Pub Date : 2024-09-30DOI: 10.1016/j.chroma.2024.465410
P. Peiró-Vila, I. Luján-Roca, J.J. Baeza-Baeza, J.R. Torres-Lapasió, M.C. García-Alvarez-Coque
Considerable progress has been made in enhancing resolution in reversed-phase liquid chromatography for the analysis of complex samples, particularly within the field of natural products, through the application of global retention models using multi-linear gradients. Global models effectively differentiate solute retention effects from those originating from the column and solvent, offering predictive capabilities comparable to conventional individual retention models, without the requirement for standards for all compounds. While conventional individual models result in higher accuracy, they frequently demand standards that are unavailable for natural product samples. Moreover, the creation of individual models can be time-consuming due to the need for repetitive work for additional compounds. Experimental validation of global models has demonstrated that the accuracy is enough for the prediction of complex chromatograms. Through a carefully designed experimental work, this study reports the correct determination of global parameters for column and solvent, with excellent consistency across various medicinal plant samples. The successful transfer of predictions and optimisation of resolution across diverse plant species (lemon balm, peppermint, and pennyroyal) is confirmed. This highlights the applicability of predictions using global models across botanical varieties.
{"title":"Transferability of global retention models in reversed-phase liquid chromatography for natural products","authors":"P. Peiró-Vila, I. Luján-Roca, J.J. Baeza-Baeza, J.R. Torres-Lapasió, M.C. García-Alvarez-Coque","doi":"10.1016/j.chroma.2024.465410","DOIUrl":"10.1016/j.chroma.2024.465410","url":null,"abstract":"<div><div>Considerable progress has been made in enhancing resolution in reversed-phase liquid chromatography for the analysis of complex samples, particularly within the field of natural products, through the application of global retention models using multi-linear gradients. Global models effectively differentiate solute retention effects from those originating from the column and solvent, offering predictive capabilities comparable to conventional individual retention models, without the requirement for standards for all compounds. While conventional individual models result in higher accuracy, they frequently demand standards that are unavailable for natural product samples. Moreover, the creation of individual models can be time-consuming due to the need for repetitive work for additional compounds. Experimental validation of global models has demonstrated that the accuracy is enough for the prediction of complex chromatograms. Through a carefully designed experimental work, this study reports the correct determination of global parameters for column and solvent, with excellent consistency across various medicinal plant samples. The successful transfer of predictions and optimisation of resolution across diverse plant species (lemon balm, peppermint, and pennyroyal) is confirmed. This highlights the applicability of predictions using global models across botanical varieties.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1736 ","pages":"Article 465410"},"PeriodicalIF":3.8,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142386950","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 : 2024-09-30DOI: 10.1016/j.chroma.2024.465408
Rong Chen , Yehong Han , Ligai Bai , Mingyu Wang , Hongyuan Yan
A novel cis-diol-microporous organic networks (MONs-2OH) material was synthesized via room temperature and Sonogashira coupling reactions, which exhibits exceptional adsorption properties for catecholamines (CAs). MONs-2OH demonstrates robust hydrogen bonding and π-π stacking interactions, crucial for effective adsorption. The MONs-2OH was incorporated into pipette tip solid-phase extraction and developed a new method for detecting CAs in human urine using HPLC-MS/MS. Characterization of the adsorbent revealed its high stability, large specific surface area, abundant phenolic hydroxyl groups, rapid extraction speed, and superior adsorption efficiency. The method achieved a wide linear range (0.5–500 ng/mL), low detection limits (0.06–0.26 ng/mL), high accuracy (90.4 %-99.4 %), and excellent precision (RSD ≤ 10 %). Comparative studies showed MONs-2OH outperforms commercial adsorbents in terms of recovery and adsorption capacity. The results underscore the potential of MONs-2OH for rapid and sensitive CAs determination, offering significant advantages for the auxiliary diagnosis of depression and enhancing the application of PT-SPE in sample pretreatment.
