Journal of Chromatography A最新文献

{"title":"Analysis of per-and polyfluorinated alkyl substances by chromatography-mass spectrometry: A review.","authors":"Peng Liu, Jiaoyang Li, Liangyi Hong, Huimin Zou, Xingyan Zhou, Xin Zhang, Yan Zhou, Hian Kee Lee, Zhenzhen Huang","doi":"10.1016/j.chroma.2025.466261","DOIUrl":"10.1016/j.chroma.2025.466261","url":null,"abstract":"<p><p>Per- and polyfluoroalkyl substances (PFAS), a group of synthetic chemicals that have been produced for over fifty years, are of significant concern due to their widespread environmental distribution and potential risks to human health. The transition from legacy PFAS to emerging PFAS with shorter chains and unknown structures has further amplified existing challenges in their analysis. A variety of reliable and sensitive analytical methods is available to analyze these contaminants in various biological and environmental matrices. However, current research on PFAS lacks a unified standard for their determination and there is limited guidance on selecting appropriate methods to address specific analytical challenges. In this review, up-to-date analytical methods for PFAS detection based on chromatography and mass spectrometry in the recent literature are reviewed. The survey covers (i) a discussion of the advantages, limitations, and scope of application of various sample preparation methods for PFAS analysis, (ii) recent advances in chromatographic separation and mass spectrometry with respect to targeted and non-targeted analysis, and (iii) progress in the analysis of PFAS in complex sample matrices, including a wide range of environmental and biological samples. While liquid chromatography-mass spectrometry has been the mainstay technique in most of the studies covered, greater efforts are needed to develop newer methods to deal with not only the legacy compounds but also emerging ones. A wide range of biological and environmental matrices also needs to be identified and considered in future analytical and sample preparation developmental work.</p>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1760 ","pages":"466261"},"PeriodicalIF":4.0,"publicationDate":"2025-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144815484","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":"HSCCC-Tchebichef moment regression approach for enhanced quantification of oleuropein in olive leaf extracts","authors":"Jules Muhire ,&nbsp;Fu-xin Zhang ,&nbsp;Bao-qian Liu ,&nbsp;Jinxia Hu ,&nbsp;Xiaofang Wang ,&nbsp;Dong Pei ,&nbsp;Duo-Long Di","doi":"10.1016/j.chroma.2025.466445","DOIUrl":"10.1016/j.chroma.2025.466445","url":null,"abstract":"<div><div>Oleuropein, a major bioactive phenolic compound from olive leaves, has attracted considerable interest for its health benefits. Targeted fractionation of oleuropein from crude extracts is hampered by the co-existence of numerous structurally similar metabolites, making conventional chromatographic separation inefficient. Here we describe, for the first time, a compact predictive framework that combines high-speed countercurrent chromatography (HSCCC), discrete Tchebichef moment (TM) feature extraction, and stepwise regression (SR) modelling to quantify oleuropein. Olive leaves were extracted with 80 % ethanol, and the crude extract was subjected to continuous-injection HSCCC in reverse‑phase mode using an ethyl acetate-petroleum ether-water (6:0.06:7) solvent system. HPLC analysed the resulting fractions and reference standards. Chromatograms were converted into two-dimensional matrices from which TMs up to the 20th order were computed. Forward stepwise regression identified a small set of TM coefficients that correlated strongly with oleuropein concentration and yielded a linear predictive model with high accuracy (<em>R</em>² &gt; 0.99). In comparison to the MCR-ALS, the TM-based model achieved superior predictive performance using fewer parameters. The integrated HSCCC-TM-SR approach provides a rapid and scalable method for quantifying oleuropein and may be extended to other complex natural products.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1763 ","pages":"Article 466445"},"PeriodicalIF":4.0,"publicationDate":"2025-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145264677","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":"Simple and sensitive LC-MS analysis of short chain fatty acids in cecum content and feces in mice: A derivatization-free approach.","authors":"Soo Takasu, Yumi Nagasaki, Juri Koizumi, Tetsuo Koshizuka, Yukihiro Esaka","doi":"10.1016/j.chroma.2025.466263","DOIUrl":"10.1016/j.chroma.2025.466263","url":null,"abstract":"<p><p>Short-chain fatty acids (SCFAs), such as acetic, propionic, and butyric acid, are important biomarkers that reflect gut microbiota composition, disease progression, and overall health. Conventional SCFA analysis typically involves derivatization prior to liquid or gas chromatography. However, derivatization is challenging due to the volatility of SCFAs and interference from similar carboxylic acids in biological samples and often requires complex purification steps. Consequently, the development of derivatization-free liquid chromatography-mass spectrometry (LC-MS) methods is desirable, although direct LC-MS analysis of intact SCFAs often suffers from limited sensitivity and