J Chromatogr A [JOURNAL]
Sun
200 papers
Corrigendum to "High-pressure hydrolysis: A rapid sample preparation strategy for amino acid analysis of complex biological matrices" [Journal of Chromatography A 1779 (2026) 467059].
Li S, Meng L, Qin Z … +2 more , Zhang X, Gu Y
J Chromatogr A · 2026 Aug · PMID 42161762 · Publisher ↗
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Layer-by-layer assembled quinone-amine network on silica as a robust mixed-mode stationary phase for liquid chromatography.
Luo Y, Jia J, Zhao C … +3 more , Wu H, Huang R, Luo J
J Chromatogr A · 2026 Aug · PMID 42161043 · Publisher ↗
To overcome the limited retention of hydrophobic analytes on commercial amino columns, a PBQ-PEI network coating was constructed on silica via quinone-amine coupling between polyethyleneimine and p-benzoquinone, and core...
To overcome the limited retention of hydrophobic analytes on commercial amino columns, a PBQ-PEI network coating was constructed on silica via quinone-amine coupling between polyethyleneimine and p-benzoquinone, and core-shell PBQ-PEI@SiO particles were prepared by layer-by-layer assembly as a new LC stationary phase. The resulting material enabled efficient separations of both hydrophilic compounds (nucleobases, nucleosides, imidazoles, and xanthines) and hydrophobic compounds (alkylbenzenes, polycyclic aromatic hydrocarbons, and halogenated benzenes), exhibiting a characteristic RP-HILIC mixed-mode retention behavior. Column performance evaluation demonstrated good repeatability and long-term stability (RSD < 0.59% for nine consecutive injections and <1.87% deviation over four months). For caffeine determination, the developed method showed acceptable analytical performance, including good linearity in the range of 20-260 mg·L, an LOD of 0.20 mg·L, an LOQ of 0.61 mg·L, and satisfactory recovery values of 89.30%-103.15%, and was successfully applied to the analysis of commercial tea beverage samples. This work expands the application of quinone-amine chemistry in stationary-phase fabrication and provides a new material option for mixed-mode liquid chromatography.
Surface modification and ligand loading effects in imidazolium-based zwitterionic stationary phases for hydrophilic interaction chromatography.
Thapa B, Zeger VR, Shollenberger D … +1 more , Anderson JL
J Chromatogr A · 2026 Aug · PMID 42161042 · Publisher ↗
Imidazolium-based zwitterionic stationary phases represent a promising class of materials for hydrophilic interaction chromatography (HILIC). However, systematic studies examining the influence of silica surface modifica...
Imidazolium-based zwitterionic stationary phases represent a promising class of materials for hydrophilic interaction chromatography (HILIC). However, systematic studies examining the influence of silica surface modification strategies on ligand loading, material morphology, and chromatographic mass transfer behavior remain limited. In this work, porous silica was modified using 3-mercaptopropylsilatrane (MPS) and the conventional 3-mercaptopropyltrimethoxysilane (MPTMS) approach, followed by functionalization with vinylimidazolium and octenylimidazolium zwitterionic ligands via thiol-ene click chemistry. MPS modification enabled higher sulfur surface coverage resulting in increased ligand loading compared to silica treated with the MPTMS approach. The type of ligand appears to govern material morphology and packability with vinylimidazolium-based materials exhibiting pronounced agglomeration, whereas octenylimidazolium-based materials retained a free-flowing morphology and could be readily packed into columns. In contrast, mass transfer behavior was observed to be strongly influenced by ligand loading. The octenylimidazolium zwitterionic ligand on MPTMS modified silica with approximately 1.25-fold lower ligand loading than the corresponding MPS modified ligand, exhibited a 1.90-fold lower resistance to mass transfer despite comparable immobilized water layer volumes. Nitrogen adsorption-desorption measurements showed that higher ligand loading resulted in greater reductions of surface area, pore width and volume of silica, suggesting partial occupation of the pore network by the bonded ligands and more restricted diffusion. Evaluation of acids, bases, and water-soluble vitamins further indicated that retention involves contributions from adsorption-related interactions in addition to hydrophilic partitioning. Together, these results suggest that the increased resistance to mass transfer could arise from reduced intraparticle diffusion and greater adsorption-related interactions associated with higher ligand loading.
Estimating the solubility of organic compounds in water using electrokinetic chromatography.