{"title":"Enhanced detection of catecholamines in human urine using Cis-diol-microporous organic networks with PT-SPE and HPLC-MS/MS","authors":"Rong Chen , Yehong Han , Ligai Bai , Mingyu Wang , Hongyuan Yan","doi":"10.1016/j.chroma.2024.465408","DOIUrl":"10.1016/j.chroma.2024.465408","url":null,"abstract":"<div><div>A novel cis-diol-microporous organic networks (MONs-2OH) material was synthesized via room temperature and Sonogashira coupling reactions, which exhibits exceptional adsorption properties for catecholamines (CAs). MONs-2OH demonstrates robust hydrogen bonding and π-π stacking interactions, crucial for effective adsorption. The MONs-2OH was incorporated into pipette tip solid-phase extraction and developed a new method for detecting CAs in human urine using HPLC-MS/MS. Characterization of the adsorbent revealed its high stability, large specific surface area, abundant phenolic hydroxyl groups, rapid extraction speed, and superior adsorption efficiency. The method achieved a wide linear range (0.5–500 ng/mL), low detection limits (0.06–0.26 ng/mL), high accuracy (90.4 %-99.4 %), and excellent precision (RSD ≤ 10 %). Comparative studies showed MONs-2OH outperforms commercial adsorbents in terms of recovery and adsorption capacity. The results underscore the potential of MONs-2OH for rapid and sensitive CAs determination, offering significant advantages for the auxiliary diagnosis of depression and enhancing the application of PT-SPE in sample pretreatment.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1736 ","pages":"Article 465408"},"PeriodicalIF":3.8,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398953","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 : 2024-09-29DOI: 10.1016/j.chroma.2024.465406
Zijia Zhang , Yawen Liu , Gaohan Li , Xiaoling Chen , Min Lei , Yang Zhou , Huali Long , Qinhua Chen , Jinjun Hou , Wanying Wu
The complex pathological mechanisms of non-alcoholic fatty liver disease (NAFLD) are closely related to dysregulated lipid metabolism, and the therapeutic effects of the traditional Chinese medicine Zexie-Baizhu Decoction (AA) on NAFLD have been gaining increasing attention. However, research into altered lipid metabolism, especially fatty acids, in NAFLD and the intervention of AA faces technical challenges, especially in the precise quantitative analysis of fatty acids in biological samples. The high complexity of biological matrices, particularly after drug intervention, greatly increases the difficulty of detection. Therefore, this study innovatively developed a simple and economical stable isotope derivatization technique by synthesizing d6N,N-dimethylethylenediamine (d6-DMED) in the laboratory, establishing a simple and economical method for fatty acid quantification. This method employs a chemical reaction under low-temperature conditions to ensure the efficient synthesis of d6-DMED. Using ultra-high performance liquid chromatography-triple quadrupole mass spectrometry technique (UHPLC-MS/MS), combined with optimized chromatographic separation conditions and dynamic multiple reaction monitoring mode, the study established a highly sensitive detection method for 35 fatty acid derivatives. Methodological evaluation showed that the limits of quantification ranged from 0.002 to 0.060 μM, with high linearity of R² > 0.995. Additionally, the relative recovery rates were between 93.14% and 106.63%. To further demonstrate the feasibility of this method for fatty acid quantification, it was applied to measure fatty acids in multiple tissues in a mouse NAFLD model, as well as the effects of AA intervention on fatty acid metabolism. This rapid, simple, and cost-effective detection method not only enhances the understanding of NAFLD mechanisms but also provides a new strategy for evaluating the biological complex system after drug intervention.