accuracy. In this study, we have developed a derivatization-free LC-MS method for the analysis of major SCFAs (C2-C4) in the cecum content and feces of mice. Separation was performed using a mixed-mode column combining hydrophilic interaction chromatography and anion-exchange chromatography. We found that ammonium formate, required for separation, significantly suppressed SCFA signal intensity, whereas its replacement by ammonium fluoride prevented this suppression. Furthermore, we have demonstrated that the background noise in biological sample analysis can be reduced by selective reaction monitoring (SRM) mode, in which the same m/z value was set for both the precursor and product ions, as compared with selective ion monitoring (SIM) mode. The method developed in this study showed good validation values and sensitivity in the quantification of targeted SCFAs in mouse biological samples, demonstrating the excellent practicability of this method and making it a useful tool for research on the gut microbiome.</p>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1760 ","pages":"466263"},"PeriodicalIF":4.0,"publicationDate":"2025-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144815486","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":"On the use of ethylene carbonate as a green solvent in mobile phases.","authors":"Alain Berthod, Daniel W Armstrong","doi":"10.1016/j.chroma.2025.466259","DOIUrl":"10.1016/j.chroma.2025.466259","url":null,"abstract":"<p><p>Dimethyl, diethyl, and propylene carbonate esters are polar aprotic solvents that demonstrated their capability as \"green\" solvents compared to methanol, acetonitrile or even apolar solvents in mobile phases for liquid chromatography. Ethylene carbonate (EC) has a melting point of 36 °C, so as a solid, it cannot be used as a neat solvent in liquid chromatography. However, its molten state is fully miscible with water and such solutions can be effective liquid chromatographic mobile phases. In this work, EC was used for the first time in a variety of liquid mobile phases since its freezing temperature can be lowered at or below room temperature by mixing it with other solvents. The freezing temperature of EC mixed with different proportions of a variety of common solvents as well as with other carbonate esters is presented. The viscosity changes induced by these mixtures were estimated using the experimental driving pressures (Darcy's law). A hydrophilic interaction liquid chromatography (HILIC) separation of nucleosides could be improved by replacing a large part of acetonitrile by EC. RPLC separations of phenols and less polar aromatic hydrocarbons could be performed by entirely replacing acetonitrile by EC. UV detection at 220 nm was possible, but background removal was required when a solvent gradient was used. The EC elution strength is slightly lower than that of acetonitrile. EC is definitively a very green solvent that must be considered with both HILIC and RPLC modes. However, it is not without some drawbacks in all applications since its 243 °C boiling point precludes the use of evaporative light scattering detectors and makes electrospray ionization difficult. EC is not soluble with alkanes. The EC/heptane/ethanol phase diagram showed that >72 % ethanol is needed to obtain EC monophasic mixtures. Therefore, EC will have little use in normal phase chromatography.</p>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1760 ","pages":"466259"},"PeriodicalIF":4.0,"publicationDate":"2025-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144811468","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":"Supercritical fluid chromatography for the separation of lipophilic tanshinones from Salvia miltiorrhiza Bunge.","authors":"Donghai Xia, Chunying Song, Jing Feng, Dongping Yu, Yanfang Liu, Xinmiao Liang, Gaowa Jin, Zhimou Guo","doi":"10.1016/j.chroma.2025.466270","DOIUrl":"10.1016/j.chroma.2025.466270","url":null,"abstract":"<p><p>This study systematically investigated the retention behavior of lipophilic tanshinones (Tans) on distinct stationary phases and developed a supercritical fluid chromatography (SFC) method under a binary mobile phase (CO₂ and methanol). The non-polar VCC18 column showed extremely weak retention and virtually no separation selectivity for eleven standards. Despite some improvements observed with several typical polar columns (Viridis Silica, Diol, and NH₂) and a SFC dedicated column (Torus 2-PIC), peak shapes and selectivity remained poor. However, a highly polar Click TE-Cys column exhibited good peak shapes and achieved complete separation of all standards, and was thus identified as the optimal stationary phase for Tans. These results indicate that despite the lipophilicity of Tans, their retention is primarily affected by internal polar oxygen atoms, requiring highly polar columns instead of C18 or conventional polar columns for adequate separation selectivity. In addition, the SFC separation method based on the Click TE-Cys column exhibited better separation selectivity and good orthogonality compared with RPLC. Its application potential was demonstrated by offline SFC × RPLC-MS/MS analysis, which annotated an additional 55 compounds in Tans, including 17 unknown compounds. Overall, this study provides mechanistic insights into the retention of oxygen-containing lipophilic compounds in SFC, as well as a methodological advance for Tans separation and a theoretical foundation for SFC method development of analogous compounds.