Pub Date : 2025-03-31DOI: 10.1016/j.chroma.2025.465926
Zhuoning Li , Xiaoli Wang , Leilei Wang , Lu Liu , Lingxi Zhao , Na Li , Hailong Jiang , Zhineng Hao , Jingfu Liu , Xiangfeng Chen , Rusong Zhao
Sensitive monitoring of per- and polyfluoroalkyl substances (PFASs) is critical for environmental and health risk assessment. In this work, metal-organic frameworks (MOFs) functionalized with positively charged tertiary amines (UiO-67-CH2-N(CH3)2) were synthesized by the one-pot route, which integrated solvothermal MOFs assembly and in-situ reductive amination of formyl groups. The fabricated UiO-67-CH2-N(CH3)2 exhibited exceptional performance as adsorbents for solid-phase extraction (SPE), and the efficient adsorption of PFASs was attribute to the electrostatic attraction and hydrogen bonding. The proposed SPE-HPLC-MS/MS method demonstrated low limit of detection (0.02–0.88 ng·L−1), good linearity (0.2–400 ng·L−1) and high precision (RSD < 8.18 %). The effectiveness of the established method was assessed through the analysis of PFASs in environmental waters, and recoveries in spiked samples were 84.0–117 % with RSD < 13 %. This study highlighted the efficacy of the functionalized UiO-67-CH2-N(CH3)2 in trace PFASs analysis, advancing their application in environmental monitoring.
{"title":"Tertiary amine-functionalized metal-organic frameworks for high adsorption of perfluoroalkyl and polyfluoroalkyl substances in environmental water samples","authors":"Zhuoning Li , Xiaoli Wang , Leilei Wang , Lu Liu , Lingxi Zhao , Na Li , Hailong Jiang , Zhineng Hao , Jingfu Liu , Xiangfeng Chen , Rusong Zhao","doi":"10.1016/j.chroma.2025.465926","DOIUrl":"10.1016/j.chroma.2025.465926","url":null,"abstract":"<div><div>Sensitive monitoring of per- and polyfluoroalkyl substances (PFASs) is critical for environmental and health risk assessment. In this work, metal-organic frameworks (MOFs) functionalized with positively charged tertiary amines (UiO-67-CH<sub>2</sub>-N(CH<sub>3</sub>)<sub>2</sub>) were synthesized by the one-pot route, which integrated solvothermal MOFs assembly and in-situ reductive amination of formyl groups. The fabricated UiO-67-CH<sub>2</sub>-N(CH<sub>3</sub>)<sub>2</sub> exhibited exceptional performance as adsorbents for solid-phase extraction (SPE), and the efficient adsorption of PFASs was attribute to the electrostatic attraction and hydrogen bonding. The proposed SPE-HPLC-MS/MS method demonstrated low limit of detection (0.02–0.88 ng·L<sup>−1</sup>), good linearity (0.2–400 ng·L<sup>−1</sup>) and high precision (RSD < 8.18 %). The effectiveness of the established method was assessed through the analysis of PFASs in environmental waters, and recoveries in spiked samples were 84.0–117 % with RSD < 13 %. This study highlighted the efficacy of the functionalized UiO-67-CH<sub>2</sub>-N(CH<sub>3</sub>)<sub>2</sub> in trace PFASs analysis, advancing their application in environmental monitoring.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1750 ","pages":"Article 465926"},"PeriodicalIF":3.8,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143783029","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 : 2025-03-31DOI: 10.1016/j.chroma.2025.465925
Chenhuan Wang , Qianqian Wang , Kaiyuan Si
The extensive presence of phenolic organic contaminants (POCs) poses a serious threat to humans. Meanwhile, the upcycling/reusing of waste polystyrene to reduce the exponential growth of plastic pollution is a very important environmental issue. Addressing these demands, a series of carboxyl-functional hypercrosslinked polymers (labeled PP-HCPs) were constructed by knitting waste polystyrene with pyromellitic dianhydride at different ratios through a one-step Friedel-Crafts reaction for effective adsorption of POCs. Among the prepared PP-HCPs, PP-HCP2 displayed a large specific surface area with high adsorption capacity (37.3 mg g−1) for POCs. Using PP-HCP2 as solid phase extraction sorbent, six POCs were effectively extracted from water and peach drink samples, then subjected to high-performance liquid chromatography-ultraviolet detection. The method demonstrated good linearity in the range of 0.03–100.0 ng mL−1 for water samples and 0.06–100.0 ng mL−1 for peach drinks under optimum experimental conditions. At a signal-to-noise ratio of 3, low detection limits were found to be 0.01–0.10 ng mL−1 for water samples and 0.02–0.15 ng mL−1 for peach drinks. Good accuracy and repeatability were achieved with recoveries of 85.3–111.8 % and the relative standard deviations below 8.6 %. The PP-HCP2-based approach can be employed as a dependable and sensitive tool to detect POCs in water and peach drink samples. This work delivers a simple and economically viable approach to fabricate carboxyl-functional HCPs by converting waste foam into high-value-added sorbent, with great significance for sustainable development.
