Salvia miltiorrhiza, a widely used traditional Chinese medicine, contains a complex matrix of hydrophobic diterpenoids and hydrophilic phenolic acids, presenting significant challenges in comprehensive analysis. In this study, an online polarity-partitioned two-dimensional liquid chromatography coupled with mass spectrometry (2D-LC-MS) method was developed for comprehensive analysis of both lipophilic and hydrophilic active components in Salvia miltiorrhiza. The method integrated hydrophilic interaction liquid chromatography (HILIC) and reversed-phase liquid chromatography (RPLC), facilitating the efficient separation of compounds across a wide range of polarities. An online dilution strategy was implemented, minimizing sample loss and enhancing the method's utility for quality control and chemical characterization of complex herbal matrices. Compared with other LC methods, this approach significantly improved analyte coverage, resolution, and analysis efficiency. Under optimal conditions, 150 active components were successfully identified, including 33 compounds newly discovered in Salvia miltiorrhiza. Additionally, the validated online method was applied to the quantitative determination of 16 quality markers of Salvia miltiorrhiza from different sources. The results demonstrated the online method's potential as a superior alternative to existing techniques, offering broader applicability in traditional Chinese medicine research.
{"title":"Comprehensive characterization of active components in Salvia miltiorrhiza using polarity-partitioned two-dimensional liquid chromatography coupled with mass spectrometry","authors":"Liping Zhang , Yuye Cai , Qisheng Zhong , Shijing Zhang , Lingling Shen , Taohong Huang , Ting Zhou","doi":"10.1016/j.chroma.2024.465424","DOIUrl":"10.1016/j.chroma.2024.465424","url":null,"abstract":"<div><div><em>Salvia miltiorrhiza</em>, a widely used traditional Chinese medicine, contains a complex matrix of hydrophobic diterpenoids and hydrophilic phenolic acids, presenting significant challenges in comprehensive analysis. In this study, an online polarity-partitioned two-dimensional liquid chromatography coupled with mass spectrometry (2D-LC-MS) method was developed for comprehensive analysis of both lipophilic and hydrophilic active components in <em>Salvia miltiorrhiza</em>. The method integrated hydrophilic interaction liquid chromatography (HILIC) and reversed-phase liquid chromatography (RPLC), facilitating the efficient separation of compounds across a wide range of polarities. An online dilution strategy was implemented, minimizing sample loss and enhancing the method's utility for quality control and chemical characterization of complex herbal matrices. Compared with other LC methods, this approach significantly improved analyte coverage, resolution, and analysis efficiency. Under optimal conditions, 150 active components were successfully identified, including 33 compounds newly discovered in <em>Salvia miltiorrhiza</em>. Additionally, the validated online method was applied to the quantitative determination of 16 quality markers of <em>Salvia miltiorrhiza</em> from different sources. The results demonstrated the online method's potential as a superior alternative to existing techniques, offering broader applicability in traditional Chinese medicine research.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1736 ","pages":"Article 465424"},"PeriodicalIF":3.8,"publicationDate":"2024-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142434011","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 : 2024-10-06DOI: 10.1016/j.chroma.2024.465423
Naeem Ullah , Mustafa Tuzen , Tawfik A. Saleh
The release of harmful compounds, particularly dangerous metal ions, into the environment has drawn deep concern from the scientific community. Therefore, it has become common in research to evaluate and quantify the harmful concentrations in the presence of these metal ions in several real samples (food, water, and biological samples). To increase sensitivity and lessen the impact of the matrix, sample pretreatment is a helpful strategy to implement before analysis. The limitations of conventional methods have been recently significantly reduced by developing new analytical approaches such as microextraction techniques. The miniaturization of conventional solid-phase extraction (SPE) led to solid-phase microextraction (SPME), drastically reducing both adsorbent use and extraction phase volume. SPME is defined in the present context as a modified extraction technique that employs a portable syringe system attached to micropipette tips. The SPME is considered one of the most appropriate sample preparation tools due to its compatibility with different detection techniques for different metal ions. The current review focuses on SPME based on a portable syringe (attaches to a micropipette tip) system because it has many advantages over conventional solid-phase extraction. It can be designed very simply in a syringe system, a very small quantity of the sorbent has to be kept in the tip, tube, or inside a syringe as a plug and combined with various analytical instruments. Many researchers have designed their own by using homemade tips packed with a sorbent to increase extraction capability and selectivity. According to the current review, there is a lot of potential for increasing the efficacy and efficiency of metal ion extraction from complicated matrices using portable syringe SPME. Studies have shown that when compared to conventional approaches, it performs better in terms of sensitivity, selectivity, and user-friendliness. Furthermore, its application to a wider range of sample types has been enhanced by the flexibility in constructing unique sorbent tips. Conclusively, the developments in portable syringe SPME have addressed several limitations of conventional techniques, positioning it as a robust and versatile tool for environmental monitoring and analysis of hazardous metal ions.