Atapattu SN, Li J, Fanali S
J Chromatogr A · 2026 Aug · PMID 42161041 · Publisher ↗
One of the most sought-after physicochemical properties in drug discovery, environmental assessment, chemical engineering, and food science, especially for new chemical entities, is the solubility of organic compounds in...
One of the most sought-after physicochemical properties in drug discovery, environmental assessment, chemical engineering, and food science, especially for new chemical entities, is the solubility of organic compounds in water (S). Experimentally determining water solubility is a time-consuming and tedious process; therefore, estimation methods are often opted for instead. These estimation approaches require prior knowledge of molecular descriptors or a combination of octanol-water partition coefficients and melting point data. In this work, we systematically evaluated the estimation of the solubility of organic compounds in water employing electrokinetic chromatography systems using the solvation parameter model system constants and screening tools cos θ and the d-parameter. The average absolute error for the water solubility estimation using identified micellar electrokinetic chromatography models in this study ranged from 0.291 for 75 mM sodium deoxycholate to 0.438 for 40 mM sodium dodecyl sulfate, with an expected prediction error for estimating log S of ∼0.4 log units. Identified micellar electrokinetic chromatography retention and water solubility correction models could be used for rapid screening purposes for the estimation of water solubility in various applications.
A multi-dimensional quality evaluation strategy for Siegesbeckia pubescens Makino integrating chromatographic, electrochemical, and thermodynamic fingerprints with binary similarity evaluation method.
Yan H, Zhang Z, Sun G
J Chromatogr A · 2026 Aug · PMID 42155161 · Publisher ↗
To identify the optimal quality and geographical origin of Siegesbeckia pubescens Makino (SP), a comprehensive quality evaluation strategy was established using 20 batches of SP samples collected from five distinct produ...
To identify the optimal quality and geographical origin of Siegesbeckia pubescens Makino (SP), a comprehensive quality evaluation strategy was established using 20 batches of SP samples collected from five distinct producing regions. Initially, the purity of each fingerprint peak was assessed using the dual-wavelength ratio purity test method (DRPM). Subsequently, the contents of four major components in SP were accurately determined using the one-linear multi-analyte method (OLMM), which showed excellent agreement with the conventional quantitative analysis of multi-components by a single marker (QAMS) approach. For fingerprint profiling, a 3D full-wavelength fingerprint (3DFFP) was developed by high-performance liquid chromatography (HPLC), which provided more comprehensive information compared to traditional single-wavelength fingerprints. Beyond conventional UV-absorbing components, the electroactive and thermally responsive characteristics of SP were also integrated into the quality evaluation. To this end, electrochemical (EC) and differential scanning calorimetry (DSC) quantitative fingerprints were constructed respectively using the quantitative fingerprint method (QFM). The binary similarity evaluation method (BSM) was applied as a quality evaluation method for the above fingerprints. Twenty batches were classified into distinct quality grades, and origin-based discrimination was achieved via cluster analysis and principal component analysis (PCA). Finally, partial least squares regression (PLS) was further employed to identify chromatographic peaks with major contributions to thermal effects and uncover potential antioxidant peaks. In summary, the proposed strategy enables the simultaneous quality control of UV-absorbing components, electroactive substances, and thermally responsive components of SP, offering a robust evaluation framework for the holistic quality evaluation of herbal medicines.
Multidimensional quantitative analysis, LC-Q-Orbitrap-MS combined with chemical-activity based TOPSIS modeling for comprehensive quality evaluation of Platycodon root.
Lan L, Cao Y, Yuan J … +5 more , Mao X, Ji S, Wang K, Zhou H, Hu Q
J Chromatogr A · 2026 Aug · PMID 42155160 · Publisher ↗
Platycodon grandiflorus (Jacq.) A. DC., a traditional food-as-medicine species in East Asia, faces quality inconsistencies due to the diverse cultivation practices and varied sources. This study characterized 165 compoun...
