the fastest and simplest extraction procedure and direct aqueous injection into the GC-MS for quantification of galanthamine in plant material. As compared to the LC-MS, the use of EIMS detector provides important information and advantage in the assessment of alkaloid fractions from new plant sources of galanthamine.
{"title":"A fast and simple method for GC-MS quantification of galanthamine in Hippeastrum papilio (Ravena) Van Sheepen and assessment of its alkaloid fractions.","authors":"Rumen Denev, Strahil Berkov","doi":"10.1016/j.chroma.2026.466902","DOIUrl":"https://doi.org/10.1016/j.chroma.2026.466902","url":null,"abstract":"<p><strong>Background: </strong>Galanthamine, an AChE inhibitor marketed for symptomatic treatment of mild to moderate Alzheimer's disease, is produced by both chemical synthesis and extraction from plant of the Amaryllidoideae subfamily. There are a few validated GC-MS and HPLC-MS methods for its quantification in plant material. All of these methods apply multi-step sample preparation procedures including toxic solvents. The assessment of plant material and development of extraction methodologies from new plant sources (e.g. Hippeastrum papilio) requires validation of quantitative analytical methods considering the species alkaloid pattern.</p><p><strong>Results: </strong>The extraction of galanthamine from H. papilio raw material was optimized selecting 0.072% of HCl water solution as the most effective extractant. An aliquot (1 µL) of the total extract (1 mL) was directly injected into the GC-MS system avoiding any purification steps with toxic solvents. Selectivity, linearity, sensitivity, precision, accuracy, stability and robustness were determined. The LLOQ and LLOD in SIM mode were found at a concentration of 10 ng/mL and 2 ng/mL, respectively. The method was used for assessment of plant raw material, alkaloid fractions and extraction effectiveness.</p><p><strong>Significance: </strong>The method describes the fastest and simplest extraction procedure and direct aqueous injection into the GC-MS for quantification of galanthamine in plant material. As compared to the LC-MS, the use of EIMS detector provides important information and advantage in the assessment of alkaloid fractions from new plant sources of galanthamine.</p>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1774 ","pages":"466902"},"PeriodicalIF":4.0,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147490343","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-15Epub Date: 2026-01-22DOI: 10.1016/j.chroma.2026.466726
Yue Deng , Shuang Feng , Xiaoyan Zhang , Jiarui Zhang , Jiale Liu , Xinyue Zhou , Shimeng Fu , Yong Zhang , Lei Yin , Meiyun Shi
This study presents an innovative analytical approach utilizing ultra-performance convergence chromatography tandem mass spectrometry (UPCC-MS/MS) for the systematic separation and quantification of 20 oligomers (n = 9–28) of polyethylene glycol 1000 (PEG1K) in rat urine. A key innovation involves the use of ammonium adducts ( [M+NH₄]⁺ and [M + 2NH₄]²⁺) as precursor ions, significantly enhancing sensitivity and selectivity, particularly for higher oligomers (n > 21), where doubly charged species predominated. Coupled with a post-column compensation strategy, ionization efficiency was improved by 1–10-fold. Chromatographic separation was achieved under isocratic conditions using a green mobile phase based on supercritical CO₂ with a methanol–formic acid co-solvent, enabling efficient baseline resolution within a short runtime while minimizing organic solvent consumption. The method was validated per FDA guidelines, demonstrating excellent linearity, precision, and accuracy. Its applicability was confirmed through excretion kinetics studies in rats tail vein injection of PEG1K, revealing rapid renal clearance with 23% of the dose excreted within 4 h and cumulative excretion reaching 64% at 48 h. Green analytical chemistry metric assessments (BAGI and GEMAM) highlighted the method's superior environmental profile. This work establishes a sensitive, efficient, and sustainable platform for polymer pharmacokinetic research.
