Pub Date : 2025-01-26DOI: 10.1016/j.chroma.2025.465727
Ines C. Santos, Zhihui Zhang, Lina Luo, Brian Melo, Y-J Xue, Jim X. Shen
Individual stereoisomers of a chiral drug can possess different pharmacokinetic (PK)/pharmacodynamic (PD) properties, leading to different therapeutic/toxicological effects. Therefore, chiral bioanalytical methods are required for individual stereoisomers to assess their PK properties and potential chiral inversion in vivo. Supercritical fluid chromatography (SFC) has not been a mainstay in bioanalytical labs due to limitations of robustness/reliability of old generations of SFC instrumentation. With the significant advances of newer generation SFC instruments and chiral columns, the time is ripe for implementing this technology in bioanalytical labs, particularly for difficult analysis of chiral separations where traditional normal/reversed phase and polar organic mode chromatography are not adequate or require long run times. In this publication, we used six BMS model chiral compounds to systematically examine the key aspects of SFC-MS/MS for chiral bioanalysis (e.g., chiral columns, organic modifiers/additives). The preliminary method development results showed that SFC can provide superior chiral separations in comparison with LC. Subsequent method qualifications and validation and study sample analysis for four of these chiral compounds showed that the developed chiral SFC methods performed well and met the regulatory requirements for bioanalytical method validation and study sample analysis. Our comprehensive evaluation demonstrated that UHPSFC-MS/MS offered robust/reliable chiral assays, with good sensitivity, peak resolution, and sample throughput and is well suited for chiral separation in regulated bioanalysis.
{"title":"Emerging applications of quantitative supercritical fluid chromatography-tandem mass spectrometry for chiral bioanalysis","authors":"Ines C. Santos, Zhihui Zhang, Lina Luo, Brian Melo, Y-J Xue, Jim X. Shen","doi":"10.1016/j.chroma.2025.465727","DOIUrl":"10.1016/j.chroma.2025.465727","url":null,"abstract":"<div><div>Individual stereoisomers of a chiral drug can possess different pharmacokinetic (PK)/pharmacodynamic (PD) properties, leading to different therapeutic/toxicological effects. Therefore, chiral bioanalytical methods are required for individual stereoisomers to assess their PK properties and potential chiral inversion in vivo. Supercritical fluid chromatography (SFC) has not been a mainstay in bioanalytical labs due to limitations of robustness/reliability of old generations of SFC instrumentation. With the significant advances of newer generation SFC instruments and chiral columns, the time is ripe for implementing this technology in bioanalytical labs, particularly for difficult analysis of chiral separations where traditional normal/reversed phase and polar organic mode chromatography are not adequate or require long run times. In this publication, we used six BMS model chiral compounds to systematically examine the key aspects of SFC-MS/MS for chiral bioanalysis (e.g., chiral columns, organic modifiers/additives). The preliminary method development results showed that SFC can provide superior chiral separations in comparison with LC. Subsequent method qualifications and validation and study sample analysis for four of these chiral compounds showed that the developed chiral SFC methods performed well and met the regulatory requirements for bioanalytical method validation and study sample analysis. Our comprehensive evaluation demonstrated that UHPSFC-MS/MS offered robust/reliable chiral assays, with good sensitivity, peak resolution, and sample throughput and is well suited for chiral separation in regulated bioanalysis.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1744 ","pages":"Article 465727"},"PeriodicalIF":3.8,"publicationDate":"2025-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143073120","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-26DOI: 10.1016/j.chroma.2025.465729
Yunfeng Yuan , Xiaoge Wang , Jinhua Zhu , Abdelhadi El Jaouhari , Xiuhua Liu , Md． Zaved H． Khan
Flavonoids are bioactive components in natural products, which possess anti-inflammatory, antibacterial, antioxidant, and cardiovascular protective properties. However, due to the complexity and low content of the components in these samples, developing rapid and sensitive methods for the isolation and extraction of flavonoids still remains a challenge in medical and food science. Herein, a 4-formylphenylboronic acid functionalized magnetic Fe3O4 nanomaterial (Fe3O4@FPBA) was synthesized and applied as a sorbent of magnetic solid-phase extraction (MSPE) to covalently extract flavonoids from leaves of Lonicera japonica Thunb.. The structure, morphology and magnetic properties of Fe3O4@FPBA particles were characterized by fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), vibrating sample magnetometer (VSM) and scanning electron microscope (SEM) technologies. Employing luteoloside, luteolin, lonicerin, hyperoside, quercetin and rutin as model compounds, Fe3O4@FPBA as sorbent, a MSPE coupling with capillary electrophoresis (CE) method was developed and optimized to detect the flavonoids. Adsorption kinetics display that the adsorption of flavonoids by Fe3O4@FPBA is in line with the Quasi-second-order model, which is controlled by chemisorption mechanism, with the equilibrium adsorption capacity ranging from 3.66 to 6.16 mg/g. The isothermal adsorption model shows that the adsorption is more consistent with Freundlich isotherm equation, and the exponent n is around 1. In addition, the material was applied to the leaves of Lonicera japonica Thunb. extract. Four kinds of flavonoids and three other o-hydroxyl compounds were covalently extracted and magnetically separated. Moreover, the material can still maintain high adsorption properties after recycling 5 times. The material possesses strong magnetism and boric acid ligands, which can realize rapid and high-capacity separation and enrichment of flavonoids in liquid samples. Therefore, the strategy offers an innovative method for the extraction and purification of flavonoids from complex natural plants and also provides a research basis for the discovery of new medicinal compounds based on natural products.