Platycodon grandiflorus (Jacq.) A. DC., a traditional food-as-medicine species in East Asia, faces quality inconsistencies due to the diverse cultivation practices and varied sources. This study characterized 165 compounds in the 70% methanol extract and 27 oligosaccharides in the aqueous extract using UHPLC-Q-Orbitrap-MS, and developed a chemical-activity integrated quality evaluation system for Platycodon root using TOPSIS analysis. Multidimensional indicators (moisture, ash, extract, saponins, saccharides, nucleotides, and antioxidant activity) were investigated. Fifteen chemical markers, constituting 20.1%-40.2% of the measurable composition, were quantified via HPLC-ELSD, HPLC-DAD, and UV-Vis. Antioxidant capacity was assessed using DPPH and ABTS assays. An unweighted TOPSIS model incorporating 17 chemical and activity indicators was established, identifying two- and three-year-old roots as superior. This framework provides a robust, theory-based methodology for quality standardization, traceability, and grading of Platycodon root, offering a referential model for other herbal medicines.
The identification of VX chemical attribution signatures from different synthetic routes.
McDowall LJ, Ovenden SPB, McGill NW … +3 more , Petricevic M, Webster RL, Zanatta SD
J Chromatogr A · 2026 Aug · PMID 42150445 · Publisher ↗
Despite it being banned under the Chemical Warfare Convention, VX is still being used, as demonstrated in 2017 with the assassination of Kim Jong Nam in Malaysia. In addition to conducting the typical forensic investigat...
Despite it being banned under the Chemical Warfare Convention, VX is still being used, as demonstrated in 2017 with the assassination of Kim Jong Nam in Malaysia. In addition to conducting the typical forensic investigations, incidence of the deliberate use of chemical warfare agents (CWA) such as VX could also include undertaking chemical forensics to address questions including method of production, precursor-product-matching and batch-matching. The identification of residual impurities in VX, known as chemical attribution signatures (CAS), that allow for these questions to be addressed, would be beneficial to agencies undertaking these investigations. To increase the knowledge pool regarding CAS specific to a particular production method, five synthetic routes of VX formation were chemically profiled and subjected to multivariate analysis. In total, forty-one impurities of interest were identified that could be attributed to a production method. The structures of thirty-four were confirmed through a combination of database matching, accurate mass measurement, literature analysis and comparison with authentic standards. Several of these impurities were identified as candidate CAS for method attribution. Additionally, the longevity of the CAS was assessed by analysing samples after storage for 18 months at room temperature. While samples could not be classified (via MVA) to a specific production method, nineteen candidate CAS were still able to be identified. These results are suggestive that VX method of production may still be able to be elucidated on long term storage.
High-resolution GC × GC fingerprinting reveals atmosphere-dependent volatilome trajectories in pork spoilage.
Chen L, Trapani F, Caratti A … +2 more , Devlieghere F, Cordero C
J Chromatogr A · 2026 Aug · PMID 42150444 · Publisher ↗
The microbial spoilage of raw meat is modulated by the packaging atmosphere, yet the volatile fingerprints underlying these processes remain only partially resolved. This study establishes a structured volatilome fingerp...
The microbial spoilage of raw meat is modulated by the packaging atmosphere, yet the volatile fingerprints underlying these processes remain only partially resolved. This study establishes a structured volatilome fingerprinting workflow based on comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC × GC-TOFMS) to analyze pork spoilage under air, high-N, and high-O/CO packaging conditions. The applied approach achieved a more comprehensive and confident chemical characterization of the volatilome when compared to currently available results with conventional gas chromatography mass spectrometry (GC-MS) or real-time mass spectrometry. A total of 199 volatile organic compounds (VOCs) were detected, including numerous low-abundance and metabolically related compounds that were annotated by complementary orthogonal criteria. Multivariate analysis based on selected VOCs revealed atmosphere-specific volatilome trajectories and identified key spoilage markers including pyruvate-derived metabolites (acetoin, 2,3-butanedione, 2,3-butanediol), 3-methyl-1-butanol and several aldehydes and ketones. Overall, GC × GC provides enhanced chemical resolution and thus delivers new insights into raw pork spoilage mechanisms via uncovering additional trace-level metabolites not previously observed by other approaches. Expanding and rigorously annotating the meat volatilome would reinforce spoilage assessment and targeted preservation strategies, through resolving microbial metabolism and accurately discriminating spoilage trajectories.
Correlation between chromatographic behavior and microfluidic phase distribution in the phase-separation mode of HPLC.
Sakata H, Hirose R, Iharada T … +1 more , Tsukagoshi K
J Chromatogr A · 2026 Aug · PMID 42143821 · Publisher ↗
We previously proposed the phase-separation mode in high-performance liquid chromatography (HPLC), in which phase-separation multiphase flow (PSMF) is used as the mobile phase. Although chromatographic behavior in this m...