{"title":"Construction of carboxyl-functionalized hyper-cross-linked porous polymers using waste polystyrene for effective adsorption of phenolic contaminants","authors":"Chenhuan Wang , Qianqian Wang , Kaiyuan Si","doi":"10.1016/j.chroma.2025.465925","DOIUrl":"10.1016/j.chroma.2025.465925","url":null,"abstract":"<div><div>The extensive presence of phenolic organic contaminants (POCs) poses a serious threat to humans. Meanwhile, the upcycling/reusing of waste polystyrene to reduce the exponential growth of plastic pollution is a very important environmental issue. Addressing these demands, a series of carboxyl-functional hypercrosslinked polymers (labeled PP-HCPs) were constructed by knitting waste polystyrene with pyromellitic dianhydride at different ratios through a one-step Friedel-Crafts reaction for effective adsorption of POCs. Among the prepared PP-HCPs, PP-HCP2 displayed a large specific surface area with high adsorption capacity (37.3 mg g<sup>−1</sup>) for POCs. Using PP-HCP2 as solid phase extraction sorbent, six POCs were effectively extracted from water and peach drink samples, then subjected to high-performance liquid chromatography-ultraviolet detection. The method demonstrated good linearity in the range of 0.03–100.0 ng mL<sup>−1</sup> for water samples and 0.06–100.0 ng mL<sup>−1</sup> for peach drinks under optimum experimental conditions. At a signal-to-noise ratio of 3, low detection limits were found to be 0.01–0.10 ng mL<sup>−1</sup> for water samples and 0.02–0.15 ng mL<sup>−1</sup> for peach drinks. Good accuracy and repeatability were achieved with recoveries of 85.3–111.8 % and the relative standard deviations below 8.6 %. The PP-HCP2-based approach can be employed as a dependable and sensitive tool to detect POCs in water and peach drink samples. This work delivers a simple and economically viable approach to fabricate carboxyl-functional HCPs by converting waste foam into high-value-added sorbent, with great significance for sustainable development.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1750 ","pages":"Article 465925"},"PeriodicalIF":3.8,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143759218","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 : 2025-03-30DOI: 10.1016/j.chroma.2025.465898
Zhi-Cheng Ye , Jia-Yuan Liu , Chao-Jung Chen , Yen-Yi Chen , Wen-Chun Li , Mine-Yine Liu
A micellar electrokinetic chromatography (MEKC) method has been developed to investigate the binding products between human apolipoproteins (Apos) and oxidized 1-palmitoyl-2-arachidonoyl-sn‑glycero-3-phosphocholine (ox-PAPC) products. The optimal MEKC separation buffer was composed of a solution mixture of 10 mM sodium phosphate, 50 mM bile salts (50 % sodium cholate and 50 % sodium deoxycholate), 30 % (v/v)1-propanol and 70 % (v/v) water, pH 7.4. The optimal MEKC sample buffer was composed of 70 % (v/v) PBS buffer and 30 % (v/v) MeOH. The selected separation voltage was 20 kV, and the capillary temperature was 25℃. The MEKC profiles of ox-PAPC products showed good separations and repeatability. The MEKC profiles of apos and their binding products also showed good repeatability.
For the analysis of native PAPC (n-PAPC), the method is linear in the range of 0.00–6.00 mg/mL with a correlation coefficient 0.9984. The concentration limit of detection (LOD) is 0.29 mg/mL. The concentration limit of quantitation (LOQ) is 0.98 mg/mL.
The binding reactions between several important human apolipoproteins (Apos A-I, A-II, C-I, C-II, C-III and E) and native PAPC, ox-PAPC products have been investigated. The concentrations of Apos and ox-PAPC products for binding reactions have been examined. The optimal binding buffer selected was 70 % (v/v) PBS buffer and 30 % (v/v) MeOH. The binding reaction was performed at 37 ℃ for 3 hr.