{"title":"Phenylboronic acid functionalized magnetic ferroferric oxide nanoparticles and capillary electrophoresis for efficient isolation of flavonoid compounds from leaves of Lonicera japonica Thunb","authors":"Yunfeng Yuan , Xiaoge Wang , Jinhua Zhu , Abdelhadi El Jaouhari , Xiuhua Liu , Md． Zaved H． Khan","doi":"10.1016/j.chroma.2025.465729","DOIUrl":"10.1016/j.chroma.2025.465729","url":null,"abstract":"<div><div>Flavonoids are bioactive components in natural products, which possess anti-inflammatory, antibacterial, antioxidant, and cardiovascular protective properties. However, due to the complexity and low content of the components in these samples, developing rapid and sensitive methods for the isolation and extraction of flavonoids still remains a challenge in medical and food science. Herein, a 4-formylphenylboronic acid functionalized magnetic Fe<sub>3</sub>O<sub>4</sub> nanomaterial (Fe<sub>3</sub>O<sub>4</sub>@FPBA) was synthesized and applied as a sorbent of magnetic solid-phase extraction (MSPE) to covalently extract flavonoids from leaves of <em>Lonicera japonica</em> Thunb.. The structure, morphology and magnetic properties of Fe<sub>3</sub>O<sub>4</sub>@FPBA particles were characterized by fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), vibrating sample magnetometer (VSM) and scanning electron microscope (SEM) technologies. Employing luteoloside, luteolin, lonicerin, hyperoside, quercetin and rutin as model compounds, Fe<sub>3</sub>O<sub>4</sub>@FPBA as sorbent, a MSPE coupling with capillary electrophoresis (CE) method was developed and optimized to detect the flavonoids. Adsorption kinetics display that the adsorption of flavonoids by Fe<sub>3</sub>O<sub>4</sub>@FPBA is in line with the Quasi-second-order model, which is controlled by chemisorption mechanism, with the equilibrium adsorption capacity ranging from 3.66 to 6.16 mg/g. The isothermal adsorption model shows that the adsorption is more consistent with Freundlich isotherm equation, and the exponent n is around 1. In addition, the material was applied to the leaves of <em>Lonicera japonica</em> Thunb. extract. Four kinds of flavonoids and three other o-hydroxyl compounds were covalently extracted and magnetically separated. Moreover, the material can still maintain high adsorption properties after recycling 5 times. The material possesses strong magnetism and boric acid ligands, which can realize rapid and high-capacity separation and enrichment of flavonoids in liquid samples. Therefore, the strategy offers an innovative method for the extraction and purification of flavonoids from complex natural plants and also provides a research basis for the discovery of new medicinal compounds based on natural products.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1744 ","pages":"Article 465729"},"PeriodicalIF":3.8,"publicationDate":"2025-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143063031","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-25DOI: 10.1016/j.chroma.2024.465620
Anna Buettner , Julia Polley , Bjoern Hardebusch , Karl Speer
Current manual multi-methods for analysis of pesticides are limited due to their complexity and scope of pesticides, high demand for time and solvent or unsuitability for broad types of food of animal origin. The following research presents a novel automated sample preparation and purification method for various food matrices of animal origin, including milk, raw milk, dairy products, cheese, eggs, fish, fish products, and offal. The Ultra-Turrax® Tube Drive System enables quick fat extraction using a solvent mixture of cyclohexane/ethyl acetate/acetonitrile. From the resulting fat extract one aliquot is taken for clean-up and another aliquot for fat content determination, applicable to products with fat contents ranging from 1% to 30%. The automated clean-up, using gel permeation chromatography and solid-phase extraction (primary secondary amine and C18 cartridge), was successfully validated for more than 40 gas chromatography-amenable pesticides relevant to food of animal origin at a level of 10 µg/kg across each matrix. Additionally, 70% of analytes in milk (28 out of 40), 80% in cheese (34 out of 40), 82% in dairy products (38 out of 40), 82% in eggs (46 out of 56), and 85% in fish and offal (48 out of 56) were validated even at a lower level of 0.5 µg/kg.