We previously proposed the phase-separation mode in high-performance liquid chromatography (HPLC), in which phase-separation multiphase flow (PSMF) is used as the mobile phase. Although chromatographic behavior in this mode has been examined, its relationship with microfluidic phase organization inside packed structures has not been directly clarified. In this study, we correlated chromatographic behavior with fluorescence visualization of PSMF in a silica bead-packed microchannel. A water/acetonitrile/NaCl mixture was used as the eluent, and six solvent compositions ranging from water-rich to organic-rich conditions were examined at 40 °C and 0 °C. At 40 °C, the eluents remained homogeneous, whereas phase separation occurred at 0 °C. In water-rich systems under phase-separation conditions, hydrophilic 2,6-naphthalenedisulfonic acid eluted earlier than hydrophobic 1-naphthol, whereas the opposite tendency was observed in organic-rich systems. Fluorescence microscopy revealed that the phase with the larger volume fraction flowed mainly through regions away from the silica bead surfaces, while the minor phase was localized near the surfaces and moved more slowly. This phase-volume-dependent localization explained the observed elution order and retention behavior. The results demonstrate that separation in the phase-separation mode is governed by the combined effects of analyte distribution between the two coexisting liquid phases and their different flow velocities within the packed structure. This study provides direct experimental support for the separation mechanism of the phase-separation mode in HPLC.
Affinity of four different extraction chromatographic resin for Pd and Ag: Toward efficient separation of Pd from Ag.
Stiplošek LR, Van Ginkel M, Toma M … +1 more , Štrok M
J Chromatogr A · 2026 Aug · PMID 42143820 · Publisher ↗
In this study, the affinity of four extraction chromatographic resins from TrisKem International (TK200 Resin, Ni Resin, LN Resin, and TBP Resin) for retaining Pd and Ag in nitric and hydrochloric acid medium of various...
In this study, the affinity of four extraction chromatographic resins from TrisKem International (TK200 Resin, Ni Resin, LN Resin, and TBP Resin) for retaining Pd and Ag in nitric and hydrochloric acid medium of various molarities was systematically investigated. Batch experiments were performed in which the resins were contacted with Pd and Ag solutions prepared in nitric and hydrochloric acids of different molarities. Affinity of specific resin for Pd and Ag was assessed with the help of distribution coefficients (K), defined as the ratio of the concentration of a specific element between resin and solution under equilibrium conditions, as a function of nitric and hydrochloric acid concentration. The results provided fundamental insight into behaviour of Pd and Ag in connection with different resin under varying chemical conditions and enabled design of optimum Pd and Ag column separation protocol. Among the resins investigated, Ni Resin and TK200 Resin exhibited the most favourable selectivity and separation performance, allowing efficient and reproducible Pd-Ag separation with high recoveries. For Ni Resin, the overall recovery was 92% for Pd and 98% for Ag, with a Pd separation factor of 2500±300. For TK200 Resin, the overall recovery was 89% for Pd and 98% for Ag, with a Pd separation factor of 770±80. However, an additional separation step would be required to achieve a higher separation factor when using TK200 Resin.
A chromatographic process design and optimization multi-agent platform powered by large language models: A case application on extract of Ginkgo biloba leaf.
Tang Z, Wu S, Zhao X … +2 more , Wang Y, Gong X
J Chromatogr A · 2026 Aug · PMID 42143819 · Publisher ↗
Chromatographic separation technology has been widely applied in pharmaceutical, chemical, and food industries due to its high efficiency. However, traditional human-dependent chromatographic process development faces ch...
Chromatographic separation technology has been widely applied in pharmaceutical, chemical, and food industries due to its high efficiency. However, traditional human-dependent chromatographic process development faces challenges such as reliance on expert experience, long development cycles, and labor intensity. ChromR, a large language model (LLM)-driven platform for chromatographic process design and optimization, is presented in this work. The platform integrates ChromLLM, a domain-specific LLM trained for chromatography, along with a multi-agent system and an automated chromatographic experimental device. The multi-agent system comprises four agents: domain knowledge answering, experimental design, experimental execution, and data analysis. As a proof-of-concept, ChromR demonstrates the capability to automate the entire workflow-including initial process parameter recommendation, experimental design, automated execution, data analysis, and multi-objective optimization. By utilizing ChromR, dependency on expert knowledge is effectively reduced, while labor input and development time are significantly decreased. Chromatographic purification of the extract of Ginkgo biloba leaf (EGBL) was selected as a case application. ChromR successfully developed a chromatographic process within one week that meets multiple objectives, including fraction quality and production efficiency, reducing development time to approximately 1/7 of that required by the conventional paradigm. An intelligent and automated new paradigm was established, demonstrating significant potential for accelerating the chromatographic process development of complex mixtures.