The results indicated that ox-PAPC products bound to Apos A-I, A-II, C-I, and E more strongly than n-PAPC. However, both ox-PAPC products and n-PAPC did not bind to Apos C-II and C-III strongly. The results suggested pro-inflammatory properties of Apos A-I, A-II, C-I, and E, and implied one of the molecular mechanisms resulting in dysfunctional HDL particles. This study also demonstrated the feasibility of investigating the binding reactions between human apolipoproteins and ox-PAPC products by MEKC.
{"title":"Investigating the binding products between human apolipoproteins and oxidized 1-palmitoyl-2-arachidonyl-sn-glycerol-3-phosphocholine by micellar electrokinetic chromatography","authors":"Zhi-Cheng Ye , Jia-Yuan Liu , Chao-Jung Chen , Yen-Yi Chen , Wen-Chun Li , Mine-Yine Liu","doi":"10.1016/j.chroma.2025.465898","DOIUrl":"10.1016/j.chroma.2025.465898","url":null,"abstract":"<div><div>A micellar electrokinetic chromatography (MEKC) method has been developed to investigate the binding products between human apolipoproteins (Apos) and oxidized 1-palmitoyl-2-arachidonoyl-sn‑glycero-3-phosphocholine (ox-PAPC) products. The optimal MEKC separation buffer was composed of a solution mixture of 10 mM sodium phosphate, 50 mM bile salts (50 % sodium cholate and 50 % sodium deoxycholate), 30 % (v/v)1-propanol and 70 % (v/v) water, pH 7.4. The optimal MEKC sample buffer was composed of 70 % (v/v) PBS buffer and 30 % (v/v) MeOH. The selected separation voltage was 20 kV, and the capillary temperature was 25℃. The MEKC profiles of ox-PAPC products showed good separations and repeatability. The MEKC profiles of apos and their binding products also showed good repeatability.</div><div>For the analysis of native PAPC (n-PAPC), the method is linear in the range of 0.00–6.00 mg/mL with a correlation coefficient 0.9984. The concentration limit of detection (LOD) is 0.29 mg/mL. The concentration limit of quantitation (LOQ) is 0.98 mg/mL.</div><div>The binding reactions between several important human apolipoproteins (Apos A-I, A-II, C-I, C-II, C-III and E) and native PAPC, ox-PAPC products have been investigated. The concentrations of Apos and ox-PAPC products for binding reactions have been examined. The optimal binding buffer selected was 70 % (v/v) PBS buffer and 30 % (v/v) MeOH. The binding reaction was performed at 37 ℃ for 3 hr.</div><div>The results indicated that ox-PAPC products bound to Apos A-I, A-II, C-I, and E more strongly than n-PAPC. However, both ox-PAPC products and n-PAPC did not bind to Apos C-II and C-III strongly. The results suggested pro-inflammatory properties of Apos A-I, A-II, C-I, and E, and implied one of the molecular mechanisms resulting in dysfunctional HDL particles. This study also demonstrated the feasibility of investigating the binding reactions between human apolipoproteins and ox-PAPC products by MEKC.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1751 ","pages":"Article 465898"},"PeriodicalIF":3.8,"publicationDate":"2025-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143821007","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 : 2025-03-29DOI: 10.1016/j.chroma.2025.465923
Alexander Nitschke, Moritz Hitzemann, Jonas Winkelholz, Ansgar T. Kirk, Christoph Schaefer, Tim Kobelt, Christian Thoben, Martin Lippmann, Jan A. Wittwer, Stefan Zimmermann
For higher analytical performance, ion mobility spectrometers (IMS), especially when analyzing complex mixtures, are often coupled with gas chromatographs (GC). However, analysis time remains a critical parameter in gas chromatography. Therefore, a hyper-fast GC is a promising approach for GC-IMS to combine highest sensitivity of IMS with increased peak capacity while allowing for rapid analysis within the double-digit second range. For simultaneously recording of both ion polarities, a new dual drift tube IMS in axial configuration has been developed that is particularly designed for resolving even hyper-fast GC peaks. Key is a directed sample gas flow through the ionization region giving a small effective detector volume. To avoid condensation of the sample gas, the IMS is isothermally heated to 120 °C. A drift tube length of only LD = 41 mm with a drift voltage of UD = 2.7 kV leads to an IMS repetition rate of 100 Hz and high resolving power of Rp = 60, even for ions with low reduced ion mobility down to 0.43 cm2V-1s-1. This setup can resolve very short GC peaks with full width at half maximum of only 140 ms. For demonstration, two different hop varieties and a mixture of explosives were analyzed within a short time of just 20 s.