{"title":"A comprehensive review of portable syringe systems using micropipette-based extraction techniques for metal analysis","authors":"Naeem Ullah , Mustafa Tuzen , Tawfik A. Saleh","doi":"10.1016/j.chroma.2024.465423","DOIUrl":"10.1016/j.chroma.2024.465423","url":null,"abstract":"<div><div>The release of harmful compounds, particularly dangerous metal ions, into the environment has drawn deep concern from the scientific community. Therefore, it has become common in research to evaluate and quantify the harmful concentrations in the presence of these metal ions in several real samples (food, water, and biological samples). To increase sensitivity and lessen the impact of the matrix, sample pretreatment is a helpful strategy to implement before analysis. The limitations of conventional methods have been recently significantly reduced by developing new analytical approaches such as microextraction techniques. The miniaturization of conventional solid-phase extraction (SPE) led to solid-phase microextraction (SPME), drastically reducing both adsorbent use and extraction phase volume. SPME is defined in the present context as a modified extraction technique that employs a portable syringe system attached to micropipette tips. The SPME is considered one of the most appropriate sample preparation tools due to its compatibility with different detection techniques for different metal ions. The current review focuses on SPME based on a portable syringe (attaches to a micropipette tip) system because it has many advantages over conventional solid-phase extraction. It can be designed very simply in a syringe system, a very small quantity of the sorbent has to be kept in the tip, tube, or inside a syringe as a plug and combined with various analytical instruments. Many researchers have designed their own by using homemade tips packed with a sorbent to increase extraction capability and selectivity. According to the current review, there is a lot of potential for increasing the efficacy and efficiency of metal ion extraction from complicated matrices using portable syringe SPME. Studies have shown that when compared to conventional approaches, it performs better in terms of sensitivity, selectivity, and user-friendliness. Furthermore, its application to a wider range of sample types has been enhanced by the flexibility in constructing unique sorbent tips. Conclusively, the developments in portable syringe SPME have addressed several limitations of conventional techniques, positioning it as a robust and versatile tool for environmental monitoring and analysis of hazardous metal ions.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1736 ","pages":"Article 465423"},"PeriodicalIF":3.8,"publicationDate":"2024-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142446045","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 : 2024-10-06DOI: 10.1016/j.chroma.2024.465425
Jiaxin Duan, Wenting Li, Yun Wei
Recycling rare earth ions from wastewater is an important task, as rare earth elements have a wide range of applications and can cause harm to the environment if discharged arbitrarily. In this work, a simple and inexpensive hydroxyethylidene diphosphate-based adsorbent (SA@HEDP) for adsorbing lanthanum was designed and fabricated. The adsorbent SA@HEDP with the surface rich in phosphate and hydroxyl functional groups provided active sites for adsorption of lanthanum. Research on adsorption performance was conducted by testing the amount of HEDP added, the amount of adsorbent used, the effect of initial pH of La (III), adsorption time, and temperature. The results showed that the adsorption capacity of the adsorbent was 158.0 mg/g. Adsorption of La (III) in real wastewater was tested, when the initial concentration of La (III) was 319.2 mg/L, it could be basically all recovered through three adsorption processes. SEM, EDS mapping, XPS, FTIR, and Zeta potential were used to characterize and analyze the mechanism, and mass transfer kinetics was used to analyze the adsorption process of the adsorbent for La (III).
