Journal of Chromatography A最新文献

英文中文

Assessment of LC-QTOF-MS data independent acquisition for quantification and suspect screening of pesticides in agriculture impacted water samples 评估独立于 LC-QTOF-MS 数据采集的农业影响水样中农药定量和可疑筛选方法

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-04-13 DOI: 10.1016/j.chroma.2025.465957

V. Fernández-Fernández, G. Castro, M. Ramil, I. Rodríguez

Assessing the impact of agricultural pesticides, and their potential transformation products, in surface (SW) and groundwater (GW) requires the application of target and screening methodologies to cover the maximum number of species. This research investigates the performance of the data independent acquisition (DIA) mode for the quantification of target compounds and the suspect screening of additional pesticides in SW and GW based on a single chromatographic run. Samples were analysed using a liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) platform, combined with an on-line solid-phase extraction (SPE) step. A suite of fungicides and insecticides, widely employed in intensive viticulture areas, was selected to assess the performance of target and screening methodologies in combination with a database of product ion spectra for more than 700 pesticides. As regards quantification of targets, the method achieved limits of quantification (LOQs) between 2 ng l^-1 and 25 ng l^-1, with linear responses from LOQs up to 500 ng l^-1. Accuracy remained between 70 % and 120 %, based on the use of ultrapure water calibration standards. Suspect screening permitted the identification of 90 % of tested compounds when added to SW and GW at levels above 50 ng l^-1, improving the percentage of correct identifications versus those attained operating the LC-QTOF-MS platform in the data dependent acquisition (DDA) mode.

{"title":"Assessment of LC-QTOF-MS data independent acquisition for quantification and suspect screening of pesticides in agriculture impacted water samples","authors":"V. Fernández-Fernández, G. Castro, M. Ramil, I. Rodríguez","doi":"10.1016/j.chroma.2025.465957","DOIUrl":"10.1016/j.chroma.2025.465957","url":null,"abstract":"<div><div>Assessing the impact of agricultural pesticides, and their potential transformation products, in surface (SW) and groundwater (GW) requires the application of target and screening methodologies to cover the maximum number of species. This research investigates the performance of the data independent acquisition (DIA) mode for the quantification of target compounds and the suspect screening of additional pesticides in SW and GW based on a single chromatographic run. Samples were analysed using a liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) platform, combined with an on-line solid-phase extraction (SPE) step. A suite of fungicides and insecticides, widely employed in intensive viticulture areas, was selected to assess the performance of target and screening methodologies in combination with a database of product ion spectra for more than 700 pesticides. As regards quantification of targets, the method achieved limits of quantification (LOQs) between 2 ng l<sup>-1</sup> and 25 ng l<sup>-1</sup>, with linear responses from LOQs up to 500 ng l<sup>-1</sup>. Accuracy remained between 70 % and 120 %, based on the use of ultrapure water calibration standards. Suspect screening permitted the identification of 90 % of tested compounds when added to SW and GW at levels above 50 ng l<sup>-1</sup>, improving the percentage of correct identifications versus those attained operating the LC-QTOF-MS platform in the data dependent acquisition (DDA) mode.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1751 ","pages":"Article 465957"},"PeriodicalIF":3.8,"publicationDate":"2025-04-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143828622","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

The complete 2025 Wayne State University compound descriptor database for use with the solvation parameter model

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-04-13 DOI: 10.1016/j.chroma.2025.465958

Colin F. Poole

The solvation parameter model is a well-established quantitative structure-property relationship model suitable for describing the contribution of intermolecular interactions in a wide range of separation, chemical, biological, and environmental processes. The model employs six descriptors (seven for compounds that exhibit variable hydrogen-bond basicity) to characterize the capability of non-ionic compounds to interact with their environment. McGowan's characteristic volume (V) and excess molar refraction (E) for liquids at 20 °C can be calculated from structure and a refractive index value in the case of E. The other descriptors identified as dipolarity/polarizability (S), overall hydrogen-bond acidity (A),overall hydrogen-bond basicity (B or B°), the gas-liquid partition constant at 25 °C (L), and E for solids at 20 °C are experimental values assigned from retention factor measurements by gas, reversed-phase liquid, and micellar and microemulsion electrokinetic chromatography and liquid-liquid partition constants using the Solver method. The assembled descriptor database of 387 varied compounds (hydrocarbons, alcohols, aldehydes, anilines, amides, halohydrocarbons, esters, ethers, ketones, nitrohydrocarbons, phenols, steroids, organosiloxanes, and N-heterocyclic compounds) provide improved precision and predictive capability compared with the WSU-2020 descriptor database. The expanded and updated WSU-2025 descriptor database replaces the WSU-2020 descriptor database.