{"title":"A dual-polarity ion mobility spectrometer for capturing hyper-fast chromatographic peaks","authors":"Alexander Nitschke, Moritz Hitzemann, Jonas Winkelholz, Ansgar T. Kirk, Christoph Schaefer, Tim Kobelt, Christian Thoben, Martin Lippmann, Jan A. Wittwer, Stefan Zimmermann","doi":"10.1016/j.chroma.2025.465923","DOIUrl":"10.1016/j.chroma.2025.465923","url":null,"abstract":"<div><div>For higher analytical performance, ion mobility spectrometers (IMS), especially when analyzing complex mixtures, are often coupled with gas chromatographs (GC). However, analysis time remains a critical parameter in gas chromatography. Therefore, a hyper-fast GC is a promising approach for GC-IMS to combine highest sensitivity of IMS with increased peak capacity while allowing for rapid analysis within the double-digit second range. For simultaneously recording of both ion polarities, a new dual drift tube IMS in axial configuration has been developed that is particularly designed for resolving even hyper-fast GC peaks. Key is a directed sample gas flow through the ionization region giving a small effective detector volume. To avoid condensation of the sample gas, the IMS is isothermally heated to 120 °C. A drift tube length of only <em>L<sub>D</sub></em> = 41 mm with a drift voltage of <em>U<sub>D</sub></em> = 2.7 kV leads to an IMS repetition rate of 100 Hz and high resolving power of <em>R<sub>p</sub></em> = 60, even for ions with low reduced ion mobility down to 0.43 cm<sup>2</sup>V<sup>-1</sup>s<sup>-1</sup>. This setup can resolve very short GC peaks with full width at half maximum of only 140 ms. For demonstration, two different hop varieties and a mixture of explosives were analyzed within a short time of just 20 s.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1750 ","pages":"Article 465923"},"PeriodicalIF":3.8,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143759298","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 : 2025-03-29DOI: 10.1016/j.chroma.2025.465922
Ling Fang , Xiaokang Liu , Lin Feng , Kangnan Liu , Zhenwei Li , Yaling An , Daidi Zhang , Wenzhi Yang , De-an Guo
Mycotoxin contamination in Platycladi semen has become an increasing concern worldwide due to its significant threat to public health. In this study, a modified QuEChERS-based UPLC-MS/MS method was established to detect multi-mycotoxins in 190 batches of Platycladi semen samples obtained from various channels in China. Out of these samples, 188 tested positive for one or more mycotoxins, with an incidence of 98.95 %. Alternariol monomethyl ether was the most commonly detected with an incidence rate of 92.63 %, followed by fumonisin B2 at 91.58 % and sterigmatocystin at 87.89 %. Notably, the aflatoxin B1 contents in 26 samples and the total aflatoxins contents in 18 samples exceeded their respective official maximum residue limits. Given the toxicity and high contamination levels of mycotoxins, the risk of human exposure to them via the consumption of Platycladi semen was assessed using Monte Carlo simulation-based probabilistic models. The risk assessment using the margin of exposure and hazard quotient approach indicated that Platycladi semen is particularly susceptible to aflatoxins and sterigmatocystin, which pose significant threats to human health. This study provides the regulatory authority with a powerful platform for monitoring multi-mycotoxins in Platycladi semen, offering valuable data to safeguard consumers from potential health risks associated with mycotoxin contamination.