Design of fluorinated cross-linked poly(ionic liquid) stationary phases for green liquid chromatography and multiple applications in food and drug analysis.
Wang X, Zou Z, Liu J … +3 more , Long B, Zeng H, Peng J
J Chromatogr A · 2026 Aug · PMID 42143818 · Publisher ↗
Green liquid chromatography has garnered increasing attention due to heightened environmental awareness among the public. In this work, a cross-linked poly(ionic liquid)-modified stationary phase was developed and was fu...
Green liquid chromatography has garnered increasing attention due to heightened environmental awareness among the public. In this work, a cross-linked poly(ionic liquid)-modified stationary phase was developed and was further functionalized with fluorine using 2,3,4,5,6-pentafluorostyrene. Chromatographic evaluations demonstrated the comprehensive separation capabilities of the mixed-mode HILIC/RPLC/IEX configuration, highlighting the potential to replace multiple single-mode columns with a mixed-mode column. High repeatable retention was achieved in green per aqueous liquid chromatography. The fluorine modification enhanced the stationary phase's capacity to separate organic halides and their isomers. Finally, this stationary phase was used to separate and detect multiple analytes in everyday products, achieving satisfactory relative standard deviations (RSDs) and recoveries that typically require diverse columns and instruments under conventional methods. Overall, the results underscore the advantages of preparing green chromatography stationary phases using cross-linked poly(ionic liquid), as well as the superiority of mixed-mode chromatography for diverse routine analyses.
Environmentally benign and sustainability-optimized extraction of alkaloids from Tetradium ruticarpum using custom-designed deep eutectic solvents.
He Q, Kuang Y, Hu Y … +6 more , Ruan Q, Zou Y, Peng D, Chen D, Qiu H, Li X
J Chromatogr A · 2026 Aug · PMID 42143524 · Publisher ↗
This study presents, for the first time, the development of a green and efficient hydrophobic deep eutectic solvents-based ultrasound-assisted extraction (HDEs-UAE) method for the extraction of alkaloids from Tetradium r...
This study presents, for the first time, the development of a green and efficient hydrophobic deep eutectic solvents-based ultrasound-assisted extraction (HDEs-UAE) method for the extraction of alkaloids from Tetradium ruticarpum, thereby effectively overcoming the limitations associated with conventional solvents and traditional extraction techniques. A total of 35 distinct DESs were synthesized, and their successful formation was confirmed through ¹H NMR and FT-IR spectroscopic analyses. Among them, the hydrophobic DES-21 (Menthol-Formic acid, Mol-FA) exhibited superior extraction efficiency and enabled the simultaneous extraction of seven alkaloid-based bioactive compounds in a single step, significantly outperforming conventional solvents such as water, methanol, and ethyl acetate. The extraction process and associated parameters, including the molar ratio of Mol:FA, ultrasonic power, extraction temperature, extraction time, and liquid-to-solid ratio, were systematically investigated and optimized using response surface methodology. The optimal conditions were established as an ultrasonic power of 300 W, an extraction temperature of 30 °C, an extraction time of 39.7 min, a liquid-to-solid ratio of 19.7 mL/g, and a molar ratio of 1:2 (Mol:FA), achieving a maximum total alkaloid extraction yield of 70.56 mg/g. The extraction mechanism was systematically investigated through complementary analytical techniques, including SEM, FT-IR, and density functional theory (DFT) calculations. Notably, DFT calculations and non-covalent interaction (NCI) analyses reveal that the enhanced extraction efficiency is attributable to the exergonic stability of the DES-21-EVOD complex, along with the increased availability of hydrogen-bond donors and acceptors provided by DES-21. In conclusion, the proposed HDESs-UAE method, characterized by its simplicity and environmental benignity, offers a highly efficient and sustainable approach for the extraction of bioactive alkaloid compounds from traditional Chinese medicine.
Comparative analysis of volatile profiles in 39 cultivars of Chinese chives and establishment of flavor fingerprints.