{"title":"Fabrication of sodium alginate doped phosphoric acid composite hydrogel and its application of the adsorption of La (III) in wastewater","authors":"Jiaxin Duan, Wenting Li, Yun Wei","doi":"10.1016/j.chroma.2024.465425","DOIUrl":"10.1016/j.chroma.2024.465425","url":null,"abstract":"<div><div>Recycling rare earth ions from wastewater is an important task, as rare earth elements have a wide range of applications and can cause harm to the environment if discharged arbitrarily. In this work, a simple and inexpensive hydroxyethylidene diphosphate-based adsorbent (SA@HEDP) for adsorbing lanthanum was designed and fabricated. The adsorbent SA@HEDP with the surface rich in phosphate and hydroxyl functional groups provided active sites for adsorption of lanthanum. Research on adsorption performance was conducted by testing the amount of HEDP added, the amount of adsorbent used, the effect of initial pH of La (III), adsorption time, and temperature. The results showed that the adsorption capacity of the adsorbent was 158.0 mg/g. Adsorption of La (III) in real wastewater was tested, when the initial concentration of La (III) was 319.2 mg/L, it could be basically all recovered through three adsorption processes. SEM, EDS mapping, XPS, FTIR, and Zeta potential were used to characterize and analyze the mechanism, and mass transfer kinetics was used to analyze the adsorption process of the adsorbent for La (III).</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1736 ","pages":"Article 465425"},"PeriodicalIF":3.8,"publicationDate":"2024-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142405822","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 : 2024-10-06DOI: 10.1016/j.chroma.2024.465422
Karen Gaudin , Josep Valls-Fonayet , Rémy Cordazzo , Wiktoria Serafin , Emma Lafon , Alexandra Gaubert , Tristan Richard , Stéphanie Cluzet
The characterization of plant extracts is usually accomplished by reverse-phase liquid chromatography, but the development of new complementary approaches, such as HILIC, offers an orthogonal method. In this study, five HILIC stationary phases were evaluated to assess their ability to retain polyphenols. They were selected to cover the main different HILIC mechanisms: bare silica; silica with ethylene bridge; neutral amide; amino; zwitterionic. A total of 31 polyphenol standards were used for the screening, including 9 stilbenes, 8 flavonoids, 6 anthocyanins, and 8 phenolic acids. Three different detections were tested: diode array detector, charged aerosol detector and mass spectrometry.
Results indicated that silica supports were not suitable for retaining polyphenols, with no or low retention observed except for anthocyanins. The effectiveness of stationary phases in retention of phenolics following the order related to increased retention: zwitterionic, amide, and amino.
The choice of mobile phase also influenced retention. Mobile phases containing TFA as pH modifier limited retention, while formic acid was found to be more effective for polyphenol retention. Ammonium buffers also improved retention but often compromised peak shape. pH changes mainly impacted ionizable compounds, such as phenolic acids, by increasing their retention when they were ionized.
DAD was wellsuited for detecting polyphenols that possess aromatic rings, though peak wavelengths depend on the structures of the polyphenols. CAD, while less sensitive than DAD and MS, provided an almost similar response for structurally related compounds, even with gradient elution. MS was the preferred detector for quantification when resolution between compounds was challenging, as it is often the case with natural extracts.
The study successfully demonstrated that best HILIC conditions were obtained using an amino stationary phase composed of a polyethylenimine and formic acid-based mobile phase. These conditions were successfully applied to the analysis of stilbenoid-rich extracts from different parts of the vine. The elution order of stilbenoids followed the degree of polymerization. With CAD, the chromatographic profile was more representative of sample composition. It was demonstrated for the first time the interest of a combination of HILIC and CAD for analyzing stilbenes, offering a complementary approach to the classic RP analysis.