{"title":"Monte Carlo simulation-based risk assessment of human exposure to multi-mycotoxins in Platycladi semen","authors":"Ling Fang , Xiaokang Liu , Lin Feng , Kangnan Liu , Zhenwei Li , Yaling An , Daidi Zhang , Wenzhi Yang , De-an Guo","doi":"10.1016/j.chroma.2025.465922","DOIUrl":"10.1016/j.chroma.2025.465922","url":null,"abstract":"<div><div>Mycotoxin contamination in <em>Platycladi semen</em> has become an increasing concern worldwide due to its significant threat to public health. In this study, a modified QuEChERS-based UPLC-MS/MS method was established to detect multi-mycotoxins in 190 batches of <em>Platycladi semen</em> samples obtained from various channels in China. Out of these samples, 188 tested positive for one or more mycotoxins, with an incidence of 98.95 %. Alternariol monomethyl ether was the most commonly detected with an incidence rate of 92.63 %, followed by fumonisin B<sub>2</sub> at 91.58 % and sterigmatocystin at 87.89 %. Notably, the aflatoxin B<sub>1</sub> contents in 26 samples and the total aflatoxins contents in 18 samples exceeded their respective official maximum residue limits. Given the toxicity and high contamination levels of mycotoxins, the risk of human exposure to them via the consumption of <em>Platycladi semen</em> was assessed using Monte Carlo simulation-based probabilistic models. The risk assessment using the margin of exposure and hazard quotient approach indicated that <em>Platycladi semen</em> is particularly susceptible to aflatoxins and sterigmatocystin, which pose significant threats to human health. This study provides the regulatory authority with a powerful platform for monitoring multi-mycotoxins in <em>Platycladi semen</em>, offering valuable data to safeguard consumers from potential health risks associated with mycotoxin contamination.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1751 ","pages":"Article 465922"},"PeriodicalIF":3.8,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143791440","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 : 2025-03-29DOI: 10.1016/j.chroma.2025.465810
Karen Gaudin
This review summarizes the key points and focuses on the use of green solvents in reversed-phase high-performance liquid chromatography. Ethanol, acetone, ethyl lactate, propylene carbonate, dimethyl carbonate, methyl acetate, Cyrene, and glycerol are examined as green solvents, with an emphasis on their properties related to HPLC applications. A total of 135 articles published between 1990 and the present, which utilize ethanol-water mobile phases in RP-HPLC, highlight the established use of ethanol as a green solvent for RP-HPLC. Although ethanol is often characterized by its high viscosity and UV absorbance, it remains one of the most commonly used green solvents. This study shows that approximately 30 % of the ethanol-based methods developed employed columns with reduced particle diameters, without the need for column heating. In 26 % of cases, UV detection was used, even at wavelengths egal to or below 220 nm. However, ethanol's volatility and flammability pose risks of operator exposure and fire hazards. Consequently, alternative solvents have been explored to mitigate these issues.
Acetone, with over 20 years of use, presents similar safety concerns, compounded by its high UV absorbance. Recent advances in greener solvents, such as Cyrene, glycerol, and natural deep eutectic solvents, have been investigated to address VOC concerns in HPLC. However, these solvents still face challenges, including UV absorption, immiscibility with water, high viscosity, and limited availability in HPLC-grade quality. Therefore, additional research is needed to facilitate their broader application.
{"title":"Potential of green solvents as mobile phases in liquid chromatography","authors":"Karen Gaudin","doi":"10.1016/j.chroma.2025.465810","DOIUrl":"10.1016/j.chroma.2025.465810","url":null,"abstract":"<div><div>This review summarizes the key points and focuses on the use of green solvents in reversed-phase high-performance liquid chromatography. Ethanol, acetone, ethyl lactate, propylene carbonate, dimethyl carbonate, methyl acetate, Cyrene, and glycerol are examined as green solvents, with an emphasis on their properties related to HPLC applications. A total of 135 articles published between 1990 and the present, which utilize ethanol-water mobile phases in RP-HPLC, highlight the established use of ethanol as a green solvent for RP-HPLC. Although ethanol is often characterized by its high viscosity and UV absorbance, it remains one of the most commonly used green solvents. This study shows that approximately 30 % of the ethanol-based methods developed employed columns with reduced particle diameters, without the need for column heating. In 26 % of cases, UV detection was used, even at wavelengths egal to or below 220 nm. However, ethanol's volatility and flammability pose risks of operator exposure and fire hazards. Consequently, alternative solvents have been explored to mitigate these issues.</div><div>Acetone, with over 20 years of use, presents similar safety concerns, compounded by its high UV absorbance. Recent advances in greener solvents, such as Cyrene, glycerol, and natural deep eutectic solvents, have been investigated to address VOC concerns in HPLC. However, these solvents still face challenges, including UV absorption, immiscibility with water, high viscosity, and limited availability in HPLC-grade quality. Therefore, additional research is needed to facilitate their broader application.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1750 ","pages":"Article 465810"},"PeriodicalIF":3.8,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143747595","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 : 2025-03-28DOI: 10.1016/j.chroma.2025.465915
Yuki Obata, Hiroshi Sakamaki
A diastereomer peak broadening has been observed in phosphorothioate (PS) oligonucleotide analysis in several modes of high-performance liquid chromatography (HPLC). PS oligonucleotide impurities are of various types, and their physicochemical properties are similar to those of PS oligonucleotides. Consequently, quality control requires the chromatographic separation of PS oligonucleotide from impurities and separation of impurities from one another, which is challenging. In this study, to optimize the selectivity for effectively separating PS oligonucleotide from its impurities such as phosphodiester impurities (POs) and n − 1 truncated sequences (n − 1 s) in ion-pair reversed-phase (IP-RP) HPLC, the effect of mobile-phase conditions on the selectivity was investigated. Most importantly, it was demonstrated that the selectivity for the diastereomers of PS oligonucleotides is optimally reduced by the ion-pair (IP) system using alkylamine with a tertiary or quaternary structure and alkyl chain lengths of ≥4, using a method of observing the peak widths of PS oligonucleotides. Alternatively, using counterion species, such as hydrophobic alkyl carboxylic acid, improves the selectivity between the PS oligonucleotide and its impurities. Consequently, the IP system using tributylamine and heptanoic acid is proposed as the system that has optimal selectivity. This system can separate PS oligonucleotides from spiked PO and n − 1 groups involving those with different positions and has outstanding quantitative performance at the 0.2 %–5 % range. This study provides a guidance for optimizing the selectivity for IP-RP HPLC, and the proposed IP system could be useful for ensuring the quality control of antisense oligonucleotides including PS linkages.