{"title":"The complete 2025 Wayne State University compound descriptor database for use with the solvation parameter model","authors":"Colin F. Poole","doi":"10.1016/j.chroma.2025.465958","DOIUrl":"10.1016/j.chroma.2025.465958","url":null,"abstract":"<div><div>The solvation parameter model is a well-established quantitative structure-property relationship model suitable for describing the contribution of intermolecular interactions in a wide range of separation, chemical, biological, and environmental processes. The model employs six descriptors (seven for compounds that exhibit variable hydrogen-bond basicity) to characterize the capability of non-ionic compounds to interact with their environment. McGowan's characteristic volume (V) and excess molar refraction (E) for liquids at 20 °C can be calculated from structure and a refractive index value in the case of E. The other descriptors identified as dipolarity/polarizability (S), overall hydrogen-bond acidity (A),overall hydrogen-bond basicity (B or B°), the gas-liquid partition constant at 25 °C (L), and E for solids at 20 °C are experimental values assigned from retention factor measurements by gas, reversed-phase liquid, and micellar and microemulsion electrokinetic chromatography and liquid-liquid partition constants using the Solver method. The assembled descriptor database of 387 varied compounds (hydrocarbons, alcohols, aldehydes, anilines, amides, halohydrocarbons, esters, ethers, ketones, nitrohydrocarbons, phenols, steroids, organosiloxanes, and N-heterocyclic compounds) provide improved precision and predictive capability compared with the WSU-2020 descriptor database. The expanded and updated WSU-2025 descriptor database replaces the WSU-2020 descriptor database.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1752 ","pages":"Article 465958"},"PeriodicalIF":3.8,"publicationDate":"2025-04-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143834217","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

The implicit role of the hold-up volume in defining the adsorbed layer thickness

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-04-10 DOI: 10.1016/j.chroma.2025.465952

Hung-Wei Tsui , Wen-Lan Zhou , Cheng-Da Wu

The retention factor is a fundamental parameter for interpreting adsorption behavior in chromatography. However, its calculation requires a hold-up volume—often taken as the column's true void volume—without explicitly considering the thickness of the adsorbed layer. This study reveals that such an approach implicitly adopts an excess-adsorption perspective. Different definitions for the adsorbed-layer thickness affect whether a resulting isotherm is interpreted as excess or total adsorption. The results highlight the necessity of carefully aligning the choice of hold-up volume with the intended theoretical framework—such as Langmuir or BET models—to avoid misinterpretations in thermodynamic analyses. By emphasizing the subtle but critical link between the adsorbed-layer definition and adsorption data, this study provides a clearer foundation for understanding adsorption and retention mechanisms.

引用次数: 0

Separation method using column sealing technology with silicon pneumatic microvalve in capillary gas chromatography

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-04-10 DOI: 10.1016/j.chroma.2025.465950

Shigeaki Shibamoto, Wenjian Lu, Ayaka Sato

In this study, we developed a novel sampling/switching module by combining silicon pneumatic microvalves with a metal channel plate, replacing the need for conventional two-position-multiport switching valves to solve the problem of peak coelution in multi-column gas chromatography. The channel plate has a flow path volume equivalent to that of a conventional capillary column. The silicon microvalves developed in the study were characterized with minimal dead volume and high sealing performance. As a result, this module allows for mobile phase in the gaseous phase and target compounds to be sealed in the column, while enabling the control of component elution times from columns in a multi-column GC system connected to a single detector, effectively avoiding peak coelution. It is considered that the use of this module will contribute to the simplification of analytical condition settings and the miniaturization of the instrumentation.

引用次数: 0

Extended multidimensional design space studies: Comparing volatile and non-volatile buffer systems in UPLC

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-04-10 DOI: 10.1016/j.chroma.2025.465951

Arnold Zöldhegyi , Barnabás Soós , Krisztián Horváth , Imre Molnár , Róbert Kormány

Selecting the appropriate pH modifiers for separating ionizable compounds in HPLC often presents complex challenges that are frequently overlooked by industry practitioners. In Reversed-Phase Chromatography (RPC), defining pH is particularly problematic due to the presence of organic solvents, which influence the dissociation behavior of buffering agents, ionizable analytes, and residual silanol groups on the silica base material. Additional factors such as temperature changes and varying buffering capacities further complicate the interpretation of pH-effects on the separation.