Li J, Zhao C, Xie B … +5 more , Li J, Ma P, Khan KS, Xiao X, Yu J
J Chromatogr A · 2026 Aug · PMID 42143523 · Publisher ↗
Chinese chive is a nutrient-dense vegetable prized for its rich bioactive compounds, unique flavor, and potential health benefits. Despite its widespread culinary and medicinal use, the volatile profiles of diverse Chine...
Chinese chive is a nutrient-dense vegetable prized for its rich bioactive compounds, unique flavor, and potential health benefits. Despite its widespread culinary and medicinal use, the volatile profiles of diverse Chinese chive varieties remain underexplored. This study employed headspace solid-phase microextraction gas chromatography-mass spectrometry (HS-SPME/GC-MS) and electronic nose (E-nose) technology to identify and compare volatile compounds in 39 Chinese chive varieties. Results showed variability of species in the composition and content of volatile components among 39 Chinese chive varieties. Total 97 volatile compounds were detected by GC-MS, including sulfur compounds, aldehydes, ketones, esters, alcohols, nitrogen oxides, and other substances. Among all varieties, sulfur compounds exhibited the richest variety (14-24 compounds) and the highest content (4022.45-62,754.55 µg/kg). Twenty-five characteristic volatile compounds with OAV≥1 were identified, with dimethyl trisulfide, dimethyl disulfide, and trans-β-ionone presenting the highest OAV values, and imparting garlic, onion, and floral aromas. Multivariate and correlation analysis between GC-MS and electronic nose comprehensively and accurately revealed samples differences. These findings not only establish a reliable methodology for flavor quality assessment but also highlight the potential health-promoting volatile sulfur compounds in Chinese chives. This work provides a foundation for future research on flavor optimization and the functional benefits of Chinese chive varieties.
In-syringe solid-phase extraction coupled with UPLC-MS/MS for simultaneous determination of reducing sugars, animo acids and Amadori compounds in tobacco.
Wang X, Lai Y, Guo S … +6 more , Qin H, Liu Z, Xia L, Wang X, Wu J, Li G
J Chromatogr A · 2026 Aug · PMID 42140040 · Publisher ↗
Considering the critical role of Maillard reaction-related compounds in determining the sensory and chemical stability of tobacco, this study develops an in-syringe SPE coupled with UPLC-MS/MS method for simultaneous det...
Considering the critical role of Maillard reaction-related compounds in determining the sensory and chemical stability of tobacco, this study develops an in-syringe SPE coupled with UPLC-MS/MS method for simultaneous determination of 43 Maillard reaction-related compounds in tobacco, covering reducing sugars (3), amino acids (17), Amadori compounds (17), and structurally related intermediates (6). The sample pretreatment utilizes HLB-packed self-assembled columns for SPE, followed by methanol elution. The extracted solution is then analyzed using a Titank C column (150×2.1 mm, 1.8 μm), with acetonitrile and 0.1% formic acid aqueous solution employed as the mobile phase for gradient elution. Data were acquired in multiple reaction monitoring mode using electrospray ionization. Operation parameters were optimized systematically, including the type and amount of filler, solution pH, loading rate, elution solvent composition, and sample extraction volume. This method demonstrated excellent linearity for all 43 target compounds, with correlation coefficients exceeding 0.9980. The limit of detections was 0.10-0.50 µg/L for animo acids, 1.0×10- 2.5×10 µg/L for reducing sugars, 0.10-5.0 µg/L for related Amadori compounds. This approach was successfully applied to the analysis of tobacco samples and extracts, providing a robust tool for studying the Maillard reaction and contributing to food safety assessment and optimization of food processing techniques.
Magnetic graphene-imine-linked covalent organic polymer composites for fast extraction and UPLC-MS/MS quantification of 14 trace drugs of abuse and their metabolites in wastewater.
Zhu R, Hu C, Yan H … +5 more , Cui J, Zheng X, Yuan S, Li Y, Xiang P
J Chromatogr A · 2026 Aug · PMID 42140039 · Publisher ↗
Wastewater-based epidemiology has emerged as a robust and effective tool for monitoring and assessing drug abuse trends. However, the analysis of drugs in wastewater remains challenging due to their ultra-trace concentra...