{"title":"Improving the chromatographic separation of phosphorothioate oligonucleotide from impurities by optimizing selectivity through mobile-phase conditions in Ion-pair reversed-phase high-performance liquid chromatography","authors":"Yuki Obata, Hiroshi Sakamaki","doi":"10.1016/j.chroma.2025.465915","DOIUrl":"10.1016/j.chroma.2025.465915","url":null,"abstract":"<div><div>A diastereomer peak broadening has been observed in phosphorothioate (PS) oligonucleotide analysis in several modes of high-performance liquid chromatography (HPLC). PS oligonucleotide impurities are of various types, and their physicochemical properties are similar to those of PS oligonucleotides. Consequently, quality control requires the chromatographic separation of PS oligonucleotide from impurities and separation of impurities from one another, which is challenging. In this study, to optimize the selectivity for effectively separating PS oligonucleotide from its impurities such as phosphodiester impurities (POs) and <em>n</em> − 1 truncated sequences (<em>n</em> − 1 s) in ion-pair reversed-phase (IP-RP) HPLC, the effect of mobile-phase conditions on the selectivity was investigated. Most importantly, it was demonstrated that the selectivity for the diastereomers of PS oligonucleotides is optimally reduced by the ion-pair (IP) system using alkylamine with a tertiary or quaternary structure and alkyl chain lengths of ≥4, using a method of observing the peak widths of PS oligonucleotides. Alternatively, using counterion species, such as hydrophobic alkyl carboxylic acid, improves the selectivity between the PS oligonucleotide and its impurities. Consequently, the IP system using tributylamine and heptanoic acid is proposed as the system that has optimal selectivity. This system can separate PS oligonucleotides from spiked PO and <em>n</em> − 1 groups involving those with different positions and has outstanding quantitative performance at the 0.2 %–5 % range. This study provides a guidance for optimizing the selectivity for IP-RP HPLC, and the proposed IP system could be useful for ensuring the quality control of antisense oligonucleotides including PS linkages.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1750 ","pages":"Article 465915"},"PeriodicalIF":3.8,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143777135","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 : 2025-03-28DOI: 10.1016/j.chroma.2025.465921
Víctor Cutillas, Carmen Ferrer, María Jesús Martínez-Bueno, Amadeo R. Fernández-Alba
The growing importance of environmental sustainability has driven advancements in analytical chemistry, particularly in the development of green chromatographic techniques. This review explores various chromatographic methods that align with green chemistry principles, offering environmentally friendly alternatives to traditional gold-standard approaches. Techniques such as supercritical fluid chromatography (SFC), miniaturized liquid chromatography (LC), and gas chromatography (GC) with alternative carrier gases (e.g., hydrogen and nitrogen) are discussed in depth for their ability to reduce solvent consumption, minimize waste, and improve operational efficiency. These methods not only maintain high sensitivity and accuracy but also reduce the ecological impact of contaminant analysis. By comparing these sustainable approaches to conventional techniques, this review highlights their potential to meet regulatory standards while supporting eco-friendly practices within routine analysis laboratories.