{"title":"Separation of polyphenols by HILIC methods with diode array detection, charged aerosol detection and mass spectrometry: Application to grapevine extracts rich in stilbenoids","authors":"Karen Gaudin , Josep Valls-Fonayet , Rémy Cordazzo , Wiktoria Serafin , Emma Lafon , Alexandra Gaubert , Tristan Richard , Stéphanie Cluzet","doi":"10.1016/j.chroma.2024.465422","DOIUrl":"10.1016/j.chroma.2024.465422","url":null,"abstract":"<div><div>The characterization of plant extracts is usually accomplished by reverse-phase liquid chromatography, but the development of new complementary approaches, such as HILIC, offers an orthogonal method. In this study, five HILIC stationary phases were evaluated to assess their ability to retain polyphenols. They were selected to cover the main different HILIC mechanisms: bare silica; silica with ethylene bridge; neutral amide; amino; zwitterionic. A total of 31 polyphenol standards were used for the screening, including 9 stilbenes, 8 flavonoids, 6 anthocyanins, and 8 phenolic acids. Three different detections were tested: diode array detector, charged aerosol detector and mass spectrometry.</div><div>Results indicated that silica supports were not suitable for retaining polyphenols, with no or low retention observed except for anthocyanins. The effectiveness of stationary phases in retention of phenolics following the order related to increased retention: zwitterionic, amide, and amino.</div><div>The choice of mobile phase also influenced retention. Mobile phases containing TFA as pH modifier limited retention, while formic acid was found to be more effective for polyphenol retention. Ammonium buffers also improved retention but often compromised peak shape. pH changes mainly impacted ionizable compounds, such as phenolic acids, by increasing their retention when they were ionized.</div><div>DAD was wellsuited for detecting polyphenols that possess aromatic rings, though peak wavelengths depend on the structures of the polyphenols. CAD, while less sensitive than DAD and MS, provided an almost similar response for structurally related compounds, even with gradient elution. MS was the preferred detector for quantification when resolution between compounds was challenging, as it is often the case with natural extracts.</div><div>The study successfully demonstrated that best HILIC conditions were obtained using an amino stationary phase composed of a polyethylenimine and formic acid-based mobile phase. These conditions were successfully applied to the analysis of stilbenoid-rich extracts from different parts of the vine. The elution order of stilbenoids followed the degree of polymerization. With CAD, the chromatographic profile was more representative of sample composition. It was demonstrated for the first time the interest of a combination of HILIC and CAD for analyzing stilbenes, offering a complementary approach to the classic RP analysis.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1736 ","pages":"Article 465422"},"PeriodicalIF":3.8,"publicationDate":"2024-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142386947","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 : 2024-10-05DOI: 10.1016/j.chroma.2024.465392
Wenmin Zhang , Baodi Liao , Shiye Xie , Lan Zhang
Membrane-based micro-solid phase extraction (M-μSPE) has garnered great attention in sample pretreatment, suffering an inherent contradiction between permeability and adsorption capacity. In this study, a pure microporous organic network (TEB-DIB-MON) fiber membrane was prepared by combining electrostatic spinning technology, Sonogashira-Hagihara reaction and template sacrifice method. The prepared TEB-DIB-MON membrane exhibited a large specific surface area with a hollow and porous structure, thereby providing excellent solvent permeability and high adsorption capacity for okadaic acid (OA, an algal toxin). Under the optimized conditions, a sensitive analytical method was established by coupling M-μSPE with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The established method has a low detection limit (0.5 pg mL−1), a wide linear range (1.5–1000 pg mL−1, R ≥ 0.9991), and good reproducibility (RSD ≤ 9.4 %, n = 6), which was then successfully applied for OA detection in marine organisms. Trace amounts of OA (59.3–89.0 pg mL−1) was detected in the oyster and prawn samples. This work demonstrated that the excellent application potential of MON membranes in sample pretreatment, while also presents a novel synthesis strategy for MONs membranes.