</p>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1760 ","pages":"466270"},"PeriodicalIF":4.0,"publicationDate":"2025-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144811469","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 sensitive UPLC-MS/MS method for simultaneous determination of 15 Bisphenol A analogues in human serum and urine: Application of paired samples and global exposure assessment.","authors":"Guangting Hu, Zhichun Zhang, Yi Huang, Deyu Fang, Ming Zhan, Weidong Qu, Ying Zhou","doi":"10.1016/j.chroma.2025.466217","DOIUrl":"10.1016/j.chroma.2025.466217","url":null,"abstract":"<p><p>The global replacement of Bisphenol A (BPA) with structurally similar yet understudied analogues demands precise biomonitoring tools to assess human exposure and health risks. To bridge critical gaps, we developed a novel ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method for simultaneous quantification of 15 emerging BPA analogues including Bisphenol AF (BPAF), Bisphenol AP (BPAP), Bisphenol B (BPB), Bisphenol C (BPC), Bisphenol E (BPE), Bisphenol F (BPF), Bisphenol G (BPG), Bisphenol FL (BPFL), Bisphenol M (BPM), Bisphenol P (BPP), Bisphenol pH (BPPH), Bisphenol S (BPS), Bisphenol TMC (BPTMC), Bisphenol Z (BPZ), and Bisphenol A diglycidyl ether (BFDGE)-in human serum and urine matrices. The method achieved ultrahigh sensitivity with limits of detection (LODs) of 0.008-0.032 μg/L in urine and 0.010-0.030 μg/L in serum, high accuracy (recoveries: 84.58-113.53 %), and reproducibility (relative standard deviation (RSD) ≤14.7 %). Rigorous validation was conducted through uncertainty assessment and green chemistry metrics (GAC) evaluation. The following scores were obtained: Analytical GREEnness metric approach (AGREE):0.65, Analytical GREEnness Metric for Sample Preparation (AGREEprep):0.64, Modified Green analytical procedure index (MoGAPI) :72, Complex modified Green analytical procedure index (ComplexMoGAPI):73, RGB model: 74.2 %, Blue Applicability Grade Index (BAGI):60, Click Analytical Chemistry Index (CACI):69 and Carbon Footprint Reduction Index (CaFRI):71, respectively. These results confirm the method's reliability and environmental sustainability. Applied to 44 paired samples from Chinese children, the study revealed serum biomarkers (BPPH + BPTMC) as superior indicators of internal exposure compared to urinary metabolites, providing the first-reported paired biospecimen data for these analogues. Furthermore, dual-matrix biomonitoring (serum + urine) significantly improved cumulative exposure assessment accuracy. This work establishes a robust analytical framework for tracking emerging BPA substitutes, supporting evidence-based chemical regulation and advancing environmental health research.</p>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1760 ","pages":"466217"},"PeriodicalIF":4.0,"publicationDate":"2025-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144811467","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 extraction of two different sulfonamide antibiotics from lipstick by magnetic solid-phase extraction based on c-MMWCNT@CDs/Fe₃O₄.","authors":"Xiao Dai, Xianhong Zhu, Shiyu Li, Ze Wu, Chenyang Zhao, Xun Gao, Longshan Zhao","doi":"10.1016/j.chroma.2025.466266","DOIUrl":"10.1016/j.chroma.2025.466266","url":null,"abstract":"<p><p>Some illegal businesses often add antibiotics such as sulfonamides to expand the functional range of lipstick. However, the abuse of antibiotics will lead to serious adverse reactions and increase the drug resistance of bacteria. To ensure the safety of lipstick, it is necessary to monitor the antibiotic content, which urgently needs to develop an efficient and highly sensitive analytical method. In this study, a magnetic solid-phase extraction (MSPE) method was developed using a composite adsorbent based on carboxylated multi-walled carbon nanotubes (c-MMWCNT) and carbon dots (CDs) for sample pretreatment. A magnetic dispersive solid-phase extraction coupled with high-performance liquid chromatography method was established using silanized serine‑modified carbon dots (Sil-Ser-OCDs) as the sorbent for the determination of sulfapyridine (SPY) and sulfamethazine (SMT). Key extraction parameters including adsorbent dosage, extraction time, and pH were optimized using response surface methodology. The optimal extraction conditions were determined to be an adsorbent dosage of 72 mg, extraction time of 4.5 min, and pH 6.0. Under the optimal conditions, the recoveries of SPY and SMT were in the range of 88.0%-93.4%, and the RSD values of intra-day and inter-day precision were under 4.2% and 5.4%, respectively, indicating that the approach has excellent accuracy and precision.