{"title":"High-throughput and green UPCC-MS/MS assay for simultaneous quantification of 20 oligomers of PEG1K coupled with ammonium adduct and post-column infusion strategies to enhance sensitivity","authors":"Yue Deng , Shuang Feng , Xiaoyan Zhang , Jiarui Zhang , Jiale Liu , Xinyue Zhou , Shimeng Fu , Yong Zhang , Lei Yin , Meiyun Shi","doi":"10.1016/j.chroma.2026.466726","DOIUrl":"10.1016/j.chroma.2026.466726","url":null,"abstract":"<div><div>This study presents an innovative analytical approach utilizing ultra-performance convergence chromatography tandem mass spectrometry (UPCC-MS/MS) for the systematic separation and quantification of 20 oligomers (<em>n</em> = 9–28) of polyethylene glycol 1000 (PEG1K) in rat urine. A key innovation involves the use of ammonium adducts ( [M+NH₄]⁺ and [M + 2NH₄]²⁺) as precursor ions, significantly enhancing sensitivity and selectivity, particularly for higher oligomers (<em>n</em> > 21), where doubly charged species predominated. Coupled with a post-column compensation strategy, ionization efficiency was improved by 1–10-fold. Chromatographic separation was achieved under isocratic conditions using a green mobile phase based on supercritical CO₂ with a methanol–formic acid co-solvent, enabling efficient baseline resolution within a short runtime while minimizing organic solvent consumption. The method was validated per FDA guidelines, demonstrating excellent linearity, precision, and accuracy. Its applicability was confirmed through excretion kinetics studies in rats tail vein injection of PEG1K, revealing rapid renal clearance with 23% of the dose excreted within 4 h and cumulative excretion reaching 64% at 48 h. Green analytical chemistry metric assessments (BAGI and GEMAM) highlighted the method's superior environmental profile. This work establishes a sensitive, efficient, and sustainable platform for polymer pharmacokinetic research.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1770 ","pages":"Article 466726"},"PeriodicalIF":4.0,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146090510","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-15Epub Date: 2026-01-23DOI: 10.1016/j.chroma.2026.466746
Daniel Frerichs , Alexandra Höltzel , Andreas Steinhoff , Fabrice Gritti , Kevin D. Wyndham , Thomas H. Walter , Ulrich Tallarek
As a first step towards predicting retention for mixed-mode liquid chromatography (MMLC) separations of small, hydrophilic, ionizable analytes, we created a slit-pore model of a silica-based, endcapped, reversed-phase/anion-exchange (RP/AEX) stationary phase and performed molecular dynamics simulations of its solvation by a water‒acetonitrile (W‒ACN) mobile phase under conditions where the AEX function is neutral or charged. In the latter case, sodium and chloride ions were added as co-ions and counterions, respectively, to the 60/40 (v/v) W/ACN mobile phase. The silica surface functionalization, which modeled existing column technology, yielded a unique surface topology, where bonded-phase islands formed by octadecylsilyl chains around a central tertiary alkylamine group are interspersed with hydroxylated silica patches that are exposed to the mobile phase. The two MMLC systems were analyzed regarding the solvent density, structure, and orientation with respect to the density distribution of hydrophobic and hydrophilic bonded-phase elements (alkyl groups and nitrogen atoms, respectively) at different distances from the silica surface. Effects originating from the surface functionalization were captured by comparison with a conventional RPLC stationary phase, whereas effects originating from the presence of charge were quantified by comparing the two simulated MMLC systems (neutral vs. charged surface). The analysis of ion density distributions and ion contact profiles, in particular, suggested that the surface topology of the MMLC stationary phase shields the AEX function from contact with hydrophilic counterions and favors the accumulation of analyte compounds with both hydrophobic and hydrophilic structural elements.
{"title":"Molecular dynamics simulations of mixed-mode chromatography: Generation and solvation of a silica-based, reversed-phase/anion-exchange stationary phase","authors":"Daniel Frerichs , Alexandra Höltzel , Andreas Steinhoff , Fabrice Gritti , Kevin D. Wyndham , Thomas H. Walter , Ulrich Tallarek","doi":"10.1016/j.chroma.2026.466746","DOIUrl":"10.1016/j.chroma.2026.466746","url":null,"abstract":"<div><div>As a first step towards predicting retention for mixed-mode liquid chromatography (MMLC) separations of small, hydrophilic, ionizable analytes, we created a slit-pore model of a silica-based, endcapped, reversed-phase/anion-exchange (RP/AEX) stationary phase and performed molecular dynamics simulations of its solvation by a water‒acetonitrile (W‒ACN) mobile phase under conditions where the AEX function is neutral or charged. In the latter case, sodium and chloride ions were added as co-ions and counterions, respectively, to the 60/40 (v/v) W/ACN mobile phase. The silica surface functionalization, which modeled existing column technology, yielded a unique surface topology, where bonded-phase islands formed by octadecylsilyl