The spectrum of pesticides was expanded by employing a more comprehensive mix containing 196 gas chromatography-amenable analytes, spiked at a level of 10 µg/kg. Compared to the modified EN 1528 method, the quantification of analytes increased by 40%, representing an increase from 90 to 150 analytes out of 196 in each matrix. In conclusion, this automated analytical method can be directly implemented as a routine monitoring system for residual pesticide analysis in various matrices of animal origin, providing a robust tool for ensuring food safety.
{"title":"Automation of a modular method (EN 1528) for analysis of GC-amenable pesticides in food of animal origin","authors":"Anna Buettner , Julia Polley , Bjoern Hardebusch , Karl Speer","doi":"10.1016/j.chroma.2024.465620","DOIUrl":"10.1016/j.chroma.2024.465620","url":null,"abstract":"<div><div>Current manual multi-methods for analysis of pesticides are limited due to their complexity and scope of pesticides, high demand for time and solvent or unsuitability for broad types of food of animal origin. The following research presents a novel automated sample preparation and purification method for various food matrices of animal origin, including milk, raw milk, dairy products, cheese, eggs, fish, fish products, and offal. The Ultra-Turrax® Tube Drive System enables quick fat extraction using a solvent mixture of cyclohexane/ethyl acetate/acetonitrile. From the resulting fat extract one aliquot is taken for clean-up and another aliquot for fat content determination, applicable to products with fat contents ranging from 1% to 30%. The automated clean-up, using gel permeation chromatography and solid-phase extraction (primary secondary amine and C18 cartridge), was successfully validated for more than 40 gas chromatography-amenable pesticides relevant to food of animal origin at a level of 10 µg/kg across each matrix. Additionally, 70% of analytes in milk (28 out of 40), 80% in cheese (34 out of 40), 82% in dairy products (38 out of 40), 82% in eggs (46 out of 56), and 85% in fish and offal (48 out of 56) were validated even at a lower level of 0.5 µg/kg.</div><div>The spectrum of pesticides was expanded by employing a more comprehensive mix containing 196 gas chromatography-amenable analytes, spiked at a level of 10 µg/kg. Compared to the modified EN 1528 method, the quantification of analytes increased by 40%, representing an increase from 90 to 150 analytes out of 196 in each matrix. In conclusion, this automated analytical method can be directly implemented as a routine monitoring system for residual pesticide analysis in various matrices of animal origin, providing a robust tool for ensuring food safety.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1741 ","pages":"Article 465620"},"PeriodicalIF":3.8,"publicationDate":"2025-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142913442","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-25DOI: 10.1016/j.chroma.2024.465600
Ana M. Ares, José Bernal, Laura Toribio
The simultaneous separation of the enantiomers of six anticoagulant rodenticides, derived from 4-hydroxycoumarin, has been studied in this work. Ten different stationary phases (zwitterionic, Pirkle-type, polysaccharides and macrocyclic antibiotics derivatives) were evaluated by using supercritical fluid chromatography coupled to two different detectors (circular dichroism and mass spectrometry-single quadrupole). The effect of the type of organic modifier and temperature on the chiral separation was investigated, and the best results were obtained with the column Regis S,S-Whelk-O1 at 25 °C when using a gradient elution program with methanol as organic modifier. Considering detection, the highest sensitivity was obtained with the single quadrupole mass spectrometry detector. Under these conditions, eighteen stereoisomers were baseline resolved within 18 min. It should be also mentioned that the columns Chiralpak AS-H, Lux Cellulose-2, Chiralpak AD and Chiralpak Zwix (+) provided also good results for the enantiomeric separation of some individual compounds.