Wastewater-based epidemiology has emerged as a robust and effective tool for monitoring and assessing drug abuse trends. However, the analysis of drugs in wastewater remains challenging due to their ultra-trace concentrations and the inherent complexity of the wastewater matrix. In this study, a magnetic graphene-imine-linked covalent organic polymer composite (MG-COP) was first prepared via a simple, mild, and scalable synthetic route and applied as a magnetic solid-phase extraction (MSPE) adsorbent to simultaneously separate and enrich 14 target drugs of abuse and their metabolites in wastewater. The synthesized MG-COP demonstrated a high specific surface area, high thermal stability, and good magnetic separation properties. Subsequently, an efficient and rapid analytical method was established by coupling MSPE with ultra-performance liquid chromatography-tandem mass spectrometry for the determination of 14 target analytes in wastewater. Under the optimized conditions, the method exhibited excellent sensitivity (limits of detection ranging from 1.0 to 10 ng L), high reproducibility (relative standard deviations within the range of 0.8-11.3%), and robust linearity with coefficient of determination (R) ≥ 0.9932. Notably, the MSPE process required only 1 min for extraction and a small sample volume of 10 mL. Furthermore, the established method was successfully applied to real wastewater samples, revealing methamphetamine, morphine, and codeine as the dominant drugs of abuse in the analyzed wastewater. The MG-COP-based MSPE method, characterized by simplicity, rapidity, and efficiency, provides an effective sample pretreatment approach for determining trace drugs of abuse in complex wastewater matrices.
Ion-pair-free reversed-phase liquid chromatographic profiling of oligonucleotides through selective phosphorothioate alkylation.
Bui QD, Anh DT, Eßer D … +3 more , Noten B, Deschrijver T, Eeltink S
J Chromatogr A · 2026 Aug · PMID 42140038 · Publisher ↗
Phosphorothioate (PS) oligonucleotides typically contain critical impurities, including phosphodiester linkages and shortmer variants. Owing to their high structural similarity, these species are difficult to resolve by...
Phosphorothioate (PS) oligonucleotides typically contain critical impurities, including phosphodiester linkages and shortmer variants. Owing to their high structural similarity, these species are difficult to resolve by reversed-phase liquid chromatography, without the addition of ion-pairing agents. In this study, a selective alkylation strategy targeting the sulfur atom was investigated, enabling differentiation of oligonucleotides with varying numbers of PS modifications and thereby facilitating comprehensive impurity profiling using ion-pair-free RPLC. Whereas conventional oligonucleotides display a pronounced on-off retention mechanism, alkylation leads to a weakened on-off retention mechanism. Diastereomeric separations of oligonucleotides containing multiple PS modifications were achieved using an optimized method, employing two 150 mm columns in series and applying 5 °C column temperature. For oligonucleotide sequences containing three and four PS modifications, 6 out of 8 and 11 out of 16 diastereomers could be resolved, respectively.
Tetrahedral framework DNA-aptamer clicked affinity monolith with enhanced specificity for online profiling of Okadaic acid.
Peng Q, Luo D, Chen C … +4 more , Liu K, Lin C, Weng Q, Lin X
J Chromatogr A · 2026 Aug · PMID 42140037 · Publisher ↗
Developing high-performance aptamer-mediated affinity monolith represent a powerful strategy for highly efficient recognition and online precise target profiling (e.g. shellfish toxin). However, challenges including spon...
Developing high-performance aptamer-mediated affinity monolith represent a powerful strategy for highly efficient recognition and online precise target profiling (e.g. shellfish toxin). However, challenges including spontaneous aggregation and interchain entanglement of aptamers, still remain and severely impede high-specificity performance in affinity monoliths. Herein, a novel affinity interface engineering approach based on tetrahedral framework nucleic acid-aptamer conjugates (tFNA-apts) was proposed for building the brush-like tFNA-apt architecture and corresponding affinity monoliths. tFNA-apts with rigid scaffold and upright-top aptamers were clicked on polymer clusters, enabling robust structure, dispersive orientation and favourable conformational freedom of each aptamer in the brush-like architecture, therefore suppressed inter-strand entanglement and maximized target accessibility. Thanks to these merits, the prevalent defects including inter-strand entanglement or self-folding and substrate interfacial interactions of conventional single-strand aptamers (SS-apts) were addressed, thereby significantly boosting the specificity of affinity monolith for more efficient recognition. Excellent recognition performance was achieved on the tFNA-apts-clicked monolith with a low aptamer density of 152 μmol L, as was just 1/5∼1/50 of that used in traditional SS-apts monoliths. By using okadaic acid (OA) as the model analyte, the recovery yield was significantly improved from 56∼71% (SS-apts monolith) to 90∼97% (tFNA-apts monolith), and even outperformed the monoliths with saturated aptamer loading in real shellfishes analysis. Applied to bivalves seafood (eg. clam, mussel and oyster), acceptable OA recovery yields in 90.01 ± 0.85% ∼ 101.36 ± 1.28% (n = 3) were achieved with a limit of detection (LOD) of 0.075 ng mL⁻¹, and the superior analytical performance to that of classical HLB cartridge was also achieved. This work posed a facile yet efficient strategy for constructing high-performance tFNA-apt affinity monoliths, enabling improved specific recognition and precise profiling of shellfish toxins.