chains around a central tertiary alkylamine group are interspersed with hydroxylated silica patches that are exposed to the mobile phase. The two MMLC systems were analyzed regarding the solvent density, structure, and orientation with respect to the density distribution of hydrophobic and hydrophilic bonded-phase elements (alkyl groups and nitrogen atoms, respectively) at different distances from the silica surface. Effects originating from the surface functionalization were captured by comparison with a conventional RPLC stationary phase, whereas effects originating from the presence of charge were quantified by comparing the two simulated MMLC systems (neutral vs. charged surface). The analysis of ion density distributions and ion contact profiles, in particular, suggested that the surface topology of the MMLC stationary phase shields the AEX function from contact with hydrophilic counterions and favors the accumulation of analyte compounds with both hydrophobic and hydrophilic structural elements.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1770 ","pages":"Article 466746"},"PeriodicalIF":4.0,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146090509","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-15Epub Date: 2026-01-22DOI: 10.1016/j.chroma.2026.466731
Miroslav Lísa , Roman Hájek
Gangliosides are biologically significant molecules with essential physiological roles in the organism. They are increasingly studied as biomarkers for disease diagnosis and progression. Due to their extreme structural diversity and typically low abundance in biological samples, efficient and sensitive liquid chromatography–mass spectrometry (LC-MS) methods are required for their analysis. In this study, we present a comprehensive comparison of the performance of two widely used LC-MS approaches: reversed-phase (RP) and hydrophilic interaction liquid chromatography (HILIC). Both methods were independently optimized following an identical protocol, with a focus on chromatographic performance and MS response. Notably, salt concentration had a pronounced impact on ganglioside retention, peak shape, isomer separation, and MS signal intensity in both chromatographic modes. In HILIC, adjusting the initial gradient composition and profile enabled effective separation of gangliosides from highly abundant matrix lipids. The RP method demonstrated superior ganglioside signal intensity and a 3.5-fold reduction in analysis time. Both approaches allowed the separation of gangliosides based on the number of sialic acid and saccharide residues. Additionally, the RP method enabled separation according to ceramide composition. We established rules for RP separation based on the number of carbon atoms in the ceramide moiety, which can be used to predict ganglioside retention times. Based on our findings, each method offers distinct advantages for specific analytical goals. The HILIC approach is better suited for untargeted ganglioside profiling using accurate m/z and interclass separation, while the RP method is ideal for sensitive, high-throughput targeted analysis in complex biological matrices.
{"title":"Comprehensive evaluation of reversed-phase and hydrophilic interaction liquid chromatography – mass spectrometry for analysis of gangliosides","authors":"Miroslav Lísa , Roman Hájek","doi":"10.1016/j.chroma.2026.466731","DOIUrl":"10.1016/j.chroma.2026.466731","url":null,"abstract":"<div><div>Gangliosides are biologically significant molecules with essential physiological roles in the organism. They are increasingly studied as biomarkers for disease diagnosis and progression. Due to their extreme structural diversity and typically low abundance in biological samples, efficient and sensitive liquid chromatography–mass spectrometry (LC-MS) methods are required for their analysis. In this study, we present a comprehensive comparison of the performance of two widely used LC-MS approaches: reversed-phase (RP) and hydrophilic interaction liquid chromatography (HILIC). Both methods were independently optimized following an identical protocol, with a focus on chromatographic performance and MS response. Notably, salt concentration had a pronounced impact on ganglioside retention, peak shape, isomer separation, and MS signal intensity in both chromatographic modes. In HILIC, adjusting the initial gradient composition and profile enabled effective separation of gangliosides from highly abundant matrix lipids. The RP method demonstrated superior ganglioside signal intensity and a 3.5-fold reduction in analysis time. Both approaches allowed the separation of gangliosides based on the number of sialic acid and saccharide residues. Additionally, the RP method enabled separation according to ceramide composition. We established rules for RP separation based on the number of carbon atoms in the ceramide moiety, which can be used to predict ganglioside retention times. Based on our findings, each method offers distinct advantages for specific analytical goals. The HILIC approach is better suited for untargeted ganglioside profiling using accurate <em>m/z</em> and interclass separation, while the RP method is ideal for sensitive, high-throughput targeted analysis in complex biological matrices.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1770 ","pages":"Article 466731"},"PeriodicalIF":4.0,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146083746","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-15Epub Date: 2026-01-20DOI: 10.1016/j.chroma.2026.466720