A key practical question arises: can a volatile acetate buffer effectively replace an equimolar non-volatile phosphate buffer within the same pH range? To explore this, we utilized an Analytical Quality by Design (AQbD) modeling approach with DryLab to construct and compare three-dimensional (t_G-T-pH) separation models for terazosin and selected impurities across a pH range of 6.0–8.0. These Design Space (DS) models provided a comprehensive understanding of the dynamic changes occurring within each separation system. Notably, our findings revealed not only equivalent separation performance, as indicated by overlapping Method Operable Design Regions (MODRs), but also critical insights into buffer-specific differences in the selectivity of HPLC-separations.

{"title":"Extended multidimensional design space studies: Comparing volatile and non-volatile buffer systems in UPLC","authors":"Arnold Zöldhegyi , Barnabás Soós , Krisztián Horváth , Imre Molnár , Róbert Kormány","doi":"10.1016/j.chroma.2025.465951","DOIUrl":"10.1016/j.chroma.2025.465951","url":null,"abstract":"<div><div>Selecting the appropriate pH modifiers for separating ionizable compounds in HPLC often presents complex challenges that are frequently overlooked by industry practitioners. In Reversed-Phase Chromatography (RPC), defining pH is particularly problematic due to the presence of organic solvents, which influence the dissociation behavior of buffering agents, ionizable analytes, and residual silanol groups on the silica base material. Additional factors such as temperature changes and varying buffering capacities further complicate the interpretation of pH-effects on the separation.</div><div>A key practical question arises: can a volatile acetate buffer effectively replace an equimolar non-volatile phosphate buffer within the same pH range? To explore this, we utilized an Analytical Quality by Design (AQbD) modeling approach with DryLab to construct and compare three-dimensional (t<sub>G</sub>-T-pH) separation models for terazosin and selected impurities across a pH range of 6.0–8.0. These Design Space (DS) models provided a comprehensive understanding of the dynamic changes occurring within each separation system. Notably, our findings revealed not only equivalent separation performance, as indicated by overlapping Method Operable Design Regions (MODRs), but also critical insights into buffer-specific differences in the selectivity of HPLC-separations.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1751 ","pages":"Article 465951"},"PeriodicalIF":3.8,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143823617","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Integrated mammalian cell culture and growth measurement using headspace analysis: Experimental and modeling results

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-04-09 DOI: 10.1016/j.chroma.2025.465947

Hui-Jun Jin , Zi-Dong Qiu , Chun-Yun Zhang , Yu Peng

Closed-system mammalian cell culture methods have gained prominence due to their potential to minimize contamination risks and support compact experimental designs. However, complete closed-systems often encounter challenges such as pH regulation and oxygen supplementation. This study introduces a novel approach that integrates headspace analysis with mammalian cell culture. The method enables in-situ measurement of CO₂ production by cells, providing quantitative understanding of cell growth. Importantly, we developed mathematical models to elucidate the dynamics of pH changes and oxygen depletion, offering predictive insights for optimizing culture conditions for different cell lines. Using HepG2 cells as a model cell line, the present method agreed well with the reference method (i.e., sulforhodamine B assay) on determining the cell growth curve (R² = 0.98). Furthermore, the method demonstrated good precision, with biological replicates showing relative standard deviations below 7 % across 24-, 36-, and 48-hour culture periods. This integrated approach not only provides solutions for mitigating the limitations of closed-system cell culture but also establishes a framework for high-throughput and efficient applications in biomanufacturing and biomedical research.

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引用次数: 0

Analytical methodology for challenging persistent, mobile, and toxic substances in vegetal matrices after irrigation with contaminated water

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-04-07 DOI: 10.1016/j.chroma.2025.465948

Sergi Gregorio-Lozano, Victoria Bolos-Sánchez, Jorge Pitarch-Motellón, Elena Pitarch, Lubertus Bijlsma

