Journal of Chromatography A最新文献

{"title":"Developing 2D mzCompare for single comprehensive two-dimensional chromatography time-of-flight mass spectrometry chromatograms: Substantial resolution enhancement in the context of statistical overlap theory","authors":"Wenjing Ma,&nbsp;Caitlin N. Cain,&nbsp;Robert E. Synovec","doi":"10.1016/j.chroma.2025.466669","DOIUrl":"10.1016/j.chroma.2025.466669","url":null,"abstract":"<div><div>Accurate identification of all detectable analyte components in a single comprehensive two-dimensional (2D) gas chromatography time-of-flight mass spectrometry (GC × GC-TOFMS) chromatogram is a fundamental interest in the field. While commercial software tools intended for this purpose are available, the performance of these tools to generate an accurate peak table has generally not been validated. To address this, we developed a new algorithmic software approach called 2D mzCompare to generate accurate peak tables for GC × GC-TOFMS. Extending from our original method for one-dimensional GC–MS data, the 2D mzCompare algorithm discovers selective mass channels (<em>m/z</em>) for each analyte to resolve overlapping peaks and improve analyte identification, by leveraging the similarity in retention time and peak shape across <em>m/z</em> of the same analyte. The 2D mzCompare algorithm calculates the peak shape similarity between <em>m/z</em> at every modulation, followed by clustering and focusing steps, to generate a final peak table. To evaluate this software, we simulated realistic GC × GC-TOFMS data in the context of the statistical overlap theory (SOT), so the exact number and identities of analytes are known <em>a priori</em>. Utilizing an in-house mass spectrum library of similar compounds, GC × GC-TOFMS chromatograms were simulated with varying degrees of 2D chromatographic saturation (<span><math><msub><mi>α</mi><mrow><mn>2</mn><mi>D</mi></mrow></msub></math></span>). At low saturation factors (<span><math><msub><mi>α</mi><mrow><mn>2</mn><mi>D</mi></mrow></msub></math></span> = 0.01, 0.03, and 0.1), over 95% of the simulated components are found to be mathematically resolved singlets (pure analyte components) by 2D mzCompare. Meanwhile, approximately 62% were found at <span><math><msub><mi>α</mi><mrow><mn>2</mn><mi>D</mi></mrow></msub></math></span> = 1, exceeding predictions made by SOT. Application of 2D mzCompare computationally reduces the ²D peak widths, resulting in an ∼12-fold reduction in <span><math><msub><mi>α</mi><mrow><mn>2</mn><mi>D</mi></mrow></msub></math></span>. The results of this research are simultaneously two-fold. First, we provide a new algorithmic approach, 2D mzCompare, to resolve overlapped analytes in GC × GC-TOFMS data, and second, we validate the accuracy of the software performance using SOT.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1769 ","pages":"Article 466669"},"PeriodicalIF":4.0,"publicationDate":"2026-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145909699","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}

{"title":"Development of a green analytical method based on a Montmorillonite/Hydroxyapatite composite coupled with rotating disk sorptive extraction and GC–MS for monitoring steroid hormones in hospital wastewater","authors":"Maby Moll Martínez-Garzón ,&nbsp;José Martin Posada-Lotero ,&nbsp;Milton Hernando Rosero-Moreano ,&nbsp;Elisabeth Restrepo-Parra ,&nbsp;Francy Nelly Jiménez-García","doi":"10.1016/j.chroma.2026.466722","DOIUrl":"10.1016/j.chroma.2026.466722","url":null,"abstract":"<div><div>Environmental concern regarding the presence of steroid hormones in hospital wastewater treatment plants underscores the need for effective monitoring and removal strategies. Even at trace levels, steroid estrogens exhibit strong biological activity and bioaccumulation potential, classifying them as endocrine-disrupting compounds. In this study, a Montmorillonite/Hydroxyapatite (MMT/HAp) composite was proposed as an environmentally friendly and low-cost alternative for the extraction of estrone (E1), 17β-estradiol (E2), 17α-ethinylestradiol (EE2), and estriol (E3). Sample preparation was carried out using a green analytical method based on rotating disk sorptive extraction. Considering the complexity of wastewater matrices, analytes were determined using gas chromatography coupled to mass spectrometry (GC–MS) in selective ion monitoring mode. A Doehlert experimental design was applied to optimize the extraction process, yielding the following optimal conditions: extraction time of 87 min, sample volume of 16 mL, and stirring speed of 1080 rpm. Hospital wastewater samples from Manizales (Caldas, Colombia) were analyzed, and concentrations of E1, E2, EE2, and E3 were 7.2, 0.1, 6.7, and 33.2 µg L⁻¹, respectively. Limits of detection ranged from 0.06 to 0.40 µg L⁻¹, and limits of quantification from 0.16 to 1.20 µg L⁻¹. Calibration curves for all analytes showed R² values above 0.98. Recovery values obtained through standard addition calibration ranged from 56 % to 90 %, despite significant matrix effects (–67 to 230). The MMT/HAp composite demonstrated comparable performance to the commercial HLB sorbent, confirming its potential for environmental applications.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1769 ","pages":"Article 466722"},"PeriodicalIF":4.0,"publicationDate":"2026-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146045902","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}