{"title":"Simultaneous separation of the enantiomers of six anticoagulant rodenticides using chiral supercritical fluid chromatography-mass spectrometry.","authors":"Ana M. Ares, José Bernal, Laura Toribio","doi":"10.1016/j.chroma.2024.465600","DOIUrl":"10.1016/j.chroma.2024.465600","url":null,"abstract":"<div><div>The simultaneous separation of the enantiomers of six anticoagulant rodenticides, derived from 4-hydroxycoumarin, has been studied in this work. Ten different stationary phases (zwitterionic, Pirkle-type, polysaccharides and macrocyclic antibiotics derivatives) were evaluated by using supercritical fluid chromatography coupled to two different detectors (circular dichroism and mass spectrometry-single quadrupole). The effect of the type of organic modifier and temperature on the chiral separation was investigated, and the best results were obtained with the column Regis S,S-Whelk-O1 at 25 °C when using a gradient elution program with methanol as organic modifier. Considering detection, the highest sensitivity was obtained with the single quadrupole mass spectrometry detector. Under these conditions, eighteen stereoisomers were baseline resolved within 18 min. It should be also mentioned that the columns Chiralpak AS-H, Lux Cellulose-2, Chiralpak AD and Chiralpak Zwix (+) provided also good results for the enantiomeric separation of some individual compounds.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1741 ","pages":"Article 465600"},"PeriodicalIF":3.8,"publicationDate":"2025-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142870609","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-25DOI: 10.1016/j.chroma.2024.465624
Julian Reinhardt , Martin Steinhaus
Odor-active compounds are major quality parameters in food and other consumer products. In the analysis of odorants, gas chromatography (GC) plays a dominant role and is particularly indispensable for odorant screening by GC–olfactometry (GC–O). Whereas artifact formation during workup before GC analysis has been widely discussed, artifact formation during GC injection has not been adequately addressed so far. Using a set of 14 test compounds, we evaluated ten different GC injection approaches. Artifact-producing reactions were particularly 1,2-eliminations. Linalyl acetate additionally showed [1,3]-sigmatropic shifts. On-column injection was confirmed as the gold standard, with virtually zero artifact formation observed not only with classic cold on-column injection in the oven, but also with on-column injection in a programmable temperature vaporizing (PTV) injector. Substantial artifact formation was observed when a high fixed injector temperature was combined with splitless injection. This applied to the injection of liquid samples but even more so to headspace solid-phase microextraction (HS–SPME) approaches. In conclusion, we recommend using on-column injection whenever aiming at a representative odorant spectrum, such as in GC–O. In targeted analysis, critical approaches such as SPME should be carefully tested for artifact formation. For the evaluation of the artifact formation potential of different injection approaches, cedryl acetate emerged as an excellent test compound.
{"title":"Injection artifacts in odorant analysis by gas chromatography","authors":"Julian Reinhardt , Martin Steinhaus","doi":"10.1016/j.chroma.2024.465624","DOIUrl":"10.1016/j.chroma.2024.465624","url":null,"abstract":"<div><div>Odor-active compounds are major quality parameters in food and other consumer products. In the analysis of odorants, gas chromatography (GC) plays a dominant role and is particularly indispensable for odorant screening by GC–olfactometry (GC–O). Whereas artifact formation during workup before GC analysis has been widely discussed, artifact formation during GC injection has not been adequately addressed so far. Using a set of 14 test compounds, we evaluated ten different GC injection approaches. Artifact-producing reactions were particularly 1,2-eliminations. Linalyl acetate additionally showed [1,3]-sigmatropic shifts. On-column injection was confirmed as the gold standard, with virtually zero artifact formation observed not only with classic cold on-column injection in the oven, but also with on-column injection in a programmable temperature vaporizing (PTV) injector. Substantial artifact formation was observed when a high fixed injector temperature was combined with splitless injection. This applied to the injection of liquid samples but even more so to headspace solid-phase microextraction (HS–SPME) approaches. In conclusion, we recommend using on-column injection whenever aiming at a representative odorant spectrum, such as in GC–O. In targeted analysis, critical approaches such as SPME should be carefully tested for artifact formation. For the evaluation of the artifact formation potential of different injection approaches, cedryl acetate emerged as an excellent test compound.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1741 ","pages":"Article 465624"},"PeriodicalIF":3.8,"publicationDate":"2025-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142890895","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-25DOI: 10.1016/j.chroma.2024.465585
Xu Wang , Xiu-mei Luan , Jia Yang , Chen Liu , Qi-hui Sun , Zhuang-zhuang Li , Yong Yang , Rong Rong
Countercurrent chromatography (CCC) is an efficient technique for purifying bioactive natural compounds, but selecting the solvent system can be a time-consuming and crucial process for successful separation. This paper discussed the HPLC-assisted mathematical prediction method for the n-hexane/alcohol solvents/water (HAWat) and ethyl acetate/n-butanol/water (EBuWat) systems and designed an intelligent online selection system to simplify the separation process. First, the applicable rage of HAWat and EBuWat solvent systems were quantified by the methanol concentration at the column inlet when template molecules peak in a HPLC analysis (B%). Then, we analyzed the relationship between the logarithmic partition coefficient (log K) of template molecules and the alcohol solvent ratio by using different brands of chromatography columns. Moreover, the prediction function was developed by correlating the best solvent composition of CCC solvent system with the B% of template molecules. The results indicated that the HAWat system was suitable for separating compounds with B% > 85 %, while the EBuWat system was effective for compounds with 40 % < B% < 55 %. The quadratic function for HAWat systems and one universal EBuWat system (8.2:1.8:10) were determined and verified to develop the HPLC-assisted mathematical prediction function method. The method could select suitable solvent systems for separfigation easily and quickly. And a step of result correction was required for the occasional discrete value. Finally, an intelligent CCC online selection system that integrates established mathematical functions was designed to enable real-time solvent selection, on-demand solvent configuration, and automated sample separation. It eliminates the iterative process of shake-flask experiments and facilitates intelligent upgrading of CCC instrumentation.