非酒精性脂肪性肝病（NAFLD）的病理机制复杂，与脂质代谢紊乱密切相关，而中药泽泻白术汤（AA）对非酒精性脂肪性肝病的治疗效果日益受到关注。然而，非酒精性脂肪肝中脂质代谢（尤其是脂肪酸）的改变以及 AA 的干预研究面临着技术上的挑战，尤其是生物样本中脂肪酸的精确定量分析。生物基质的高度复杂性，尤其是药物干预后的生物基质，大大增加了检测的难度。因此，本研究通过在实验室合成 d6N,N-二甲基乙二胺（d6-DMED），创新性地发展了一种简单经济的稳定同位素衍生技术，建立了一种简单经济的脂肪酸定量分析方法。该方法采用低温条件下的化学反应，确保了 d6-DMED 的高效合成。该研究利用超高效液相色谱-三重四极杆质谱（UHPLC-MS/MS）技术，结合优化的色谱分离条件和动态多反应监测模式，建立了35种脂肪酸衍生物的高灵敏度检测方法。方法学评价表明，该方法的定量限为 0.002 至 0.060 μM，线性相关系数 R² > 0.995。此外，相对回收率在 93.14% 至 106.63% 之间。为了进一步证明该方法在脂肪酸定量方面的可行性，该方法被用于测量小鼠非酒精性脂肪肝模型中多个组织的脂肪酸含量，以及 AA 干预对脂肪酸代谢的影响。这种快速、简便、经济的检测方法不仅加深了人们对非酒精性脂肪肝机制的了解，而且为评估药物干预后的生物复杂系统提供了一种新策略。
{"title":"An economically viable stable isotope-enhanced multiple reaction monitoring method for total fatty acid analysis in a mouse model of non-alcoholic fatty liver disease","authors":"Zijia Zhang , Yawen Liu , Gaohan Li , Xiaoling Chen , Min Lei , Yang Zhou , Huali Long , Qinhua Chen , Jinjun Hou , Wanying Wu","doi":"10.1016/j.chroma.2024.465406","DOIUrl":"10.1016/j.chroma.2024.465406","url":null,"abstract":"<div><div>The complex pathological mechanisms of non-alcoholic fatty liver disease (NAFLD) are closely related to dysregulated lipid metabolism, and the therapeutic effects of the traditional Chinese medicine Zexie-Baizhu Decoction (AA) on NAFLD have been gaining increasing attention. However, research into altered lipid metabolism, especially fatty acids, in NAFLD and the intervention of AA faces technical challenges, especially in the precise quantitative analysis of fatty acids in biological samples. The high complexity of biological matrices, particularly after drug intervention, greatly increases the difficulty of detection. Therefore, this study innovatively developed a simple and economical stable isotope derivatization technique by synthesizing <em>d<sub>6</sub><sub><img></sub></em>N,N-dimethylethylenediamine (<em>d<sub>6</sub></em>-DMED) in the laboratory, establishing a simple and economical method for fatty acid quantification. This method employs a chemical reaction under low-temperature conditions to ensure the efficient synthesis of <em>d<sub>6</sub></em>-DMED. Using ultra-high performance liquid chromatography-triple quadrupole mass spectrometry technique (UHPLC-MS/MS), combined with optimized chromatographic separation conditions and dynamic multiple reaction monitoring mode, the study established a highly sensitive detection method for 35 fatty acid derivatives. Methodological evaluation showed that the limits of quantification ranged from 0.002 to 0.060 μM, with high linearity of R² > 0.995. Additionally, the relative recovery rates were between 93.14% and 106.63%. To further demonstrate the feasibility of this method for fatty acid quantification, it was applied to measure fatty acids in multiple tissues in a mouse NAFLD model, as well as the effects of AA intervention on fatty acid metabolism. This rapid, simple, and cost-effective detection method not only enhances the understanding of NAFLD mechanisms but also provides a new strategy for evaluating the biological complex system after drug intervention.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1736 ","pages":"Article 465406"},"PeriodicalIF":3.8,"publicationDate":"2024-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142386939","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 : 2024-09-29DOI: 10.1016/j.chroma.2024.465404
Attilio Naccarato, Rosangela Elliani, Antonio Tagarelli
This work presents a novel method for the analysis of polycyclic aromatic hydrocarbons (PAHs) in saliva samples using solid phase microextraction (SPME) coupled with gas chromatography-triple quadrupole mass spectrometry (GC-QqQ-MS). The protocol utilizes the latest commercially available overcoated fiber (PDMS/DVB/PDMS) for direct immersion extraction of the target analytes, enabling the determination of thirteen PAHs, including low-volatile compounds. The SPME extraction method was optimized using a central composite design (CCD). The evaluation of the fiber coating's robustness over time demonstrated excellent extraction performance with no significant degradation. The validation procedure confirmed good performance for all parameters, with LOQ values (100 ng/L for ten analytes and 500 ng/L for three analytes) comparable to other chromatographic methods. The environmental impact of the protocol was objectively assessed using two recently proposed metrics: the Green Analytical Procedure Index (GAPI) and the Analytical Greenness metric for sample preparation (AGREEprep). Both metrics indicated good overall environmental friendliness, with AGREEprep providing a satisfactory comprehensive score despite the use of highly impactful instrumentation. These characteristics make the developed method suitable for routine analysis in environmental and epidemiological monitoring.