{"title":"Exploring adsorption–desorption kinetics and eddy dispersion in enantioselective hydrophilic interaction chromatography using teicoplanin-based chiral stationary phase","authors":"Chiara De Luca ,&nbsp;Chiara Nosengo ,&nbsp;Amirmohammad Faraji Shovey ,&nbsp;Antonio Ricci ,&nbsp;Martina Catani ,&nbsp;Alberto Cavazzini ,&nbsp;Fabrice Gritti ,&nbsp;Simona Felletti","doi":"10.1016/j.chroma.2026.466702","DOIUrl":"10.1016/j.chroma.2026.466702","url":null,"abstract":"<div><div>This research examined the kinetic behavior of two chiral probes (FMOC-Alanine and Haloxyfop) using a zwitterionic teicoplanin-based column and an aqueous-methanol mobile phase. More specifically, experimental results, supported by literature data measured using the same elution mode, indicate that the presence of a water layer adsorbed on the particle surface hinders analyte surface diffusion leading to localized adsorption. This shows cascading effects on longitudinal diffusion, solid–liquid mass transfer resistance and eddy dispersion, which become analyte-independent. The only difference in the measured plate heights is therefore given only by slow adsorption–desorption kinetics, confirming an important correlation between analyte structure and the extent of band broadening in chiral chromatography.</div><div>The findings reported in this study can be expanded to other molecules, suggesting that similar kinetic behavior could be expected if the same experimental conditions are maintained (e.g., same column manufacturer, silica particles, and elution mode). This would help accelerating the method development and the understanding of both the chiral recognition mechanism and the sources of band broadening occurring in chiral chromatography.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1769 ","pages":"Article 466702"},"PeriodicalIF":4.0,"publicationDate":"2026-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145973877","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}

{"title":"Efficient analysis of sodium chromate by combining phase-transfer headspace strategy and GC-TCD","authors":"Wei-Qi Xie,&nbsp;Ya-Yun Wang,&nbsp;Yi-Xan Gong","doi":"10.1016/j.chroma.2025.466657","DOIUrl":"10.1016/j.chroma.2025.466657","url":null,"abstract":"<div><div>This study developed a gas-evolving phase-transfer strategy for precise sodium chromate quantification. The analytical approach utilized the chemical reaction between sodium chromate and oxalic acid to generate measurable carbon dioxide, which was subsequently quantified via headspace gas chromatography equipped with thermal conductivity detector (HS-GC-TCD). Experimental validation confirmed the method's exceptional analytical performance in sodium chromate determination. The developed phase transformation technique established a robust and efficient protocol for sodium chromate assessment while simultaneously creating a framework for extending this analytical paradigm to other gas-evolving compounds.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1769 ","pages":"Article 466657"},"PeriodicalIF":4.0,"publicationDate":"2026-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145973879","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}

{"title":"Comparative assessment of feature and component profiling workflow for supercritical fluid chromatography – high resolution mass spectrometry analysis","authors":"Samuele Pellacani ,&nbsp;Giorgio Tomasi ,&nbsp;Gerrit Renner ,&nbsp;Selina Tisler","doi":"10.1016/j.chroma.2026.466730","DOIUrl":"10.1016/j.chroma.2026.466730","url":null,"abstract":"<div><div>Supercritical fluid chromatography coupled to high-resolution mass spectrometry (SFC<img>HRMS) is gaining attention for non-target screening (NTS), yet systematic evaluations of data-processing workflows remain scarce. Here, we present the first comprehensive comparison between a component-profile (CP) approach based on Region of Interest analysis combined with Component Detection Algorithm and Multivariate Curve Resolution (ROI-CODA-MCR) and a feature-profile (FP) workflow, MS-DIAL. Using extracted ion chromatograms (EICs) as ground truth, both workflows were optimized and benchmarked for standard detection, peak intensity reliability, blank filtering performance, and suspect screening for wastewater samples. Both detected a comparable number of standards (33–35 out of 37) but ROI-derived intensities closely matched EICs (average ratio ≈1, RSD = 5.8%), while MS-DIAL intensities deviated substantially (up to two orders of magnitude, RSD &gt;200%). In non-target analysis, MS-DIAL produced ≈1000 features with many false positives, while ROI-CODA-MCR yielded ≈200 components with lower blank contributions and superior resolution of in-source fragments and adducts. MS-DIAL detected more suspect compounds, highlighting a higher risk of false negatives in the CP approach, particularly for low-intensity or sparse signals. Our results demonstrate that SFC<img>HRMS datasets, often including intense background signals, challenge key assumptions underlying both FP and CP workflows and necessitate careful parameter optimization.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1769 ","pages":"Article 466730"},"PeriodicalIF":4.0,"publicationDate":"2026-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146045905","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}