{"title":"A HPLC-assisted mathematical prediction method of ternary solvent systems to develop an intelligent online selection system for countercurrent chromatography solvent system","authors":"Xu Wang , Xiu-mei Luan , Jia Yang , Chen Liu , Qi-hui Sun , Zhuang-zhuang Li , Yong Yang , Rong Rong","doi":"10.1016/j.chroma.2024.465585","DOIUrl":"10.1016/j.chroma.2024.465585","url":null,"abstract":"<div><div>Countercurrent chromatography (CCC) is an efficient technique for purifying bioactive natural compounds, but selecting the solvent system can be a time-consuming and crucial process for successful separation. This paper discussed the HPLC-assisted mathematical prediction method for the n-hexane/alcohol solvents/water (HAWat) and ethyl acetate/n-butanol/water (EBuWat) systems and designed an intelligent online selection system to simplify the separation process. First, the applicable rage of HAWat and EBuWat solvent systems were quantified by the methanol concentration at the column inlet when template molecules peak in a HPLC analysis (B%). Then, we analyzed the relationship between the logarithmic partition coefficient (<em>log K</em>) of template molecules and the alcohol solvent ratio by using different brands of chromatography columns. Moreover, the prediction function was developed by correlating the best solvent composition of CCC solvent system with the B% of template molecules. The results indicated that the HAWat system was suitable for separating compounds with B% > 85 %, while the EBuWat system was effective for compounds with 40 % < <em>B</em>% < 55 %. The quadratic function for HAWat systems and one universal EBuWat system (8.2:1.8:10) were determined and verified to develop the HPLC-assisted mathematical prediction function method. The method could select suitable solvent systems for separfigation easily and quickly. And a step of result correction was required for the occasional discrete value. Finally, an intelligent CCC online selection system that integrates established mathematical functions was designed to enable real-time solvent selection, on-demand solvent configuration, and automated sample separation. It eliminates the iterative process of shake-flask experiments and facilitates intelligent upgrading of CCC instrumentation.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1741 ","pages":"Article 465585"},"PeriodicalIF":3.8,"publicationDate":"2025-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142875594","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}
A new thin film was fabricated using Fe3O4@SiO2-polyoxometalate (POM) as the coating and it was coupled with a HPLC-UV to develop a method for the selective determination of ibuprofen, paracetamol and diclofenac (as the model analytes) from human plasma and urine samples. The prepared magnetic POM was coated on the pores and surface of cotton yarn to prepare the extracting device. The prepared sorbent was characterized by several techniques including: FT-IR, XRD, BET, SEM, and VSM analysis. Using a multivariate optimization strategy (Plackett-Berman design (PBD) and Box-Behnken Design (BBD)), extraction factors were optimized. The optimal condition is: pH=4, extraction time=23 min, desorption time=3 min, desorption volume=400 µL, and Na2SO4 concentration=0.8 %. In the optimal condition, the linearity of the method was in the range of 0.5–200 µg l-1. LODs, LOQs, and intra-day as well as inter-day RSDs were <0.24 µg L−1, 0.81 µg L−1, and 4.1 %, respectively. The enrichment factor (EF) values for the tested substances varied from 16 to 21. The absolute recoveries (ARs%) were also between 64 and 84 %. The sorbent extracted the analytes up to 32 times with little changes in the ER (95 ± 1.5). This method was successfully applied to detect target analytes in biological fluids, achieving high recovery. This novel approach combines efficiency with practicality, making it well-suited for field applications. In addition, the greenness and whiteness of the method (sustainability assessment) were evaluated using the qualitative green assessment tools including AGREE, BAGI and the white analytical chemistry assessment tool (RGB12). The high BAGI (72.5) and RGB 12 (94.7) scores confirmed the method's strong applicability, cost-effectiveness, and sustainability.