{"title":"A direct immersion-solid-phase microextraction method for the automated determination of 3- to 6-ring polycyclic aromatic hydrocarbons in saliva by gas-chromatography-tandem mass spectrometry","authors":"Attilio Naccarato, Rosangela Elliani, Antonio Tagarelli","doi":"10.1016/j.chroma.2024.465404","DOIUrl":"10.1016/j.chroma.2024.465404","url":null,"abstract":"<div><div>This work presents a novel method for the analysis of polycyclic aromatic hydrocarbons (PAHs) in saliva samples using solid phase microextraction (SPME) coupled with gas chromatography-triple quadrupole mass spectrometry (GC-QqQ-MS). The protocol utilizes the latest commercially available overcoated fiber (PDMS/DVB/PDMS) for direct immersion extraction of the target analytes, enabling the determination of thirteen PAHs, including low-volatile compounds. The SPME extraction method was optimized using a central composite design (CCD). The evaluation of the fiber coating's robustness over time demonstrated excellent extraction performance with no significant degradation. The validation procedure confirmed good performance for all parameters, with LOQ values (100 ng/L for ten analytes and 500 ng/L for three analytes) comparable to other chromatographic methods. The environmental impact of the protocol was objectively assessed using two recently proposed metrics: the Green Analytical Procedure Index (GAPI) and the Analytical Greenness metric for sample preparation (AGREEprep). Both metrics indicated good overall environmental friendliness, with AGREEprep providing a satisfactory comprehensive score despite the use of highly impactful instrumentation. These characteristics make the developed method suitable for routine analysis in environmental and epidemiological monitoring.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1736 ","pages":"Article 465404"},"PeriodicalIF":3.8,"publicationDate":"2024-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142374845","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 : 2024-09-26DOI: 10.1016/j.chroma.2024.465402
Junchao Ma , Yinghua Qi , Mingyuan Lei , Haoran Xuan , Xuebo Li , Wenhui Lu , Jinshuang Guo , Huan Chen
Identifying the species and origin of adhesives in criminal investigations aids in narrowing inquiry scope and supporting case detection. This study introduces two advanced combined analytical techniques for distinguishing adhesive species, including attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) combined with Raman spectroscopy, and headspace gas chromatography-ion mobility spectrometry (HS-GC-IMS) together with multivariate statistical analysis. ATR-FTIR categorized seven adhesives into three groups based on the base materials, with further differentiation achieved via Raman spectra. Analysis of volatile components identified 79 volatile organic compounds (VOCs), with esters being the most concentrated. The fingerprint profile clearly illustrated the characteristic fingerprint sequence and unique marker compounds of each adhesive, effectively enabling their differentiation. Multivariate statistical analysis methods, including principal component analysis (PCA), orthogonal partial least squares-discriminant analysis (OPLS-DA), heatmap, and hierarchical cluster analysis (HCA), were utilized to visually interpret the classification of adhesives. This integrated analytical approach provides a comprehensive analysis of adhesive compositions, facilitating the diversification and precision of adhesive species identification, and broadening the scope for detecting and analyzing trace evidence in forensic science.