{"title":"Simultaneous quantification of cytidine, methylcytidine, and hydroxymethylcytidine by isotope-dilution LC–MS/MS with application to mouse liver samples","authors":"Pooja Mishra ,&nbsp;Jing Ma ,&nbsp;Huan Xie ,&nbsp;Fang Li ,&nbsp;Robert Y.L. Tsai ,&nbsp;Dong Liang","doi":"10.1016/j.chroma.2026.466721","DOIUrl":"10.1016/j.chroma.2026.466721","url":null,"abstract":"<div><div>DNA methylation and hydroxymethylation are important epigenetic modifications that play key roles in cancer development and aging processes by regulating gene expression and genome stability. Traditionally, bisulfite conversion-based or antibody-based enzyme-linked immunosorbent assays are used to find DNA methylation. These tests are non specific, tedious, and not able to differentiate the difference between methylation and hydroxymethylation. To address these issues, we developed a sensitive, reproducible, and specific LC–MS/MS method for simultaneous quantification of two major DNA methylation products, 5-methyl-2′-deoxycytidine (5-mdC) and 5-hydroxymethyl-2′-deoxycytidine (5-hmdC), as well as 2′-deoxycytidine (2-dC), using corresponding stable isotope-labeled internal standards: 5-methyl-2′-deoxycytidine-d₃, 5-(hydroxymethyl)-2′-deoxycytidine-d₃, and 2′-deoxycytidine-¹³C,¹⁵N₂. We purified DNA samples from mouse liver tissue, broke them down with enzymes, filtered them, added internal standards, and then run them through a SCIEX 6500+ Triple Quad LC–MS/MS system with an Atlantis T3 C18 column under a binary gradient. The method showed great chromatographic separation and specificity, with MRM transitions of m/z 228.154 to 112.1 for 2-dC, 242.143 to 126.2 for 5-mdC, and 258.135 to 142.1 for 5-hmdC.Peak area ratio of analyte to internal standard exhibited linearity across calibration ranges of 5–5000 ng /mL for 2-dC, 0.5–500 ng/ mL for 5-mdC, and 0.05–10 ng/mL for 5-hmdC (R² &gt; 0.999), using 2 µL injection and a total runtime of 9 min. The 5-hmdC level in female mouse liver significantly increased with aging from two to sixteen months old (0.0958 % to 0.1984 %; <em>P</em> <em>&lt;</em> <em>0.001</em>), whereas 5-mdC remained unchanged (3.47 % to 3.56 %; n.s.). These data confirm the accurate and reproducible quantification of DNA methylation and hydroxymethylation in tissue samples using the developed LC-MS/MS assay and indicate a broad application to cell culture and clinical biomarker studies.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1769 ","pages":"Article 466721"},"PeriodicalIF":4.0,"publicationDate":"2026-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146045931","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}