Doreen N.B Chandra Siri , Si Ling Ng , Ngee Sing Chong , Philip J. Marriott , Yong Foo Wong
Atmospheric-pressure solids analysis probe (ASAP) is an ambient pressure ionisation mass spectrometry technique that allows the direct analysis of liquids and solids, with or without sample preparation, producing rapid, efficient, and real-time results. In this study, portable ASAP−quadrupole mass spectrometry (ASAP−QMS) method in positive ion mode was demonstrated for the rapid analysis of 9 drugs of abuse (amphetamine, methamphetamine, oxycodone, methadone, morphine, 3,4-methylenedioxymethamphetamine, ketamine, 6-monoacetylmorphine, and cocaine), fortified in water and urine samples, with analysis time of ∼30 s. Initially, a direct analysis approach without sample preparation was applied to fortified water and urine samples. However, significant urine matrix effects were observed, leading to ion suppression and detector saturation. A simple solid-phase extraction (SPE) procedure was then applied to reduce matrix effects arising from the urine samples. The influence of cone voltages on the fragmentation and abundance of molecular ions for the illicit compounds was evaluated. The analytes exhibited limits of detection in the range of 0.3 – 2 µg mL-1, which were considerably higher than the UPLC−ESIMS (0.05 – 0.1 µg mL-1) method. Drug compounds identification was performed via MS spectrum matching against an in-house database. Comparative assessment with UPLC−ESI linear ion trap MS using United Nations Office on Drugs and Crime International Collaborative Exercises urine samples showed detection accuracies of 43% for ASAP−QMS and 100% for the UPLC−MS method. The lower accuracy of ASAP−QMS was attributed to the poor spectral library matching (similarity scores < 850) in complex urine matrices, particularly for low-concentration drug compounds. Nevertheless, portable ASAP−QMS (with SPE) achieved a higher greenness assessment score (0.54) compared to UPLC−MS (0.37), highlighting its potential as a rapid and environmentally friendly drug screening approach.
{"title":"Evaluation of portable atmospheric-pressure solids analysis probe–quadrupole mass spectrometry and UPLC−MS for the rapid screening of illicit substances in human urine","authors":"Doreen N.B Chandra Siri , Si Ling Ng , Ngee Sing Chong , Philip J. Marriott , Yong Foo Wong","doi":"10.1016/j.chroma.2026.466720","DOIUrl":"10.1016/j.chroma.2026.466720","url":null,"abstract":"<div><div>Atmospheric-pressure solids analysis probe (ASAP) is an ambient pressure ionisation mass spectrometry technique that allows the direct analysis of liquids and solids, with or without sample preparation, producing rapid, efficient, and real-time results. In this study, portable ASAP−quadrupole mass spectrometry (ASAP−QMS) method in positive ion mode was demonstrated for the rapid analysis of 9 drugs of abuse (amphetamine, methamphetamine, oxycodone, methadone, morphine, 3,4-methylenedioxymethamphetamine, ketamine, 6-monoacetylmorphine, and cocaine), fortified in water and urine samples, with analysis time of ∼30 s. Initially, a direct analysis approach without sample preparation was applied to fortified water and urine samples. However, significant urine matrix effects were observed, leading to ion suppression and detector saturation. A simple solid-phase extraction (SPE) procedure was then applied to reduce matrix effects arising from the urine samples. The influence of cone voltages on the fragmentation and abundance of molecular ions for the illicit compounds was evaluated. The analytes exhibited limits of detection in the range of 0.3 – 2 µg mL<sup>-1</sup>, which were considerably higher than the UPLC−ESIMS (0.05 – 0.1 µg mL<sup>-1</sup>) method. Drug compounds identification was performed via MS spectrum matching against an in-house database. Comparative assessment with UPLC−ESI linear ion trap MS using United Nations Office on Drugs and Crime International Collaborative Exercises urine samples showed detection accuracies of 43% for ASAP−QMS and 100% for the UPLC−MS method. The lower accuracy of ASAP−QMS was attributed to the poor spectral library matching (similarity scores < 850) in complex urine matrices, particularly for low-concentration drug compounds. Nevertheless, portable ASAP−QMS (with SPE) achieved a higher greenness assessment score (0.54) compared to UPLC−MS (0.37), highlighting its potential as a rapid and environmentally friendly drug screening approach.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1770 ","pages":"Article 466720"},"PeriodicalIF":4.0,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048916","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-15Epub Date: 2026-01-21DOI: 10.1016/j.chroma.2026.466727
Ahmed Serag , Manal E. Alosaimi , Maram H Abduljabbar , Adnan Alharbi , Faisal Alsenani , Farooq M. Almutairi , Muneef M. Aldhafeeri , Atiah H. Almalki