{"title":"Analysis and discrimination of adhesive species using ATR-FTIR combined with Raman, and HS-GC-IMS together with multivariate statistical analysis","authors":"Junchao Ma , Yinghua Qi , Mingyuan Lei , Haoran Xuan , Xuebo Li , Wenhui Lu , Jinshuang Guo , Huan Chen","doi":"10.1016/j.chroma.2024.465402","DOIUrl":"10.1016/j.chroma.2024.465402","url":null,"abstract":"<div><div>Identifying the species and origin of adhesives in criminal investigations aids in narrowing inquiry scope and supporting case detection. This study introduces two advanced combined analytical techniques for distinguishing adhesive species, including attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) combined with Raman spectroscopy, and headspace gas chromatography-ion mobility spectrometry (HS-GC-IMS) together with multivariate statistical analysis. ATR-FTIR categorized seven adhesives into three groups based on the base materials, with further differentiation achieved via Raman spectra. Analysis of volatile components identified 79 volatile organic compounds (VOCs), with esters being the most concentrated. The fingerprint profile clearly illustrated the characteristic fingerprint sequence and unique marker compounds of each adhesive, effectively enabling their differentiation. Multivariate statistical analysis methods, including principal component analysis (PCA), orthogonal partial least squares-discriminant analysis (OPLS-DA), heatmap, and hierarchical cluster analysis (HCA), were utilized to visually interpret the classification of adhesives. This integrated analytical approach provides a comprehensive analysis of adhesive compositions, facilitating the diversification and precision of adhesive species identification, and broadening the scope for detecting and analyzing trace evidence in forensic science.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1736 ","pages":"Article 465402"},"PeriodicalIF":3.8,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142363813","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 : 2024-09-26DOI: 10.1016/j.chroma.2024.465398
Yanhui Zhong , Heming Li , Zian Lin , Gongke Li
Sample preparation is crucial in analytical chemistry, impacting result accuracy, sensitivity, and reliability. Solid-phase separation media, especially adsorbents, are vital for preparing of liquid and gas samples, commonly analyzed by most analytical instruments. With the advancements in materials science, covalent organic frameworks (COFs) constructed through strong covalent bonds, have been increasingly employed in sample preparation in recent years. COFs have outstanding selectivity and/or excellent adsorption capacity for a single target or can selectively adsorb multiple targets from complex matrix, due to their large specific surface area, adjustable pore size, easy modification, and stable chemical properties. In this review, we summarize the classification of COFs, such as pristine COFs, COF composite particles, and COFs-based substrates. We aim to provide a comprehensive understanding of the different classifications of COFs in sample preparation within the last three years. The challenges and development trends of COFs in sample preparation are also presented.
{"title":"Advances in covalent organic frameworks for sample preparation","authors":"Yanhui Zhong , Heming Li , Zian Lin , Gongke Li","doi":"10.1016/j.chroma.2024.465398","DOIUrl":"10.1016/j.chroma.2024.465398","url":null,"abstract":"<div><div>Sample preparation is crucial in analytical chemistry, impacting result accuracy, sensitivity, and reliability. Solid-phase separation media, especially adsorbents, are vital for preparing of liquid and gas samples, commonly analyzed by most analytical instruments. With the advancements in materials science, covalent organic frameworks (COFs) constructed through strong covalent bonds, have been increasingly employed in sample preparation in recent years. COFs have outstanding selectivity and/or excellent adsorption capacity for a single target or can selectively adsorb multiple targets from complex matrix, due to their large specific surface area, adjustable pore size, easy modification, and stable chemical properties. In this review, we summarize the classification of COFs, such as pristine COFs, COF composite particles, and COFs-based substrates. We aim to provide a comprehensive understanding of the different classifications of COFs in sample preparation within the last three years. The challenges and development trends of COFs in sample preparation are also presented.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1736 ","pages":"Article 465398"},"PeriodicalIF":3.8,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142338396","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}
Two-dimensional gas chromatography (GC × GC) and two-dimensional liquid chromatography (LC × LC) are nowadays widely used in academia and industry due to their high separation power. However, as far as we know, the complementarity of these two techniques has not yet been thoroughly studied based on the analysis of the same sample. Therefore, this was undertaken here by analysing the liquid fraction obtained after depolymerising a natural waste – lignin – with GC × GC and off-line comprehensive LC × SFC (SFC: supercritical fluid chromatography). Using complementary techniques is also important for lignin valorisation, as thorough structural characterisation of the depolymerised product can aid with developing and improving valorisation processes. For the tentative identification, NIST library was used for GC × GC–MS results and MS-DIAL together with SIRIUS for LC × SFC-MS/MS data. This allowed to study which compounds are detectable with the different 2D methods but also to discuss the limitations of the data analysis processes. The previous knowledge that LC techniques are more suitable than GC × GC for the analysis of larger oligomers and other low volatility compounds was confirmed; however, it was seen that GC × GC enabled the analysis of smaller compounds, such as aliphatic alcohols and saturated compounds. Overall, the study demonstrates the complementarity of the two techniques but also draws attention to the different detectable compound groups and classifications that the two techniques can provide.