{"title":"Hollow microporous organic network fiber membrane for efficient extraction of okadaic acid from marine organisms","authors":"Wenmin Zhang , Baodi Liao , Shiye Xie , Lan Zhang","doi":"10.1016/j.chroma.2024.465392","DOIUrl":"10.1016/j.chroma.2024.465392","url":null,"abstract":"<div><div>Membrane-based micro-solid phase extraction (M-μSPE) has garnered great attention in sample pretreatment, suffering an inherent contradiction between permeability and adsorption capacity. In this study, a pure microporous organic network (TEB-DIB-MON) fiber membrane was prepared by combining electrostatic spinning technology, Sonogashira-Hagihara reaction and template sacrifice method. The prepared TEB-DIB-MON membrane exhibited a large specific surface area with a hollow and porous structure, thereby providing excellent solvent permeability and high adsorption capacity for okadaic acid (OA, an algal toxin). Under the optimized conditions, a sensitive analytical method was established by coupling M-μSPE with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The established method has a low detection limit (0.5 pg mL<sup>−1</sup>), a wide linear range (1.5–1000 pg mL<sup>−1</sup>, <em>R</em> ≥ 0.9991), and good reproducibility (RSD ≤ 9.4 %, <em>n</em> = 6), which was then successfully applied for OA detection in marine organisms. Trace amounts of OA (59.3–89.0 pg mL<sup>−1)</sup> was detected in the oyster and prawn samples. This work demonstrated that the excellent application potential of MON membranes in sample pretreatment, while also presents a novel synthesis strategy for MONs membranes.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1736 ","pages":"Article 465392"},"PeriodicalIF":3.8,"publicationDate":"2024-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142386943","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 : 2024-10-05DOI: 10.1016/j.chroma.2024.465419
Shuo-Wen Gao, Na Li, Yuan-Yuan Cui, Cheng-Xiong Yang
Owning to the hydrophobic characteristics of microporous organic networks (MONs), their utilizations still largely limited in non- and weak-polar analytes. To expend their applications, here we reported the synthesis of a novel hollowed H-MON-PEI1800–2 composite via sacrifice template method and subsequent modification with polyethyleneimine (PEI) for efficient solid phase extraction of polar and ionic phenolic acid (PAs) from fruit juice samples. H-MON-PEI1800–2 exhibits large surface area, rapid extraction kinetics, remarkable chemical and thermal stabilities, and provides synergistic electrostatic, π-π, hydrogen bonding, and hydrophobic interaction sites for PAs. The developed method owns low limit of detection, wide linear range, large enrichment factors, and good reusability. The recoveries of H-MON-PEI1800–2 for PAs are 1–3 orders of magnitude higher than those of commercial adsorbents like activated carbon, C18 and Oasis HLB. This work highlights the prospects of functional H-MONs for enriching polar and ionic targets from complex sample matrices.
由于微孔有机网络（MON）的疏水特性，其在非极性和弱极性分析物中的应用仍然受到很大限制。为了拓展其应用领域，我们通过牺牲模板法合成了一种新型中空 H-MON-PEI1800-2 复合材料，随后用聚乙烯亚胺（PEI）对其进行改性，用于从果汁样品中高效固相萃取极性和离子性酚酸（PA）。H-MON-PEI1800-2 具有较大的比表面积、快速的萃取动力学、显著的化学稳定性和热稳定性，并为 PAs 提供了协同静电、π-π、氢键和疏水相互作用位点。所开发的方法具有检出限低、线性范围宽、富集因子大、重复使用性好等特点。与活性炭、C18 和 Oasis HLB 等商业吸附剂相比，H-MON-PEI1800-2 对 PAs 的回收率高出 1-3 个数量级。这项工作凸显了功能性 H-MONs 从复杂样品基质中富集极性和离子目标物的前景。
{"title":"Modification of hollow microporous organic network with polyethyleneimine for efficient enrichment of phenolic acids from fruit juice samples","authors":"Shuo-Wen Gao, Na Li, Yuan-Yuan Cui, Cheng-Xiong Yang","doi":"10.1016/j.chroma.2024.465419","DOIUrl":"10.1016/j.chroma.2024.465419","url":null,"abstract":"<div><div>Owning to the hydrophobic characteristics of microporous organic networks (MONs), their utilizations still largely limited in non- and weak-polar analytes. To expend their applications, here we reported the synthesis of a novel hollowed H-MON-PEI<sub>1800</sub>–2 composite via sacrifice template method and subsequent modification with polyethyleneimine (PEI) for efficient solid phase extraction of polar and ionic phenolic acid (PAs) from fruit juice samples. H-MON-PEI<sub>1800</sub>–2 exhibits large surface area, rapid extraction kinetics, remarkable chemical and thermal stabilities, and provides synergistic electrostatic, π-π, hydrogen bonding, and hydrophobic interaction sites for PAs. The developed method owns low limit of detection, wide linear range, large enrichment factors, and good reusability. The recoveries of H-MON-PEI<sub>1800</sub>–2 for PAs are 1–3 orders of magnitude higher than those of commercial adsorbents like activated carbon, C18 and Oasis HLB. This work highlights the prospects of functional H-MONs for enriching polar and ionic targets from complex sample matrices.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1736 ","pages":"Article 465419"},"PeriodicalIF":3.8,"publicationDate":"2024-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142386944","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 : 2024-10-05DOI: 10.1016/j.chroma.2024.465405
Menglin Yang , Xiaohong He , Jin Xu , Weifang Yu
Analytical solution to ideal chromatography model has been established for binary Langmuir isotherm and rectangular injections. However, retention time of the less adsorbed species, which is of great theoretical and practical significance, cannot be given in a closed form and is conventionally solved by numerical integration with a floating boundary. A simplified approach is provided in this article. A 4th order algebraic equation was derived and used to solve the maximum concentration that can be further used to explicitly calculate retention time. Under most practical conditions, reliable initial guess can be easily acquired, allowing for the application of Newton-Raphson method for rapid determination of the root of the 4th order equation. In addition, derivatives of retention time with respective to isotherm parameters can be given in analytical forms.