{"title":"Green analytical approaches for contaminants: Sustainable alternatives to conventional chromatographic methods","authors":"Víctor Cutillas, Carmen Ferrer, María Jesús Martínez-Bueno, Amadeo R. Fernández-Alba","doi":"10.1016/j.chroma.2025.465921","DOIUrl":"10.1016/j.chroma.2025.465921","url":null,"abstract":"<div><div>The growing importance of environmental sustainability has driven advancements in analytical chemistry, particularly in the development of green chromatographic techniques. This review explores various chromatographic methods that align with green chemistry principles, offering environmentally friendly alternatives to traditional gold-standard approaches. Techniques such as supercritical fluid chromatography (SFC), miniaturized liquid chromatography (LC), and gas chromatography (GC) with alternative carrier gases (e.g., hydrogen and nitrogen) are discussed in depth for their ability to reduce solvent consumption, minimize waste, and improve operational efficiency. These methods not only maintain high sensitivity and accuracy but also reduce the ecological impact of contaminant analysis. By comparing these sustainable approaches to conventional techniques, this review highlights their potential to meet regulatory standards while supporting eco-friendly practices within routine analysis laboratories.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1750 ","pages":"Article 465921"},"PeriodicalIF":3.8,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143759297","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 : 2025-03-28DOI: 10.1016/j.chroma.2025.465919
Cheng Yang , Nian Yang , Di Zhao , Zhiyu Zhang , Junying Song , Zhenqiang Zhang , Kai Hu , Shusheng Zhang
Herein, a sulfonic-functionalized covalent organic framework@Ti3C2Tx nanocomposite (SO3HCOF@Ti3C2Tx) was synthesized and employed as solid phase microextraction (SPME) coating for isolation and extraction of monoamine neurotransmitters (MNTs) from rat serum samples. The resultant composite can combine the characteristics of hydrophilic Ti3C2Tx and SO3HCOF, which endow it has multiple adsorption sites and can provide multiple interactions such as cation exchange, hydrogen bonding and π-π with the target MNTs. The synthesized SO3HCOF@Ti3C2Tx SPME blades have excellent protein exclusion capability, ensuring high adsorption efficiency for MNTs. Under the optimized conditions, the proposed SO3HCOF@Ti3C2Tx blades-based SPME-HPLC method exhibited good linearities (r2≥0.9963), low limits of detection (0.015–0.030 ng mL-1) and low matrix effect (0.83 %-17.36 %). The recoveries of MNTs in the rat serum were in range of 90.3 %-118.3 %, with RSDs <10.8 %. The SPME-HPLC method was successfully applied for the analysis of 4 MNTs in the serum of depression model rats. This work not only details the development of a multi-functional composite, but it also presents an effective strategy for the determination of trace MNTs in serum sample.
{"title":"Sulfonic acid-functionalized covalent organic framework@Ti3C2Tx as efficient solid-phase microextraction blade coating for the extraction of monoamine neurotransmitters in rat serum samples","authors":"Cheng Yang , Nian Yang , Di Zhao , Zhiyu Zhang , Junying Song , Zhenqiang Zhang , Kai Hu , Shusheng Zhang","doi":"10.1016/j.chroma.2025.465919","DOIUrl":"10.1016/j.chroma.2025.465919","url":null,"abstract":"<div><div>Herein, a sulfonic-functionalized covalent organic framework@Ti<sub>3</sub>C<sub>2</sub>T<em><sub>x</sub></em> nanocomposite (SO<sub>3</sub>H<img>COF@Ti<sub>3</sub>C<sub>2</sub>T<em><sub>x</sub></em>) was synthesized and employed as solid phase microextraction (SPME) coating for isolation and extraction of monoamine neurotransmitters (MNTs) from rat serum samples. The resultant composite can combine the characteristics of hydrophilic Ti<sub>3</sub>C<sub>2</sub>T<em><sub>x</sub></em> and SO<sub>3</sub>H<img>COF, which endow it has multiple adsorption sites and can provide multiple interactions such as cation exchange, hydrogen bonding and π-π with the target MNTs. The synthesized SO<sub>3</sub>H<img>COF@Ti<sub>3</sub>C<sub>2</sub>T<em><sub>x</sub></em> SPME blades have excellent protein exclusion capability, ensuring high adsorption efficiency for MNTs. Under the optimized conditions, the proposed SO<sub>3</sub>H<img>COF@Ti<sub>3</sub>C<sub>2</sub>T<em><sub>x</sub></em> blades-based SPME-HPLC method exhibited good linearities (<em>r</em><sup>2</sup>≥0.9963), low limits of detection (0.015–0.030 ng mL<sup>-1</sup>) and low matrix effect (0.83 %-17.36 %). The recoveries of MNTs in the rat serum were in range of 90.3 %-118.3 %, with RSDs <10.8 %. The SPME-HPLC method was successfully applied for the analysis of 4 MNTs in the serum of depression model rats. This work not only details the development of a multi-functional composite, but it also presents an effective strategy for the determination of trace MNTs in serum sample.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1750 ","pages":"Article 465919"},"PeriodicalIF":3.8,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143747598","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 : 2025-03-28DOI: 10.1016/j.chroma.2025.465917