{"title":"Complementarity of two-dimensional gas chromatography and two-dimensional liquid chromatography for the analysis of depolymerised lignin","authors":"Eliise Tammekivi , Hugo Lilti , Magali Batteau , Chantal Lorentz , Christophe Geantet , Dorothée Laurenti , Karine Faure","doi":"10.1016/j.chroma.2024.465401","DOIUrl":"10.1016/j.chroma.2024.465401","url":null,"abstract":"<div><div>Two-dimensional gas chromatography (GC × GC) and two-dimensional liquid chromatography (LC × LC) are nowadays widely used in academia and industry due to their high separation power. However, as far as we know, the complementarity of these two techniques has not yet been thoroughly studied based on the analysis of the same sample. Therefore, this was undertaken here by analysing the liquid fraction obtained after depolymerising a natural waste – lignin – with GC × GC and off-line comprehensive LC × SFC (SFC: supercritical fluid chromatography). Using complementary techniques is also important for lignin valorisation, as thorough structural characterisation of the depolymerised product can aid with developing and improving valorisation processes. For the tentative identification, NIST library was used for GC × GC–MS results and MS-DIAL together with SIRIUS for LC × SFC-MS/MS data. This allowed to study which compounds are detectable with the different 2D methods but also to discuss the limitations of the data analysis processes. The previous knowledge that LC techniques are more suitable than GC × GC for the analysis of larger oligomers and other low volatility compounds was confirmed; however, it was seen that GC × GC enabled the analysis of smaller compounds, such as aliphatic alcohols and saturated compounds. Overall, the study demonstrates the complementarity of the two techniques but also draws attention to the different detectable compound groups and classifications that the two techniques can provide.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1736 ","pages":"Article 465401"},"PeriodicalIF":3.8,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142338397","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 : 2024-09-25DOI: 10.1016/j.chroma.2024.465396
Yuxuan Wu , Eduardo Barbieri , Ryan E. Kilgore , Brandyn D. Moore , Wenning Chu , Gina N. Mollica , Michael A. Daniele , Stefano Menegatti
Adenovirus (AdVs) is the viral vector of choice in vaccines and oncolytic applications owing to its high transduction activity and inherent immunogenicity. For decades, AdV isolation has relied on ultracentrifugation and ion-exchange chromatography, which are not suitable to large-scale production and struggle to deliver sufficient purity. Immunoaffinity chromatography resins of recent introduction feature high binding capacity and selectivity, but mandate harsh elution conditions (pH 3.0), afford low yield (< 20%), and provide limited reusability. Seeking a more efficient and affordable alternative, this study introduces the first peptide affinity ligands for AdV purification. The peptides were identified via combinatorial selection and in silico design to target hexons, the most abundant proteins in the adenoviral capsid. Selected peptide ligands AEFFIWNA and TNDGPDYSSPLTGSG were conjugated on chromatographic resins and utilized to purify AdV serotype 5 from HEK293 and Vero cell lysates. The peptide-functionalized resins feature high binding capacity (> 1010 active virions per mL at the residence time of 2 min), provide high yield (> 50%) and up to 100-fold reduction of host cell proteins and DNA. Notably, the peptide ligands enable gentle elution conditions (pH 8) that prevent the “shedding” of penton and fiber proteins, thus affording intact adenovirus particles with high cell-transduction activity. The study of the peptide ligands by surface plasmon resonance and molecular docking and dynamics simulations confirmed the selective targeting of hexon proteins and elucidated the molecular-level mechanisms underlying binding and release. Collectively, these results demonstrate the strong promise of peptide ligands presented herein for the affinity purification of AdVs from cell lysates.