Reusing wastewater for irrigation is proposed as a strategy to address water scarcity. However, the long-term environmental consequences of this practice are still unknown, especially when reclaimed water contains contaminants of emerging concern, such as persistent, mobile, and toxic (PMT) compounds, due to the inefficiency of wastewater treatment plants in removing certain pollutants. As a result, irrigation with contaminated water could lead to their uptake by crops and enter the food chain. While data on the presence of PMTs in environmental samples is starting to emerge, the analysis of certain compounds in vegetable matrices remains unexplored. In this study, an analytical methodology was developed and validated for the determination of 8 PMTs (i.e., benzophenone-3, clarithromycin, imazalil, metformin, sulpiride, terbutryn, tiapride, and tramadol) in escarole, tomatoes, and tomato leaves. The proposed analytical methodology used a QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) extraction method prior to mixed-mode liquid chromatography tandem mass spectrometry analysis. Method validation, performed according to SANTE guidelines, presented satisfactory results at studied concentrations (1, 10 and 100 ng·g^-1 for each compound/matrix combination, except for metformin in escarole (50 and 500 ng·g^-1). Recoveries ranged from 70 to 120 %, with a precision of ≤ 20 % for most compounds. Benzophenone-3 and tiapride, for which no isotopically labelled internal standard was available, could be adjusted by applying a correction factor. The limit of quantification was 1 ng·g^-1 for all compounds in the three matrices, except for benzophenone-3 and metformin in both escarole and tomato leaves. The applicability of the method was tested by analysing samples from an experimental greenhouse plot where crops were irrigated with water spiked with the selected PMTs.

{"title":"Analytical methodology for challenging persistent, mobile, and toxic substances in vegetal matrices after irrigation with contaminated water","authors":"Sergi Gregorio-Lozano, Victoria Bolos-Sánchez, Jorge Pitarch-Motellón, Elena Pitarch, Lubertus Bijlsma","doi":"10.1016/j.chroma.2025.465948","DOIUrl":"10.1016/j.chroma.2025.465948","url":null,"abstract":"<div><div>Reusing wastewater for irrigation is proposed as a strategy to address water scarcity. However, the long-term environmental consequences of this practice are still unknown, especially when reclaimed water contains contaminants of emerging concern, such as persistent, mobile, and toxic (PMT) compounds, due to the inefficiency of wastewater treatment plants in removing certain pollutants. As a result, irrigation with contaminated water could lead to their uptake by crops and enter the food chain. While data on the presence of PMTs in environmental samples is starting to emerge, the analysis of certain compounds in vegetable matrices remains unexplored. In this study, an analytical methodology was developed and validated for the determination of 8 PMTs (i.e.<em>,</em> benzophenone-3, clarithromycin, imazalil, metformin, sulpiride, terbutryn, tiapride, and tramadol) in escarole, tomatoes, and tomato leaves. The proposed analytical methodology used a QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) extraction method prior to mixed-mode liquid chromatography tandem mass spectrometry analysis. Method validation, performed according to SANTE guidelines, presented satisfactory results at studied concentrations (1, 10 and 100 ng·g<sup>-1</sup> for each compound/matrix combination, except for metformin in escarole (50 and 500 ng·g<sup>-1</sup>). Recoveries ranged from 70 to 120 %, with a precision of ≤ 20 % for most compounds. Benzophenone-3 and tiapride, for which no isotopically labelled internal standard was available, could be adjusted by applying a correction factor. The limit of quantification was 1 ng·g<sup>-1</sup> for all compounds in the three matrices, except for benzophenone-3 and metformin in both escarole and tomato leaves. The applicability of the method was tested by analysing samples from an experimental greenhouse plot where crops were irrigated with water spiked with the selected PMTs.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1751 ","pages":"Article 465948"},"PeriodicalIF":3.8,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143816449","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A flower-shaped recycled polymeric-coated cellulose paper for the isolation of organic contaminants from waters

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-04-07 DOI: 10.1016/j.chroma.2025.465949

Khwanchanok Samkampang , M. Laura Soriano , Rafael Lucena , Chongdee Thammakhet-Buranachai , Soledad Cárdenas