A sustainable salting-out assisted liquid-liquid extraction coupled with liquid chromatography-tandem mass spectrometry (SALLE-LC-MS/MS) method was developed and validated for amisulpride quantification in human plasma according to ICH M10 guidelines. Box-Behnken experimental design systematically optimized SALLE parameters through evaluation of sample pH (5.0–10.0), acetonitrile volume (500–1500 μL), salt concentration (2.0–6.0 mol/L), and centrifugation time (3.0–10.0 min). The developed polynomial model demonstrated strong predictive capability with subsequent numerical optimization identifying optimal conditions of pH 8.5, acetonitrile 1200 μL, ammonium acetate 4.5 mol/L, and 3-minute centrifugation. These conditions achieved 97.6% extraction recovery for amisulpride with minimal deviation from predicted values. Following optimization, chromatographic separation was achieved using a C18 column with isocratic elution (acetonitrile:water with 0.1% formic acid, 70:30 v/v) and 4-minute analysis time, with multiple reaction monitoring employing transitions m/z370.1→242.1 for amisulpride and m/z376.2→165.1 for haloperidol internal standard. Comprehensive validation subsequently demonstrated linearity across 2–1500 ng/mL with acceptable accuracy, precision, and stability under clinical storage conditions. Matrix effects ranged from 88–105% with low variability, while extraction recovery exceeded 98% across all quality control levels. Clinical application in healthy volunteers (n = 5) following 200 mg oral amisulpride administration successfully characterized key pharmacokinetic parameters including Cmax (506 ng/mL), tmax (3.8 h), and t1/2 (13.3 h) over 48 h. Finally, multi-metric sustainability assessment using CaFRI (75/100), BAGI (77.5/100), and RGB12 (83.1/100 whiteness) frameworks confirmed achievement of white analytical chemistry through balanced analytical performance, environmental friendliness, and practical implementation feasibility. The method offers significant advantages including minimal waste generation, reduced solvent consumption, and enhanced throughput while maintaining regulatory compliance for amisulpride therapeutic drug monitoring applications.
{"title":"Box-Behnken optimized salting-out assisted liquid-liquid extraction coupled with LC-MS/MS for sustainable amisulpride quantification in human plasma","authors":"Ahmed Serag , Manal E. Alosaimi , Maram H Abduljabbar , Adnan Alharbi , Faisal Alsenani , Farooq M. Almutairi , Muneef M. Aldhafeeri , Atiah H. Almalki","doi":"10.1016/j.chroma.2026.466727","DOIUrl":"10.1016/j.chroma.2026.466727","url":null,"abstract":"<div><div>A sustainable salting-out assisted liquid-liquid extraction coupled with liquid chromatography-tandem mass spectrometry (SALLE-LC-MS/MS) method was developed and validated for amisulpride quantification in human plasma according to ICH M10 guidelines. Box-Behnken experimental design systematically optimized SALLE parameters through evaluation of sample pH (5.0–10.0), acetonitrile volume (500–1500 μL), salt concentration (2.0–6.0 mol/L), and centrifugation time (3.0–10.0 min). The developed polynomial model demonstrated strong predictive capability with subsequent numerical optimization identifying optimal conditions of pH 8.5, acetonitrile 1200 μL, ammonium acetate 4.5 mol/L, and 3-minute centrifugation. These conditions achieved 97.6% extraction recovery for amisulpride with minimal deviation from predicted values. Following optimization, chromatographic separation was achieved using a C18 column with isocratic elution (acetonitrile:water with 0.1% formic acid, 70:30 v/v) and 4-minute analysis time, with multiple reaction monitoring employing transitions <em>m/z</em>370.1→242.1 for amisulpride and <em>m/z</em>376.2→165.1 for haloperidol internal standard. Comprehensive validation subsequently demonstrated linearity across 2–1500 ng/mL with acceptable accuracy, precision, and stability under clinical storage conditions. Matrix effects ranged from 88–105% with low variability, while extraction recovery exceeded 98% across all quality control levels. Clinical application in healthy volunteers (<em>n</em> = 5) following 200 mg oral amisulpride administration successfully characterized key pharmacokinetic parameters including C<sub>max</sub> (506 ng/mL), t<sub>max</sub> (3.8 h), and t<sub>1/2</sub> (13.3 h) over 48 h. Finally, multi-metric sustainability assessment using CaFRI (75/100), BAGI (77.5/100), and RGB12 (83.1/100 whiteness) frameworks confirmed achievement of white analytical chemistry through balanced analytical performance, environmental friendliness, and practical implementation feasibility. The method offers significant advantages including minimal waste generation, reduced solvent consumption, and enhanced throughput while maintaining regulatory compliance for amisulpride therapeutic drug monitoring applications.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1770 ","pages":"Article 466727"},"PeriodicalIF":4.0,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146090511","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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