{"title":"Simplified approach to retention times of narrow binary pulses in the case of ideal chromatography model and Langmuir isotherm","authors":"Menglin Yang , Xiaohong He , Jin Xu , Weifang Yu","doi":"10.1016/j.chroma.2024.465405","DOIUrl":"10.1016/j.chroma.2024.465405","url":null,"abstract":"<div><div>Analytical solution to ideal chromatography model has been established for binary Langmuir isotherm and rectangular injections. However, retention time of the less adsorbed species, which is of great theoretical and practical significance, cannot be given in a closed form and is conventionally solved by numerical integration with a floating boundary. A simplified approach is provided in this article. A 4th order algebraic equation was derived and used to solve the maximum concentration that can be further used to explicitly calculate retention time. Under most practical conditions, reliable initial guess can be easily acquired, allowing for the application of Newton-Raphson method for rapid determination of the root of the 4th order equation. In addition, derivatives of retention time with respective to isotherm parameters can be given in analytical forms.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1736 ","pages":"Article 465405"},"PeriodicalIF":3.8,"publicationDate":"2024-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142386948","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 : 2024-10-05DOI: 10.1016/j.chroma.2024.465420
Qianqian Wang , Yuanyuan Zheng , Bowen Deng , Di Chen , Liuqun Jia , Nian Shi
This study delineates the development of a novel automated pipette-tip solid-phase extraction (SPE) methodology, employing kapok fiber as a naturally efficient and cost-effective adsorbent for the selective extraction of eleven tyrosine kinase inhibitors (TKIs) from plasma. The uniqueness of this method lies in its assembly, where kapok fibers are ingeniously wrapped around a stainless-steel spring within the pipette tip, ensuring an obstruction-free central space for effortless solution aspiration and dispensation. This design significantly minimizes backpressure, enhancing operational efficiency and ensuring compatibility with pipettors, including the implementation of an electric pipettor to streamline the sample preparation process and facilitate automation. The method's analytical performance, rigorously validated through liquid chromatography-tandem mass spectrometry, exhibits outstanding linearity in ranges of 0.1/0.5–200 ng mL-1 (R² > 0.993), commendable accuracy (86.3%–114.8%), and consistent precision (3.4–11.3%), alongside remarkably low detection limits that span from 0.024 to 0.130 ng mL-1. The assembly of kapok fiber within the pipette tip, in this unique configuration, results in a practical, cost-effective, eco-friendly, and automated pipette-tip SPE method. This innovation signifies a significant advancement in bioanalytical methodologies, offering an efficient and sustainable approach for extracting analytes from complex biological samples. This process notably enhances both the sensitivity and selectivity of subsequent instrumental analyses.