Polymeric waste, often discarded from everyday activities, poses environmental risks. An eco-sustainable thin-film microextraction approach (TFME) utilizing flower-like filter paper coated with waste polymers as the sorptive phase is presented herein for isolating volatile organic compounds (VOCs) from water samples. This particular phase configuration allows an efficient stirring with minimal resource consumption. The sorptive phase is prepared by dip-coating, which offers simplicity and enables simple polymer reusability. Low-density polyethylene (LDPE) and expanded polystyrene (PS) residues were evaluated as polymeric coatings, the latter providing a more efficient isolation of the analytes in shorter times. The effect of the main variables involved in the synthesis (paper size, polymer selection, concentration of the polymeric precursor, and the number of dips) and extraction process (extraction and elution parameters) was thoroughly evaluated. Working under the optimum conditions and using gas chromatography-mass spectrometry (GC–MS) as the instrumental technique, quantification limits in the range of 9-10 µg L^-1 were obtained for toluene, o- and p-xylene, ethylbenzene and styrene. Intra-day and inter-day precision (expressed as relative standard deviation) better than 7.6%, and accuracy (expressed as relative recoveries) in the 92-110% range were also obtained. The developed method was applied successfully to varied drinking water samples, revealing pollutants across diverse packaging materials. In tap waters, laboratory levels of styrene were noted (18 ± 3 µg L^-1). Mineral water in biobased cartons exhibited styrene, toluene (15.2 ± 0.3 µg L^-1), o-xylene (5.5 ± 0.2 µg L^-1), along with detected styrene and toluene in polyethylene terephthalate (PET) bottles.

{"title":"A flower-shaped recycled polymeric-coated cellulose paper for the isolation of organic contaminants from waters","authors":"Khwanchanok Samkampang , M. Laura Soriano , Rafael Lucena , Chongdee Thammakhet-Buranachai , Soledad Cárdenas","doi":"10.1016/j.chroma.2025.465949","DOIUrl":"10.1016/j.chroma.2025.465949","url":null,"abstract":"<div><div>Polymeric waste, often discarded from everyday activities, poses environmental risks. An eco-sustainable thin-film microextraction approach (TFME) utilizing flower-like filter paper coated with waste polymers as the sorptive phase is presented herein for isolating volatile organic compounds (VOCs) from water samples. This particular phase configuration allows an efficient stirring with minimal resource consumption. The sorptive phase is prepared by dip-coating, which offers simplicity and enables simple polymer reusability. Low-density polyethylene (LDPE) and expanded polystyrene (PS) residues were evaluated as polymeric coatings, the latter providing a more efficient isolation of the analytes in shorter times. The effect of the main variables involved in the synthesis (paper size, polymer selection, concentration of the polymeric precursor, and the number of dips) and extraction process (extraction and elution parameters) was thoroughly evaluated. Working under the optimum conditions and using gas chromatography-mass spectrometry (GC–MS) as the instrumental technique, quantification limits in the range of 9-10 µg L<sup>-1</sup> were obtained for toluene, <em>o-</em> and <em>p-</em>xylene, ethylbenzene and styrene. Intra-day and inter-day precision (expressed as relative standard deviation) better than 7.6%, and accuracy (expressed as relative recoveries) in the 92-110% range were also obtained. The developed method was applied successfully to varied drinking water samples, revealing pollutants across diverse packaging materials. In tap waters, laboratory levels of styrene were noted (18 ± 3 µg L<sup>-1</sup>). Mineral water in biobased cartons exhibited styrene, toluene (15.2 ± 0.3 µg L<sup>-1</sup>), <em>o</em>-xylene (5.5 ± 0.2 µg L<sup>-1</sup>), along with detected styrene and toluene in polyethylene terephthalate (PET) bottles.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1751 ","pages":"Article 465949"},"PeriodicalIF":3.8,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143823611","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Machine learning-driven insights into retention mechanism in IAM chromatography of anticancer sulfonamides: Implications for biological efficacy

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-04-05 DOI: 10.1016/j.chroma.2025.465911

Wiktor Nisterenko , Beata Żołnowska , Jiayin Deng , Dominika Zgoda , Alicja Różycka , Katarzyna Ewa Greber , Aneta Pogorzelska , Krzysztof Szafrański , Anita Bułakowska , Łukasz Tomorowicz , Anna Kawiak , Wiesław Sawicki , Defang Ouyang , Jarosław Sławiński , Krzesimir Ciura

Machine learning (ML) tools offer new opportunities in drug discovery, especially for enhancing our understanding of molecular interactions with biological systems. This study develops a comprehensive quantitative structure-retention relationship (QSRR) model to elucidate sulfonamides' binding mechanisms to phospholipids via immobilized artificial membrane (IAM) chromatography. Using a dataset of over 500 sulfonamide derivatives, we combined experimental IAM-HPLC data with computational molecular descriptors and ML techniques, achieving robust predictive models. The descriptor-based LASSO regression model effectively predicts retention behavior (R² = 0.71, Q² = 0.77), providing insights into molecular interactions. Critical descriptors influencing these interactions include aqueous solubility, nitrogen-to-oxygen ratio, atomic and mass descriptors such as atom and ring count, as well as logP, indicative of molecular lipophilicity. Furthermore, the fingerprint-based predictive support vector machine model demonstrated superior performance (R² = 0.899 Q² = 0.810) highlighting structural features such as benzene rings and nitrogen-attached fragments as crucial factors in determining phospholipid affinity. Furthermore, predictive models for anticancer activities across three cell lines—HCT-116, HeLa, and MCF-7—were constructed, highlighting CHI_IAM value as a critical determinant of bioactivity. The findings underscore the utility of integrated ML and chromatographic approaches in streamlining the drug development pipeline, improving predictions of biological efficacy while reducing experimental burden.