Analysis of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in air emission samples by GCHRMS: method development, validation and a real-case application.
Sales-Alba A, Ortiz Almirall X, Diaz-Ferrero J
J Chromatogr A · 2026 Aug · PMID 42140036 · Publisher ↗
Polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) are emerging dioxin-like pollutants formed during bromine-containing thermal processes, yet not harmonized analytical methods currently exist for their determi...
Polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) are emerging dioxin-like pollutants formed during bromine-containing thermal processes, yet not harmonized analytical methods currently exist for their determination in atmospheric emissions. Most applications adapt PCDD/F protocols despite the distinct physicochemical behaviour of brominated analogues and their associated analytical challenges. Here, an improved GCHRMS method is presented for the determination of the thirteen commercially available 2,3,7,8-PBDD/F congeners in air emissions, providing an alternative sample preparation workflow avoiding dichloromethane during clean-up and fractionation. Key instrumental parameters -pulsed splitless injection, pulse conditions, inlet temperature, carrier gas flow and electron ionization energy- were optimized to enhance sensitivity across tetra- to octabrominated congeners. Sample preparation consisted of 20 h Soxhlet extraction with toluene, followed by a simplified multilayer silica column (without AgNO) and an activated carbon fractionation, enabling a selective PBDE-PBDD/F separation through planarity-based retention. Method validation, following criteria adapted from EN 1948 and EPA 1613, demonstrated satisfactory analytical performance, including linearity over at least two orders of magnitude (relative response factor RSD ≤ 9 %), repeatability of 0.8-6.1 % in real emission matrices, accuracy ranging from -7.6 % to +17.4 %, and method quantification limits of 0.014-0.429 pg Nm. Application to an eleven-month industrial monitoring campaign confirmed method robustness under routine conditions and enabled congener-resolved PBDD/F profiling and provisional I-TEQ and WHO-TEQ assessment. Overall, the present study reports a validated and integrated DCM-free analytical workflow for PBDD/F, providing a practical expansion of available strategies for future monitoring and standardisation efforts.
Investigation of adsorption behavior and scale up for hydroxysafflor yellow A purification from Safflower: a case study.
Tabesh A, Rezadoost H, Rahimi M … +3 more , Norouzi HR, Felletti S, Cavazzini A
J Chromatogr A · 2026 Aug · PMID 42134028 · Publisher ↗
Given the complexity of natural extracts, multiple purification steps are often required to satisfy strict purity requirements for the isolated product. In this context, mathematical modeling could be a useful tool to ev...
Given the complexity of natural extracts, multiple purification steps are often required to satisfy strict purity requirements for the isolated product. In this context, mathematical modeling could be a useful tool to evaluate the feasibility of large-scale purification and to find optimal elution conditions without relying on the traditional trial-and-error method. In this work, the thermodynamic behavior of Hydroxysafflor yellow A (HSYA), the primary bioactive pigment in the safflower plant, has been modeled and simulated under gradient elution conditions in analytical scale to find optimal parameters for its isolation under preparative scale. Adsorption isotherm parameters were determined through the so-called inverse method in the analytical scale and further confirmed in the preparative scale. The general rate model accurately predicted elution profiles by considering all mass transfer resistances between the stationary and mobile phases, with excellent agreement between simulated and experimental data. It resulted that the optimization of process operating variables led to an increase of the HSYA purity from 20% (crude extract) to 80% (after enrichment), and further purified to 95% using reversed-phase preparative chromatography. The proposed workflow offers a scalable and sustainable strategy for purifying a natural compound using enrichment and subsequent purification techniques.
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