{"title":"Magnetic polyoxometalate composite stabilized on the woven cotton yarn as a sorbent for thin film microextraction of some selected nonsteroidal anti-inflammatory drugs followed by high-performance liquid chromatography-ultraviolet detection","authors":"Zahraa Header Abdulameer Aljboory , Milad Ghani , Jahan Bakhsh Raoof","doi":"10.1016/j.chroma.2024.465615","DOIUrl":"10.1016/j.chroma.2024.465615","url":null,"abstract":"<div><div>A new thin film was fabricated using Fe<sub>3</sub>O<sub>4</sub>@SiO<sub>2</sub>-polyoxometalate (POM) as the coating and it was coupled with a HPLC-UV to develop a method for the selective determination of ibuprofen, paracetamol and diclofenac (as the model analytes) from human plasma and urine samples. The prepared magnetic POM was coated on the pores and surface of cotton yarn to prepare the extracting device. The prepared sorbent was characterized by several techniques including: FT-IR, XRD, BET, SEM, and VSM analysis. Using a multivariate optimization strategy (Plackett-Berman design (PBD) and Box-Behnken Design (BBD)), extraction factors were optimized. The optimal condition is: pH=4, extraction time=23 min, desorption time=3 min, desorption volume=400 µL, and Na<sub>2</sub>SO<sub>4</sub> concentration=0.8 %. In the optimal condition, the linearity of the method was in the range of 0.5–200 µg l<sup>-1</sup>. LODs, LOQs, and intra-day as well as inter-day RSDs were <0.24 µg <em>L</em><sup>−1</sup>, 0.81 µg <em>L</em><sup>−1</sup>, and 4.1 %, respectively. The enrichment factor (EF) values for the tested substances varied from 16 to 21. The absolute recoveries (ARs%) were also between 64 and 84 %. The sorbent extracted the analytes up to 32 times with little changes in the ER (95 ± 1.5). This method was successfully applied to detect target analytes in biological fluids, achieving high recovery. This novel approach combines efficiency with practicality, making it well-suited for field applications. In addition, the greenness and whiteness of the method (sustainability assessment) were evaluated using the qualitative green assessment tools including AGREE, BAGI and the white analytical chemistry assessment tool (RGB12). The high BAGI (72.5) and RGB 12 (94.7) scores confirmed the method's strong applicability, cost-effectiveness, and sustainability.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1741 ","pages":"Article 465615"},"PeriodicalIF":3.8,"publicationDate":"2025-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142875595","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-25DOI: 10.1016/j.chroma.2024.465608
Mir Ali Farajzadeh , Sina Mohammad Mehri , Mohammad Reza Afshar Mogaddam
This paper introduces an innovative technique for extracting pesticides from herbal infusions using a core-shell magnetic adsorbent (i.e., Cu-BTC@Fe3O4) where achieving a notable enrichment factor for the target pesticides by coupling with a dispersive liquid-liquid microextraction method. To validate the successful synthesis of the adsorbent, a range of analytical techniques were utilized including vibrating sample magnetometer, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, energy dispersive X-ray, and Brunauer-Emmett-Teller analyses. A vortex agitation and an external magnetic field were used during the extraction process to aid the analytes' desorption and adsorbent separation, respectively. Also, a mixture of iso-propanol and deionized water was used to desorb the analytes from the adsorbent surface. The resulting supernatant containing the desorbed pesticides was mixed with 1,2-dibromoethane as the extraction solvent and then injected into an aqueous medium. After centrifugation, 1 μL of the sedimented phase was introduced into the gas chromatograph system equipped with a flame ionization detector. The reliability of the proposed methodology was confirmed by obtaining low relative standard deviations (1.0–8.5 %), acceptable extraction recoveries (39–93 %), substantial enrichment factors (195–475), calibration curve linearity (r2=0.993–0.998), and significantly low limits of quantification (0.34–3.0 μg L−1) and detection (1.1–9.9 μg L−1). Absence of matrix effects with relative recovery values of 80–120 % for real samples, minimal use of the adsorbent and extraction solvent, a reduction in extraction time due to the elimination of two centrifugation steps (facilitated by an external magnetic field), and the use of environmentally friendly solvents collectively highlight the advantages and significant values of this approach.