{"title":"Automated kapok fiber-based pipette-tip solid-phase extraction coupled with liquid chromatography-tandem mass spectrometry for rapid and sensitive analysis of tyrosine kinase inhibitors in plasma","authors":"Qianqian Wang , Yuanyuan Zheng , Bowen Deng , Di Chen , Liuqun Jia , Nian Shi","doi":"10.1016/j.chroma.2024.465420","DOIUrl":"10.1016/j.chroma.2024.465420","url":null,"abstract":"<div><div>This study delineates the development of a novel automated pipette-tip solid-phase extraction (SPE) methodology, employing kapok fiber as a naturally efficient and cost-effective adsorbent for the selective extraction of eleven tyrosine kinase inhibitors (TKIs) from plasma. The uniqueness of this method lies in its assembly, where kapok fibers are ingeniously wrapped around a stainless-steel spring within the pipette tip, ensuring an obstruction-free central space for effortless solution aspiration and dispensation. This design significantly minimizes backpressure, enhancing operational efficiency and ensuring compatibility with pipettors, including the implementation of an electric pipettor to streamline the sample preparation process and facilitate automation. The method's analytical performance, rigorously validated through liquid chromatography-tandem mass spectrometry, exhibits outstanding linearity in ranges of 0.1/0.5–200 ng mL<sup>-1</sup> (R² > 0.993), commendable accuracy (86.3%–114.8%), and consistent precision (3.4–11.3%), alongside remarkably low detection limits that span from 0.024 to 0.130 ng mL<sup>-1</sup>. The assembly of kapok fiber within the pipette tip, in this unique configuration, results in a practical, cost-effective, eco-friendly, and automated pipette-tip SPE method. This innovation signifies a significant advancement in bioanalytical methodologies, offering an efficient and sustainable approach for extracting analytes from complex biological samples. This process notably enhances both the sensitivity and selectivity of subsequent instrumental analyses.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1736 ","pages":"Article 465420"},"PeriodicalIF":3.8,"publicationDate":"2024-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142386940","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 : 2024-10-05DOI: 10.1016/j.chroma.2024.465421
Stela Georgieva, Eduard Stefanov, Temenuzhka Radoykova
The speciation analysis of arsenic has consistently been a subject of great interest. However, it remains challenging to analyze complex matrix samples that contain both arsenic and interfering components. In this case, it can be hard to choose the right combinations of different instrumental methods, or a separation method followed by detection, which is usually done using a spectral approach (hybrid methods). In the production control of copper electrorefining, the determination of the concentration of As (III) and As (V) helps to improve the quality of the cathode copper produced. This work investigated the possibility of directly determining both arsenic forms and total As in an electrolyte bath using ion chromatography (IC) with conductometric detection. The use of the ion chromatographic approach for the determination of As(V) in complex matrix samples such as copper electrolyte must take into account the presence of potential interferences from anions such as sulphates, sulfites, selenites, selenates, etc. The results revealed that the method is accurate and precise, with As(V) quantification limits of 15 µg.L-1 and detection limits of 5 µg.L-1. This method is suitable for assessing various types of arsenic in the production of electrolytic copper, with the aim of replacing the current technique that requires liquid-liquid extraction and ICP-OES detection. This led to the following improvements: Enhanced efficiency: The method eliminates the need for extensive and time-consuming sample preparation for the initial separation of arsenic forms. At the same time, the method's characteristics are comparable to those of ICP-OES with liquid-liquid extraction, which is often used in the speciation analysis of arsenic. The method is environmentally friendly as it avoids the use of organic and poisonous extractants. The method can simultaneously analyze other anions (PO43-, SO42-, F-, Cl-, etc.) with arsenates with appropriate calibration.