{"title":"Determination of 15 phthalates metabolites and 9 bisphenols in human serum by using high-performance liquid chromatography coupled with tandem mass spectrometry","authors":"Yilin Liu ,&nbsp;Juan Wen ,&nbsp;Xu Zhang ,&nbsp;Xiao Lin ,&nbsp;Zhuangzhuang Feng ,&nbsp;Dejun Bao ,&nbsp;Xiaojian Hu ,&nbsp;Ying Zhu","doi":"10.1016/j.chroma.2026.466728","DOIUrl":"10.1016/j.chroma.2026.466728","url":null,"abstract":"<div><div>Endocrine disrupting chemicals (EDCs) are a class of emerging contaminants that have raised significant public health concerns. Human co-exposure to mixtures of specific EDCs, such as phthalate and bisphenols, and the associated health risks remain poorly understood. To support biomonitoring and epidemiological studies on these compounds, there is a critical need for sensitive and reliable methods for their quantification in human specimens. Herein, we developed and validated an analytical method based on ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) for the simultaneous determination of 15 phthalate metabolites and 9 bisphenols in human serum. A systematic comparison between liquid-liquid extraction (LLE) and high-efficiency matrix removal (HMR) clean-up approach revealed that HMR offered advantages in terms of extraction efficiency and matrix effect reduction, and was ultimately selected as the final clean-up method for this study. The developed method demonstrated satisfactory performance, with recoveries ranging from 81 % to 115 %, with the relative standard deviations (RSD) below 18 %. The calibration curves established using isotope-labeled internal standards exhibited good linearity, with correlation coefficients (<em>R²</em>) consistently above 0.997. The limits of detection (LODs) and limits of quantification (LOQs) were determined to be in the range of 0.01 ng/mL to 0.2 ng/mL and 0.04 ng/mL to 0.7 ng/mL, respectively. Both intra-day and inter-day precision were satisfactory, with RSDs values ranging from 4.2 % to 13 % and 6.9 % to 14 %, respectively. This sensitive analytical method was successfully applied to the determination of target analytes in human serum samples from 15 pregnant women, demonstrating its applicability for monitoring of these emerging contaminants in human serum.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1769 ","pages":"Article 466728"},"PeriodicalIF":4.0,"publicationDate":"2026-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146023325","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}

{"title":"Reversed-phase chromatography of peptides carrying non-canonical proline analogues, with special focus on 4R/4S-fluoroproline","authors":"Alexandre Prefontaine ,&nbsp;Justin Liba ,&nbsp;Vic Spicer ,&nbsp;Suvrat Chowdhary ,&nbsp;Christin Treiber-Kleinke ,&nbsp;Vladimir Kubyshkin ,&nbsp;Beate Koksch ,&nbsp;Ned Budisa ,&nbsp;Oleg V. Krokhin","doi":"10.1016/j.chroma.2026.466704","DOIUrl":"10.1016/j.chroma.2026.466704","url":null,"abstract":"<div><div>We investigated the reversed-phase chromatographic behaviour of peptides carrying nine non-canonical proline analogues using LC-MS/MS bottom-up proteomics analysis of <em>Escherichia coli</em> (<em>E.coli)</em> following co-translational incorporation. Of particular interest were the epimers 4<em>R</em>- and 4<em>S</em>-fluoroproline. On average, peptide interactions with the hydrophobic C18 phase increased in the order: 4<em>R</em>-Flp &lt; Pro &lt; 4<em>S</em>-Flp. The mean retention shifts were found to be -0.11 and +0.06% acetonitrile for 4<em>R</em>- and 4<em>S</em>-Flp, respectively (0.1% formic acid eluent additive). This diminutive average difference in hydrophobic properties belies the unpredictable chromatographic behaviour of modified peptides. The incorporation of either fluorinated epimer, each relatively amphipathic, can make certain peptides more hydrophobic, while for others, the peptide becomes more hydrophilic. Incorporation of a single 4<em>R</em>-fluoroproline produces a shift ranging from (2.18 to +2.55) %ACN, while <em>4S-</em>fluoroproline produces shifts ranging from (-4.82 to +4.67) %ACN on the RP HPLC elution scale. In addition to common composition-dependent factors affecting peptide retention, such as peptide length, we identified several sequence-specific features that explain deviations from the average retention characteristics. These include nearest neighbour effects and amphipathic helicity. Other analogues investigated encompassed diverse chemical features, including hydroxylation (4<em>R</em>-hydroxyproline), dehydrogenation (3,4-dehydroproline), ring expansion (pipercolic acid), heteroatom inclusion (3-thia-proline &amp; 4-thia-proline) and bridge ring structures (4,5-<em>trans</em>-methanoproline &amp; 4,5-<em>cis</em>-methanoproline).</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1769 ","pages":"Article 466704"},"PeriodicalIF":4.0,"publicationDate":"2026-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145973922","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}