{"title":"Peptide ligands for the affinity purification of adenovirus from HEK293 and vero cell lysates","authors":"Yuxuan Wu , Eduardo Barbieri , Ryan E. Kilgore , Brandyn D. Moore , Wenning Chu , Gina N. Mollica , Michael A. Daniele , Stefano Menegatti","doi":"10.1016/j.chroma.2024.465396","DOIUrl":"10.1016/j.chroma.2024.465396","url":null,"abstract":"<div><div>Adenovirus (AdVs) is the viral vector of choice in vaccines and oncolytic applications owing to its high transduction activity and inherent immunogenicity. For decades, AdV isolation has relied on ultracentrifugation and ion-exchange chromatography, which are not suitable to large-scale production and struggle to deliver sufficient purity. Immunoaffinity chromatography resins of recent introduction feature high binding capacity and selectivity, but mandate harsh elution conditions (pH 3.0), afford low yield (< 20%), and provide limited reusability. Seeking a more efficient and affordable alternative, this study introduces the first peptide affinity ligands for AdV purification. The peptides were identified via combinatorial selection and <em>in silico</em> design to target hexons, the most abundant proteins in the adenoviral capsid. Selected peptide ligands AEFFIWNA and TNDGPDYSSPLTGSG were conjugated on chromatographic resins and utilized to purify AdV serotype 5 from HEK293 and Vero cell lysates. The peptide-functionalized resins feature high binding capacity (> 10<sup>10</sup> active virions per mL at the residence time of 2 min), provide high yield (> 50%) and up to 100-fold reduction of host cell proteins and DNA. Notably, the peptide ligands enable gentle elution conditions (pH 8) that prevent the “shedding” of penton and fiber proteins, thus affording intact adenovirus particles with high cell-transduction activity. The study of the peptide ligands by surface plasmon resonance and molecular docking and dynamics simulations confirmed the selective targeting of hexon proteins and elucidated the molecular-level mechanisms underlying binding and release. Collectively, these results demonstrate the strong promise of peptide ligands presented herein for the affinity purification of AdVs from cell lysates.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1736 ","pages":"Article 465396"},"PeriodicalIF":3.8,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142338408","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 : 2024-09-25DOI: 10.1016/j.chroma.2024.465400
Samantha A. Labb , Kelly N. Kmak , John D. Despotopulos , William M. Kerlin , Ralf Sudowe
Advanced used nuclear fuel (UNF) reprocessing strategies are limited by the complex radiochemical separations and engineering required to achieve the separation of actinides (An) from neutron scavenging lanthanides (Ln). The accessibility of the hexavalent oxidation state for the actinides (U – Am) provides a pathway to achieving a group hexavalent actinide separation from the trivalent lanthanides and Cm. The solid oxidant and ion exchanger, sodium bismuthate (NaBiO3), has been demonstrated to quantitatively oxidize and separate Am from trivalent Cm in a column chromatographic system. This work expands on the use of NaBiO3 chromatography to characterize the adsorption, kinetic, and elution behavior of U, Pu, and Eu. Separation factors over 200 with rapid kinetics were observed at dilute nitric acid concentrations with a complete An/Ln separation achieved in under an hour. The adsorption and chromatographic behavior of key fission products present in various reprocessing raffinates was characterized which demonstrated potential application of a NaBiO3-based separation following a TRUEX process.
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Pub Date : 2024-09-25DOI: 10.1016/j.chroma.2024.465397
Ali Kheirkhah Barzoki , Amir Shamloo
In conventional Deterministic Lateral Displacement (DLD), the migration behavior of a particle of specific size is determined by the critical diameter (Dc), which is predefined by the device's geometry. In contrast to the typical approach that alters the angle between the pillar array and fluid streamlines by modifying the geometrical parameters, this study introduces a novel perspective that focuses on changing the direction of the streamlines. The proposed technique offers a tunable DLD chip featuring a straightforward design that allows for easy fabrication. This chip features one completely horizontal pillar array with two bypass channels on the top and bottom of the DLD chamber. The width of these bypass channels changes linearly from their inlet to their outlet. Two design configurations are suggested for this chip, characterized by either parallel or unparallel slopes of the bypass channels. This chip is capable of generating a wide range of Dc values by manipulating two distinct control parameters. The first control parameter involves adjusting the flow rates in the two bypass channels. The second control parameter entails controlling the slopes of these bypass channels. Both of these parameters influence the direction of particle-carrying streamlines resulting in a change in the path-line of the particles. By changing the angle of streamlines with pillar array, the Dc can be tuned. Prior to determining the Dc for each case, an initial estimation was made using a Python script that utilized the streamline coordinates. Subsequently, through FEM modeling of the particle trajectories, precise Dc values were ascertained and compared with the estimated values, revealing minimal disparities. By adjusting the flow rate and slope of the bypass channels, maximum Dc ranges of 4–10 μm and 8–13 μm can be achieved, respectively. This innovative chip enables the attainment of Dc values spanning from 0.5 to 14 μm.