{"title":"Application of core-shell magnetic metal-organic framework in developing dispersive micro solid phase extraction combined with dispersive liquid-liquid microextraction for the extraction and enrichment of some pesticides in orange blossom, Aloysia Citrodora, and fennel herbal infusions","authors":"Mir Ali Farajzadeh , Sina Mohammad Mehri , Mohammad Reza Afshar Mogaddam","doi":"10.1016/j.chroma.2024.465608","DOIUrl":"10.1016/j.chroma.2024.465608","url":null,"abstract":"<div><div>This paper introduces an innovative technique for extracting pesticides from herbal infusions using a core-shell magnetic adsorbent (i.e., Cu-BTC@Fe<sub>3</sub>O<sub>4</sub>) where achieving a notable enrichment factor for the target pesticides by coupling with a dispersive liquid-liquid microextraction method. To validate the successful synthesis of the adsorbent, a range of analytical techniques were utilized including vibrating sample magnetometer, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, energy dispersive X-ray, and Brunauer-Emmett-Teller analyses. A vortex agitation and an external magnetic field were used during the extraction process to aid the analytes' desorption and adsorbent separation, respectively. Also, a mixture of <em>iso</em>-propanol and deionized water was used to desorb the analytes from the adsorbent surface. The resulting supernatant containing the desorbed pesticides was mixed with 1,2-dibromoethane as the extraction solvent and then injected into an aqueous medium. After centrifugation, 1 μL of the sedimented phase was introduced into the gas chromatograph system equipped with a flame ionization detector. The reliability of the proposed methodology was confirmed by obtaining low relative standard deviations (1.0–8.5 %), acceptable extraction recoveries (39–93 %), substantial enrichment factors (195–475), calibration curve linearity (r<sup>2</sup>=0.993–0.998), and significantly low limits of quantification (0.34–3.0 μg <em>L</em><sup>−1</sup>) and detection (1.1–9.9 μg <em>L</em><sup>−1</sup>). Absence of matrix effects with relative recovery values of 80–120 % for real samples, minimal use of the adsorbent and extraction solvent, a reduction in extraction time due to the elimination of two centrifugation steps (facilitated by an external magnetic field), and the use of environmentally friendly solvents collectively highlight the advantages and significant values of this approach.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1741 ","pages":"Article 465608"},"PeriodicalIF":3.8,"publicationDate":"2025-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142890918","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-25DOI: 10.1016/j.chroma.2024.465596
Wenjia Tao , Xinfeng Che , Peipei Liu , Yu Zhang , Xiaoyu Zheng , Bin Di , Hongwei Qiao
Wastewater analysis technology has emerged as a promising tool for monitoring illicit drug consumption. However, the current reliance on the solid-phase extraction (SPE) pre-treatment method presents significant challenges for widespread adoption and high-throughput monitoring, as it consumes a large amount of time and labor as well as requires specialized instruments. This study has developed a direct injection (DI) technique for UPLC-MS/MS, enabling the detection of 77 compounds encompassing metabolites of human biomarkers, illicit drugs, and new psychoactive substances. The DI method underwent rigorous optimization and validation, demonstrating a lower limit of quantitation (LLOQ) ranging from 1 ng L–1 to 100 ng L–1 and a limit of detection (LOD) ranging from 0.5 ng L–1 to 80 ng L–1. The SPE method comprising two common SPE cartridges and the DI method were compared in terms of matrix effects, recoveries, and accuracies through analyzing spiked wastewater samples. The DI method exhibited superior capability in detecting a wider range of compounds while being more time-efficient, and it also significantly demonstrated a better recovery, lower matrix effect, and lower relative error in spiked samples. Real wastewater samples from 25 wastewater treatment plants (WWTPs) were analyzed using this method. This study expanded the targets species of wastewater analysis by DI method and provided practical strategies for conducting large-scale drug monitoring.
废水分析技术已成为监测非法药物消费的一种很有前途的工具。然而，目前对固相萃取（SPE）预处理方法的依赖对广泛采用和高通量监测提出了重大挑战，因为它消耗大量的时间和劳动力，并且需要专门的仪器。本研究开发了一种用于UPLC-MS/MS的直接注射（DI）技术，可以检测77种化合物，包括人类生物标志物的代谢物、非法药物和新的精神活性物质。该方法经过严格的优化和验证，定量下限（LLOQ）为1 ~ 100 ng L-1，检出限（LOD）为0.5 ~ 80 ng L-1。通过对加标废水样品的分析，比较了由两个常见固相萃取筒组成的固相萃取法和DI法的基质效应、回收率和准确度。该方法检测范围更广，时间效率更高，回收率更高，基质效应更低，相对误差更小。采用该方法对25家污水处理厂的实际污水样本进行了分析。本研究扩大了DI法分析废水的靶点种类，为开展大规模药物监测提供了切实可行的策略。
{"title":"Direct injection UPLC-MS/MS method for analysing 77 compounds including human biomarkers, illicit drugs, new psychoactive substances and metabolites in wastewater","authors":"Wenjia Tao , Xinfeng Che , Peipei Liu , Yu Zhang , Xiaoyu Zheng , Bin Di , Hongwei Qiao","doi":"10.1016/j.chroma.2024.465596","DOIUrl":"10.1016/j.chroma.2024.465596","url":null,"abstract":"<div><div>Wastewater analysis technology has emerged as a promising tool for monitoring illicit drug consumption. However, the current reliance on the solid-phase extraction (SPE) pre-treatment method presents significant challenges for widespread adoption and high-throughput monitoring, as it consumes a large amount of time and labor as well as requires specialized instruments. This study has developed a direct injection (DI) technique for UPLC-MS/MS, enabling the detection of 77 compounds encompassing metabolites of human biomarkers, illicit drugs, and new psychoactive substances. The DI method underwent rigorous optimization and validation, demonstrating a lower limit of quantitation (LLOQ) ranging from 1 ng L<sup>–1</sup> to 100 ng L<sup>–1</sup> and a limit of detection (LOD) ranging from 0.5 ng L<sup>–1</sup> to 80 ng L<sup>–1</sup>. The SPE method comprising two common SPE cartridges and the DI method were compared in terms of matrix effects, recoveries, and accuracies through analyzing spiked wastewater samples. The DI method exhibited superior capability in detecting a wider range of compounds while being more time-efficient, and it also significantly demonstrated a better recovery, lower matrix effect, and lower relative error in spiked samples. Real wastewater samples from 25 wastewater treatment plants (WWTPs) were analyzed using this method. This study expanded the targets species of wastewater analysis by DI method and provided practical strategies for conducting large-scale drug monitoring.