砷的标样分析一直是备受关注的课题。然而，对同时含有砷和干扰成分的复杂基质样品进行分析仍然具有挑战性。在这种情况下，很难选择不同仪器方法的正确组合，或者选择先分离后检测的方法（通常使用光谱方法（混合方法））。在电解铜的生产控制中，测定 As (III) 和 As (V) 的浓度有助于提高所生产阴极铜的质量。这项工作研究了利用离子色谱法（IC）和电导检测法直接测定电解液中砷形式和总砷的可能性。使用离子色谱法测定铜电解液等复杂基质样品中的 As(V)，必须考虑到硫酸盐、亚硫酸盐、亚硒酸盐、硒酸盐等阴离子的潜在干扰。结果表明，该方法准确、精确，As(V)的定量限为 15 µg.L-1，检出限为 5 µg.L-1。该方法适用于评估电解铜生产中的各类砷，旨在取代目前需要液液萃取和 ICP-OES 检测的技术。这带来了以下改进：提高效率：该方法无需进行大量耗时的样品制备来初步分离砷形态。同时，该方法的特性可与常用于砷标样分析的液液萃取 ICP-OES 方法相媲美。该方法避免了有机和有毒萃取剂的使用，因此非常环保。通过适当的校准，该方法可同时分析砷酸盐和其他阴离子（PO43-、SO42-、F-、Cl- 等）。
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Pub Date : 2024-10-05DOI: 10.1016/j.chroma.2024.465417
Francisco T.C. de Souza , Maria Z.F. da Silva , Humberto H. de Carvalho , Carla B. Vidal , Ronaldo F. do Nascimento , Elisane Longhinotti
Benzene, toluene, ethylbenzene, and the xylene isomers (m, p, and o-xylene) (BTEX) are known for their harmful effects on human health and have been extensively studied across various environmental matrices. However, quantifying BTEX in exhaust gases poses challenges due to the complexity of the matrices. In this study, we investigated a method development strategy involving solid-phase microextraction (SPME) and gas chromatography coupled with a dielectric barrier discharge ionization Detector (BID) for quantifying BTEX emitted from internal combustion engines operating at idle. Sampling was conducted using 1.0 L Tedlar bags, followed by withdrawal of aliquots and dilution with atmospheric air using a novel device (graduated vial) designed for gaseous samples. The SPME-GC-BID method was developed and validated for the conditions: BTEX extraction in CAR/PDMS 75 μm fiber at a contact time of 5.0 min at a temperature of 27 °C, followed by GC-BID analysis. Method validation to ensure the reliability of quantitative results used the merit figures e.g., limits of detection (LOD) and quantification (LOQ), precision, and accuracy (recovery). LOD varied from 0.194 to 0.340 mg m−3, LOQ varied from 0.587 to 1.03 mg m−3, precision ranged from 1.47 to 7.14 %, and recovery varied from 82.34 to 109.5 %. BTEX concentration in vehicle exhaust varied from 3.40 to 16.4 mg m−3. The results showed, concerning the figures of merit analyzed, that the SPME-GC-BID method provides good sensibility, precision, and accuracy for evaluating the presence of BTEX in the exhaust of internal combustion engines, contributing to the understanding of health risks associated with vehicle emissions.
{"title":"Evaluating BTEX in vehicle exhaust gas: A fast and efficient approach using SPME and GC-BID","authors":"Francisco T.C. de Souza , Maria Z.F. da Silva , Humberto H. de Carvalho , Carla B. Vidal , Ronaldo F. do Nascimento , Elisane Longhinotti","doi":"10.1016/j.chroma.2024.465417","DOIUrl":"10.1016/j.chroma.2024.465417","url":null,"abstract":"<div><div>Benzene, toluene, ethylbenzene, and the xylene isomers (m, p, and o-xylene) (BTEX) are known for their harmful effects on human health and have been extensively studied across various environmental matrices. However, quantifying BTEX in exhaust gases poses challenges due to the complexity of the matrices. In this study, we investigated a method development strategy involving solid-phase microextraction (SPME) and gas chromatography coupled with a dielectric barrier discharge ionization Detector (BID) for quantifying BTEX emitted from internal combustion engines operating at idle. Sampling was conducted using 1.0 L Tedlar bags, followed by withdrawal of aliquots and dilution with atmospheric air using a novel device (graduated vial) designed for gaseous samples. The SPME-GC-BID method was developed and validated for the conditions: BTEX extraction in CAR/PDMS 75 μm fiber at a contact time of 5.0 min at a temperature of 27 °C, followed by GC-BID analysis. Method validation to ensure the reliability of quantitative results used the merit figures e.g., limits of detection (LOD) and quantification (LOQ), precision, and accuracy (recovery). LOD varied from 0.194 to 0.340 mg <em>m</em><sup>−3</sup>, LOQ varied from 0.587 to 1.03 mg <em>m</em><sup>−3</sup>, precision ranged from 1.47 to 7.14 %, and recovery varied from 82.34 to 109.5 %. BTEX concentration in vehicle exhaust varied from 3.40 to 16.4 mg <em>m</em><sup>−3</sup>. The results showed, concerning the figures of merit analyzed, that the SPME-GC-BID method provides good sensibility, precision, and accuracy for evaluating the presence of BTEX in the exhaust of internal combustion engines, contributing to the understanding of health risks associated with vehicle emissions.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1736 ","pages":"Article 465417"},"PeriodicalIF":3.8,"publicationDate":"2024-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142386942","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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