</p>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1760 ","pages":"466266"},"PeriodicalIF":4.0,"publicationDate":"2025-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144815485","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":"Time-controlled online SPE: strategic approach for N-acylethanolamines quantification in complex matrices","authors":"Nicoletta Gatti ,&nbsp;Valentina Greco ,&nbsp;Salvatore Cuzzocrea ,&nbsp;Rosalia Crupi ,&nbsp;Enrico Gugliandolo ,&nbsp;Alessandro Giuffrida","doi":"10.1016/j.chroma.2025.466449","DOIUrl":"10.1016/j.chroma.2025.466449","url":null,"abstract":"<div><div>Quantifying and monitoring the level of N-acylethanolamines (NAEs) in biological fluids is becoming increasingly important to better understand their role in health and disease. The complexity of biological matrices, however, poses significant challenges for accurate quantification, with traditional pretreatment methods often proving insufficient in certain cases. This study introduces a novel approach utilizing Online Solid Phase Extraction (SPE) to quantify NAEs in equine plasma, specifically Palmitoyl Ethanolamide (PEA) and Oleoyl Ethanolamide (OEA). In the original analytical method here developed and validated, established toluene liquid-liquid extraction was used to isolate the lipid-like fraction, followed by an innovative Time-Controlled Online SPE coupled to HPLC-MS/MS. This strategic temporal approach allows target analytes to rapidly elute to the analytical column while retaining lipidic interferents, preventing matrix contamination and ensuring selective analysis. The method validation demonstrated excellent linearity, while providing high recovery and suitable matrix effects. The limits of detection (LOD) and quantification (LOQ) were determined as 0.27 ng/mL and 0.83 ng/mL for PEA; 0.04 ng/mL and 0.11 ng/mL for OEA. The innovative approach here presented allowed for reliable NAE quantification in equine plasma and provided unprecedented data on the endogenous levels of PEA and OEA in this species. This method has potential applications for the analysis of other complex biological matrices with high levels of interferents that share chemical similarities with the target compounds. This novel approach significantly advances the understanding of the endocannabinoid system in equines and serves as a valuable tool for future research in this domain.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1763 ","pages":"Article 466449"},"PeriodicalIF":4.0,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145264675","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":"Enhanced affinity of C18 and L-lactyl co-modified silica particles toward chlorogenic acid for sensing applications","authors":"Yoshimi Kanie ,&nbsp;Makoto Fujiwara ,&nbsp;Osamu Kanie","doi":"10.1016/j.chroma.2025.466448","DOIUrl":"10.1016/j.chroma.2025.466448","url":null,"abstract":"<div><div>Porous silica offers high surface area and chemical stability, making it ideal for chemical sensing applications. Its surface can be easily modified with functional groups to tailor molecular interactions, especially in aqueous environments. Alkyl-modified silica, widely used in chromatography, also shows promise for sensing due to its tunable hydrophobicity. Raman spectroscopy enables label-free, water-compatible detection, however often requires relatively high analyte concentrations. Modified silica surfaces may overcome this disadvantage by concentrating analytes in the detection area. Thus, simple, tunable platforms based on functionalized silica could offer an effective alternative to complex systems like SERS or molecular imprinting. We modified porous silica with various acyl groups (C3, C6, C9, C18) and <span>D</span>-/L-lactyl groups via amide bond formation following the introduction of aminopropyl groups. Elemental analysis was used to estimate the degree of modification, and residual amino groups were acetylated to suppress nonspecific interactions. We evaluated the interactions between the modified silica and chlorogenic acid in aqueous solutions using confocal Raman microscopy. We found that interaction strength was influenced by acyl chain length; higher C18 content reduced binding, likely due to limited accessibility of surface silanol groups. While <span>D</span>- or <span>L</span>-lactyl modification alone had minimal impact, co-modification with C18 and <span>L</span>-lactyl groups produced a synergistic enhancement, consistent with combined chiral and hydrophilic effects. Silica co-modified at a 1:1 molar ratio (40 % total modification) achieved ∼50-fold enrichment of chlorogenic acid compared with unmodified silica. Co-modification of porous silica with hydrophobic and chiral hydrophilic groups enables efficient enrichment of chlorogenic acid in aqueous environments, sufficient for direct detection by confocal Raman microscopy without SERS enhancement. This simple, tunable platform could be extended to other small bioactive molecules and applied to complex matrices such as taste sensing.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1763 ","pages":"Article 466448"},"PeriodicalIF":4.0,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145263804","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":"New trends in the chromatographic analysis of natural products.","authors":"Paola Dugo, Francesco Cacciola, Petr Česla","doi":"10.1016/j.chroma.2025.466428","DOIUrl":"https://doi.org/10.1016/j.chroma.2025.466428","url":null,"abstract":"","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":" ","pages":"466428"},"PeriodicalIF":4.0,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145273291","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}