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1741 ","pages":"Article 465596"},"PeriodicalIF":3.8,"publicationDate":"2025-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142870564","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-25DOI: 10.1016/j.chroma.2024.465587
Sanka N. Atapattu , Colin F. Poole
Reversed-phase liquid chromatography (RPLC) offers significant advantages over traditional methods for estimating octanol-water partition constants, which are a critical parameter in drug discovery. In contrast to classical methods for determining the octanol-water partition constant, such as shake-flask techniques, RPLC is less time-consuming and easier to automate. In this study, we explored three alternative organic solvent modifiers: acetone, 2-propanol, and tetrahydrofuran for the indirect determination of the octanol-water partition constant for neutral compounds by RPLC using either isocratic retention factors or retention factors extrapolated to 100 % water for several stationary phases. The Kinetex XB C18 column with acetone-water mobile phase compositions gave the best results for the construction of correlation models for the prediction of the octanol-water partition constant of varied compounds employing isocratic retention factors for 20 % (v/v) acetone-water and retention factors extrapolated to 100 % water. Retention factors extrapolated to 100 % water were nearly as good as the isocratic retention factors with a standard error of 0.136 and Fisher statistic of 1446 for the correlation model compared with a standard error of 0.122 and Fisher statistic of 1456 for the 20 % (v/v) acetone-water model. An XTerra MS C18 column with 10 % (v/v) tetrahydrofuran-water gave the best model for predicting the octanol-water partition constants with a standard error of 0.106 and Fisher statistic of 2806.
辛醇-水分配常数是药物发现的关键参数，反相液相色谱法（RPLC）在辛醇-水分配常数的估算方面比传统方法具有显著的优势。与测定辛醇-水分配常数的经典方法（如摇瓶技术）相比，RPLC耗时更少，更容易自动化。在这项研究中，我们探索了三种替代的有机溶剂改性剂：丙酮、2-丙醇和四氢呋喃，通过RPLC间接测定中性化合物的辛醇-水分配常数，使用等密度保留因子或保留因子外延到几个固定相的100%水。采用丙酮-水流动相组成的Kinetex XB C18柱，采用等温保留因子为20% （v/v）丙酮-水和外推保留因子为100%水，建立相关模型预测不同化合物的辛醇-水分配常数的最佳结果。与20% （v/v）丙酮-水模型的标准误差0.122和Fisher统计量1456相比，外推到100%水的保留因子几乎与等压保留因子一样好，相关模型的标准误差为0.136，Fisher统计量为1446。在XTerra MS C18色谱柱中，四氢呋喃-水浓度为10% (v/v)，预测辛醇-水分配常数的标准误差为0.106，Fisher统计量为2806。
{"title":"Prediction of the octanol-water partition constant of neutral compounds by reversed-phase liquid chromatography using alternative organic solvent modifiers","authors":"Sanka N. Atapattu , Colin F. Poole","doi":"10.1016/j.chroma.2024.465587","DOIUrl":"10.1016/j.chroma.2024.465587","url":null,"abstract":"<div><div>Reversed-phase liquid chromatography (RPLC) offers significant advantages over traditional methods for estimating octanol-water partition constants, which are a critical parameter in drug discovery. In contrast to classical methods for determining the octanol-water partition constant, such as shake-flask techniques, RPLC is less time-consuming and easier to automate. In this study, we explored three alternative organic solvent modifiers: acetone, 2-propanol, and tetrahydrofuran for the indirect determination of the octanol-water partition constant for neutral compounds by RPLC using either isocratic retention factors or retention factors extrapolated to 100 % water for several stationary phases. The Kinetex XB C18 column with acetone-water mobile phase compositions gave the best results for the construction of correlation models for the prediction of the octanol-water partition constant of varied compounds employing isocratic retention factors for 20 % (v/v) acetone-water and retention factors extrapolated to 100 % water. Retention factors extrapolated to 100 % water were nearly as good as the isocratic retention factors with a standard error of 0.136 and Fisher statistic of 1446 for the correlation model compared with a standard error of 0.122 and Fisher statistic of 1456 for the 20 % (v/v) acetone-water model. An XTerra MS C18 column with 10 % (v/v) tetrahydrofuran-water gave the best model for predicting the octanol-water partition constants with a standard error of 0.106 and Fisher statistic of 2806.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1741 ","pages":"Article 465587"},"PeriodicalIF":3.8,"publicationDate":"2025-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142870567","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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