机器学习（ML）工具为药物发现提供了新的机遇，尤其是在增强我们对分子与生物系统相互作用的理解方面。本研究建立了一个全面的定量结构-保留关系（QSRR）模型，通过固定人工膜（IAM）色谱法阐明磺胺类药物与磷脂的结合机制。利用包含 500 多种磺胺衍生物的数据集，我们将 IAM-HPLC 实验数据与计算分子描述符和 ML 技术相结合，建立了稳健的预测模型。基于描述符的 LASSO 回归模型有效地预测了保留行为（R² = 0.71，Q² = 0.77），为分子相互作用提供了见解。影响这些相互作用的关键描述符包括水溶性、氮氧比、原子和质量描述符（如原子数和环数）以及表明分子亲脂性的 logP。此外，基于指纹的支持向量机预测模型表现出卓越的性能（R² = 0.899 Q² = 0.810），突出了苯环和附氮片段等结构特征是决定磷脂亲和性的关键因素。此外，还构建了三种细胞系（HCT-116、HeLa 和 MCF-7）的抗癌活性预测模型，强调 CHIIAM 值是生物活性的关键决定因素。这些发现强调了集成 ML 和色谱方法在简化药物开发流程、改进生物药效预测同时减轻实验负担方面的实用性。

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引用次数: 0

Solid-phase microextraction coupled to gas chromatography–Mass spectrometry as an advanced method for the determination of bioplasticizers in environmental and bottled water samples 固相微萃取-气相色谱-质谱联用法作为测定环境和瓶装水样品中生物增塑剂的先进方法

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-04-04 DOI: 10.1016/j.chroma.2025.465943

Nicolette Viktoryová , Agneša Szarka , Raquel Capilla-Flores , Francisco Javier Arrebola Liébanas

The aim of this work was the development of a novel analytical method for the extraction, separation, and determination of 21 bioplasticizers in water using direct immersion – solid phase microextraction in combination with gas chromatography-tandem mass spectrometry (DI-SPME-GC–MS/MS) to monitor these substances in the environment at low concentration levels. Incubation, extraction, and desorption parameters of the SPME procedure were optimised. All solutions were incubated in a heating chamber for 10 min at 70 °C, followed by SPME extraction for 60 minutes using 50/30 µm DVB/CAR/PDMS fiber. Thermal desorption followed at 270 °C for 3 min. Bioplasticizers were determined by GC–MS/MS. The method was validated, with LODs in range of 0.3 – 3 ng/mL, and LOQs 1 – 10 ng/mL for investigated bioplasticizers. The new method was applied for the analysis of real water samples. Positive results were found in real samples of agricultural water and bottled water in concentrations over 1 ng/mL. Five of the identified bioplasticizers were determined at concentrations in the range 1.43 – 3.44 ng/mL.

这项工作的目的是开发一种新型分析方法，利用直接浸没-固相微萃取结合气相色谱-串联质谱法（DI-SPME-GC-MS/MS）对水中的 21 种生物增塑剂进行萃取、分离和测定，以监测这些物质在环境中的低浓度水平。对 SPME 程序的孵育、萃取和解吸参数进行了优化。所有溶液均在 70 °C 的加热箱中孵育 10 分钟，然后使用 50/30 µm DVB/CAR/PDMS 纤维进行 60 分钟的 SPME 萃取。然后在 270 °C 下热解吸附 3 分钟。生物增塑剂通过 GC-MS/MS 进行测定。经验证，该方法对所研究的生物增塑剂的检出限为 0.3 - 3 ng/mL，定量限为 1 - 10 ng/mL。新方法被用于分析真实水样。在浓度超过 1 纳克/毫升的农业用水和瓶装水真实样本中发现了阳性结果。在已确定的生物增塑剂中，有五种生物增塑剂的浓度范围为 1.43 - 3.44 纳克/毫升。

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