Liang Lai , Hongying Lan , Hui Huang , Tong Li , Kesara Ar-sanork , Jia-Huan Qu , Dongsheng Xu , Zhengjin Jiang
In this study, the chromatographic performance of a novel dual-zwitterionic hydrophilic stationary phase were investigated. Three zwitterionic HILIC monoliths were prepared using 3-(4-((methacryloyloxy)methyl)-1-methylpiperidin-1-ium-1-yl)propane-1-sulfonate (MAMMPS), 2-methacryloyloxyethyl phosphorylcholine (MPC), and a combination of MAMMPS and MPC (1:1, molar ratio) with N,N'-methylenebisacrylamide (MBA), separately. The monoliths exhibited good repeatability and stability. A high column efficiency of 120,000 plates/m was reached on the novel dual-zwitterionic functionalized poly(MAMMPS@MPC-co-MBA) monolith. Through the analysis and testing with different standards, the poly(MAMMPS@MPC-co-MBA) monolith exhibited the strongest retention capacity for negatively charged benzoic acid derivatives due to its high hydrophilicity and weak electronegativity. In contrast, the poly(MPC-co-MBA) monolith, functionalized with a single zwitterion, facilitated electrostatic interactions with negatively charged analytes. Baseline separation was achieved on all three monoliths for selected nucleobases, nucleosides, phenol derivatives, and amine compounds. However, their retention strength was mainly related to the hydrophilicity of the stationary phases, while hydrogen bonding and electrostatic interactions played secondary roles. Among the monoliths, the poly(MAMMPS-co-MBA) monolith demonstrated the best separation for neutral, acidic, and alkaline compounds. These findings offer valuable insights for the future selection and application of dual-zwitterionic HILIC monoliths for chromatographic separations.
{"title":"Fabrication and evaluation of a dual-zwitterionic functionalized hydrophilic monolith for chromatographic separation","authors":"Liang Lai , Hongying Lan , Hui Huang , Tong Li , Kesara Ar-sanork , Jia-Huan Qu , Dongsheng Xu , Zhengjin Jiang","doi":"10.1016/j.chroma.2025.465917","DOIUrl":"10.1016/j.chroma.2025.465917","url":null,"abstract":"<div><div>In this study, the chromatographic performance of a novel dual-zwitterionic hydrophilic stationary phase were investigated. Three zwitterionic HILIC monoliths were prepared using 3-(4-((methacryloyloxy)methyl)-1-methylpiperidin-1-ium-1-yl)propane-1-sulfonate (MAMMPS), 2-methacryloyloxyethyl phosphorylcholine (MPC), and a combination of MAMMPS and MPC (1:1, molar ratio) with <em>N,N'</em>-methylenebisacrylamide (MBA), separately. The monoliths exhibited good repeatability and stability. A high column efficiency of 120,000 plates/m was reached on the novel dual-zwitterionic functionalized poly(MAMMPS@MPC-<em>co</em>-MBA) monolith. Through the analysis and testing with different standards, the poly(MAMMPS@MPC-<em>co</em>-MBA) monolith exhibited the strongest retention capacity for negatively charged benzoic acid derivatives due to its high hydrophilicity and weak electronegativity. In contrast, the poly(MPC-<em>co</em>-MBA) monolith, functionalized with a single zwitterion, facilitated electrostatic interactions with negatively charged analytes. Baseline separation was achieved on all three monoliths for selected nucleobases, nucleosides, phenol derivatives, and amine compounds. However, their retention strength was mainly related to the hydrophilicity of the stationary phases, while hydrogen bonding and electrostatic interactions played secondary roles. Among the monoliths, the poly(MAMMPS-<em>co</em>-MBA) monolith demonstrated the best separation for neutral, acidic, and alkaline compounds. These findings offer valuable insights for the future selection and application of dual-zwitterionic HILIC monoliths for chromatographic separations.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1751 ","pages":"Article 465917"},"PeriodicalIF":3.8,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143785293","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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