{"title":"Synthesis of modified siloxane-based three-dimensional porous polymer as adsorbent for high-efficiency enrichment of phenyl urea herbicides from vegetables","authors":"Miao Jing ,&nbsp;Juntao Wang ,&nbsp;Ruiyang Ma ,&nbsp;Yaxing Guo ,&nbsp;Zichen Zhao ,&nbsp;Qiuhua Wu ,&nbsp;Zhi Wang","doi":"10.1016/j.chroma.2025.466664","DOIUrl":"10.1016/j.chroma.2025.466664","url":null,"abstract":"<div><div>A porous hyper-crosslinked polymer (OPS/BCM-HCP) was synthesized for the first time using cage-shaped octaphenyl POSS as the monomer and biphenyl-p-dichlorobenzene as the cross-linker for the efficient enrichment of phenylurea herbicides (chlorotoluron, isoproturon, monolinuron and buturon). High performance extraction for the phenylureas was realized by using the OPS/BCM-HCP as the SPE adsorbent from water, cabbage and white radish samples. Under the optimized conditions, the newly established method by coupling the SPE with HPLC-UV had a good linear response for phenylureas in the range of 0.06–100.0 ng mL⁻¹ for water, 2.10–200.0 ng g⁻¹ for cabbage, and 1.20–200.0 ng g⁻¹ for white radish samples, with the determination coefficient larger than 0.9912. The limits of detection (LODs, S/<em>N</em> = 3) and limits of quantification (LOQs, S/<em>N</em> = 9) were 0.02–0.03 and 0.06–0.09 ng mL⁻¹ for water, 0.70–0.95 and 2.10–2.85 ng g⁻¹ for cabbage, and 0.40–0.85 and 1.20–2.55 ng g⁻¹ for white radish, respectively. The method recoveries were 80.0 %-116 % with the RSDs from 3.6 % to 8.9 %. The experimental results showed that OPS/BCM-HCP had an excellent adsorption effect on phenylurea herbicides, and the method provided an alternative way for the effective quantification of the herbicides in vegetable samples.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1769 ","pages":"Article 466664"},"PeriodicalIF":4.0,"publicationDate":"2026-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145883754","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ionic liquid-based aqueous two-phase extraction as a pretreatment strategy for the determination of 38 pharmaceuticals and personal care products in aquatic environments by HPLC-MS/MS","authors":"Shuo Xie ,&nbsp;Wenbin Zhang ,&nbsp;Yike Han ,&nbsp;Xinyan Dong ,&nbsp;Wanning Li ,&nbsp;Penghui Li ,&nbsp;Liyun Kong","doi":"10.1016/j.chroma.2026.466670","DOIUrl":"10.1016/j.chroma.2026.466670","url":null,"abstract":"<div><div>The accurate determination of pharmaceuticals and personal care products (PPCPs) in wastewater is crucial for comprehensive environmental risk assessment and human exposure evaluation. Given the complex matrices of aqueous environmental samples, efficient sample preparation remains a critical challenge in analytical procedures. This study presents an ionic liquid-based aqueous two-phase system (IL-ATPS) extraction methodology used as a pretreatment step prior to high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) for the simultaneous determination of 38 PPCPs. A mechanistic investigation revealed that target analytes with more hydrogen-bonding sites and higher hydrogen-bond donor (HBD) capacity exhibited enhanced solubility in ILs. In addition, IL anions with stronger hydrogen-bond acceptor (HBA) capacity further improved the solubility of the 38 PPCPs. These findings indicate that hydrogen bonding between analytes and ILs likely played a critical role in the dissolution mechanism. The established IL-salt ATPS extraction method utilized a 15 mL aqueous sample, 0.2 g tetraethylammonium acetate ([N₂₂₂₂][OAc]), and 12 g K₂HPO₄, with a 1-minute vortex mixing. Compared with traditional solid phase extraction (SPE), this approach significantly reduced the sample volume from 1 L to 15 mL, avoided the use of volatile organic solvents, simplified the overall processing, and enabled rapid (&lt;15 minutes) pretreatment. The method demonstrated excellent sensitivity with limits of detection (LODs) ranging from 0.00013 to 0.11 ng/mL. Method validation via standard addition experiments demonstrated satisfactory accuracy, yielding recoveries between 74.3 and 129.8 %. Precision was assessed using both intra-day and inter-day measurements. The intra-day relative standard deviations (RSDs) ranged from 0.7 % to 19.9 %, while the inter-day RSDs ranged from 1.4 % to 18.4 %, demonstrating that the method provides consistent and reproducible results under controlled laboratory conditions. These findings underscore the present IL-based ATPS extraction method, followed by HPLC-MS/MS analysis, as an eco-friendly, robust, and scalable approach for PPCPs monitoring in aqueous environmental samples, offering potential applications in environmental monitoring and risk assessment.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1769 ","pages":"Article 466670"},"PeriodicalIF":4.0,"publicationDate":"2026-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145909693","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}