在传统的确定性侧向位移（DLD）中，特定尺寸颗粒的迁移行为由临界直径（Dc）决定，而临界直径是由设备的几何形状预先确定的。典型的方法是通过修改几何参数来改变支柱阵列与流体流线之间的角度，与此不同的是，本研究引入了一种新的视角，重点在于改变流线的方向。所提出的技术提供了一种可调 DLD 芯片，其设计简单明了，易于制造。该芯片采用一个完全水平的支柱阵列，在 DLD 腔体的顶部和底部设有两个旁路通道。这些旁路通道的宽度从入口到出口呈线性变化。为这种芯片提出了两种设计配置，其特点是旁路通道的坡度平行或不平行。通过操纵两个不同的控制参数，该芯片能够产生较大范围的 Dc 值。第一个控制参数涉及调整两个旁路通道的流速。第二个控制参数涉及控制这些旁路通道的斜率。这两个参数都会影响颗粒携带流线的方向，从而改变颗粒的路径线。通过改变流线与支柱阵列的角度，可以调整 Dc。在确定每种情况的 Dc 值之前，使用 Python 脚本利用流线坐标进行了初步估算。随后，通过对粒子轨迹进行有限元建模，确定了精确的 Dc 值，并将其与估计值进行比较，结果显示差异极小。通过调整旁路通道的流速和坡度，最大 Dc 值范围可分别达到 4-10 μm 和 8-13 μm。这种创新型芯片可实现 0.5 至 14 μm 的 Dc 值。
{"title":"Streamline-directed tunable deterministic lateral displacement chip: A numerical approach to efficient particle separation","authors":"Ali Kheirkhah Barzoki , Amir Shamloo","doi":"10.1016/j.chroma.2024.465397","DOIUrl":"10.1016/j.chroma.2024.465397","url":null,"abstract":"<div><div>In conventional Deterministic Lateral Displacement (DLD), the migration behavior of a particle of specific size is determined by the critical diameter (D<sub>c</sub>), which is predefined by the device's geometry. In contrast to the typical approach that alters the angle between the pillar array and fluid streamlines by modifying the geometrical parameters, this study introduces a novel perspective that focuses on changing the direction of the streamlines. The proposed technique offers a tunable DLD chip featuring a straightforward design that allows for easy fabrication. This chip features one completely horizontal pillar array with two bypass channels on the top and bottom of the DLD chamber. The width of these bypass channels changes linearly from their inlet to their outlet. Two design configurations are suggested for this chip, characterized by either parallel or unparallel slopes of the bypass channels. This chip is capable of generating a wide range of D<sub>c</sub> values by manipulating two distinct control parameters. The first control parameter involves adjusting the flow rates in the two bypass channels. The second control parameter entails controlling the slopes of these bypass channels. Both of these parameters influence the direction of particle-carrying streamlines resulting in a change in the path-line of the particles. By changing the angle of streamlines with pillar array, the D<sub>c</sub> can be tuned. Prior to determining the D<sub>c</sub> for each case, an initial estimation was made using a Python script that utilized the streamline coordinates. Subsequently, through FEM modeling of the particle trajectories, precise D<sub>c</sub> values were ascertained and compared with the estimated values, revealing minimal disparities. By adjusting the flow rate and slope of the bypass channels, maximum D<sub>c</sub> ranges of 4–10 μm and 8–13 μm can be achieved, respectively. This innovative chip enables the attainment of D<sub>c</sub> values spanning from 0.5 to 14 μm.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1736 ","pages":"Article 465397"},"PeriodicalIF":3.8,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142338409","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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