Journal of Chromatography A最新文献_第8页

Highly sensitive tandem mass spectrometry detection for high resolution HILIC separation of biomass burning markers 高灵敏度串联质谱法检测生物质燃烧标志物的高分辨率HILIC分离

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-03-14 DOI: 10.1016/j.chroma.2025.465878

Harrison Stevens , Estrella Sanz Rodriguez , Mingxia Lai , Tessa R. Vance , Mark Curran , Harald Ritchie , Andrew R. Bowie , Brett Paull

Levoglucosan (LEV) and two of its isomers, mannosan (MAN) and galactosan (GAL), are commonly used as biomass burning tracers, however 1,6-anhydro-β-D-glucofuranose (AGF), another isomer derived from biomass burning, is rarely identified or quantified in existing literature. When present in environmental samples, AGF may be unknowingly co-eluting with another isomer, thus potentially compromising the accuracy of previously reported results. We present a novel hydrophilic interaction liquid chromatography (HILIC)-based separation method, coupled with tandem triple quadrupole mass spectrometry (MS/MS), capable of separating and quantifying all four fire-marker monosaccharide anhydrides (MAs). This separation relies on the hydrophilic penta‑hydroxy ligand functionality of HALO Penta-HILIC columns. Parameters such as mobile phase composition, column temperature, spray voltage, and selected reaction monitoring transitions were optimised to achieve a baseline separation to both confirm and improve detection of each isomer. Under optimal conditions, the limits of detection for LEV, MAN, GAL, and AGF were 0.39, 0.62, 0.52, and 0.04 µg/L, respectively. The accuracy of the method was validated via the analysis of the NIST Urban Dust 1649b certified reference material, with LEV, MAN, GAL concentrations in good agreement with previously determined results, and the concentration of AGF reported for the first time. The method was applied to a range of environmental samples (aerosols, sediments, and ice cores) to prove its applicability for different matrices. Due to its speed (< 10 min), selectivity, and sensitivity, this HILIC-MS/MS based method can be utilised in future studies to quantify all four fire-marker isomers, allowing the calculation of additional isomer ratios, which may assist with biomass burning source identification.

左旋葡聚糖（LEV）及其两种异构体甘露聚糖（MAN）和半乳糖聚糖（GAL）通常被用作生物质燃烧示踪剂，然而，另一种来自生物质燃烧的异构体1,6-无水-β- d -葡聚糖（AGF）在现有文献中很少被鉴定或量化。当存在于环境样品中时，AGF可能会不知不觉地与另一种异构体共洗脱，从而潜在地损害先前报道结果的准确性。我们提出了一种新的基于亲水性相互作用液相色谱（HILIC）的分离方法，结合串联三重四极杆质谱（MS/MS），能够分离和定量所有四种火标记单糖酸酐（MAs）。这种分离依赖于HALO penta - hilic柱的亲水五羟基配体功能。优化了流动相组成、柱温、喷雾电压和选定的反应监测转变等参数，以实现基线分离，以确认和提高对每种异构体的检测。在最佳条件下，LEV、MAN、GAL和AGF的检出限分别为0.39、0.62、0.52和0.04µg/L。通过对NIST Urban Dust 1649b认证标准物质的分析验证了该方法的准确性，LEV、MAN、GAL浓度与先前确定的结果吻合良好，AGF浓度为首次报道。该方法应用于一系列环境样品（气溶胶，沉积物和冰芯），以证明其适用于不同的基质。由于它的速度(<；10分钟)，选择性和灵敏度，这种基于HILIC-MS/MS的方法可以在未来的研究中用于量化所有四种火标记异构体，允许计算额外的异构体比例，这可能有助于生物质燃烧源鉴定。

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引用次数: 0

Purification of a non-enveloped virus using sequential aqueous two-phase extraction 连续水两相萃取法纯化非包膜病毒

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-03-13 DOI: 10.1016/j.chroma.2025.465866

Natalie M. Nold , Seth A. Kriz , Sheridan Waldack , Grace James , Trisha Colling , Taravat Sarvari , Vaishali Sharma , Alexis Pohkrel , Ethan Burghardt , Pratik U. Joshi , Caryn L. Heldt

Virus-based vaccines and therapies require a purification method that is both cost-effective and easily scalable. An aqueous two-phase system (ATPS) consisting of polyethylene glycol (PEG) and citrate salt has been proven to deliver high virus recoveries along with high impurity removal. However, these systems often place the virus into a viscous PEG-rich phase or at the two-phase interface, leading to difficulties in subsequent downstream processes. This study explored a second ATPS to extract the virus product back into the citrate-rich phase by changing the chemical conditions, a required step for future application of ATPS in industrial processes. ATPS performance was tested as a function of phase component concentration, phase component volume ratios, PEG molecular weight, salt type, pH, and glycine addition to identify the most impactful parameters for the extraction of non-enveloped porcine parvovirus (PPV). By shifting the pH, lowering phase component concentrations, and increasing the volume ratio of the citrate-rich phase between the first and second ATPS steps, 66 % of infectious PPV was recovered with 2.0 logs of host cell protein removal and 1.0 logs of host cell DNA removal. Using a PEG molecular weight of 8 kDa enabled a pH shift between the first and second ATPS steps without precipitation. Glycine addition during the first step of ATPS and phosphate salt use during the second step of ATPS did not significantly increase the overall recovery. In future studies, the optimized process will be implemented for multiple viral vector types and continuously to demonstrate continuous and low-cost viral vector manufacturing.

基于病毒的疫苗和疗法需要一种既具有成本效益又易于扩展的纯化方法。由聚乙二醇（PEG）和柠檬酸盐组成的水两相体系（ATPS）已被证明具有高病毒回收率和高杂质去除率。然而，这些系统通常将病毒置于粘性的富含peg的阶段或两相界面，导致后续下游工艺的困难。本研究探索了第二种ATPS，通过改变化学条件将病毒产物提取回富含柠檬酸盐的相，这是未来ATPS在工业过程中应用的必要步骤。以相组份浓度、相组份体积比、PEG分子量、盐类型、pH和甘氨酸添加量作为ATPS性能的函数，确定对非包膜猪细小病毒（PPV）提取影响最大的参数。通过改变pH值，降低相组分浓度，增加第一步和第二步之间富含柠檬酸盐的相的体积比，以2.0 log的宿主细胞蛋白质去除和1.0 log的宿主细胞DNA去除，恢复了66%的感染性PPV。使用分子量为8 kDa的PEG，可以在第一步和第二步之间实现pH值的转移，而不会产生沉淀。在ATPS的第一步中添加甘氨酸和在ATPS的第二步中使用磷酸盐并没有显著提高总回收率。在未来的研究中，优化的工艺将在多种病毒载体类型中持续实施，以证明连续低成本的病毒载体制造。

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引用次数: 0

Exploration of synergic solvent extraction and extraction chromatographic materials for the separation of 161Tb from enriched 160Gd targets 协同溶剂萃取萃取色谱材料从富集的160Gd中分离161Tb的探索

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-03-13 DOI: 10.1016/j.chroma.2025.465869

Connor K. Holiski , Lauren Hoekstra , Nicholas Becker , Heather M. Hennkens , Mary F. Embree , Meng-Jen (Vince) Wang , Glenn E. Sjoden , Tara Mastren

One rare earth element (REE) radionuclide of considerable interest for nuclear medicine is ¹⁶¹Tb (t_1/₂ = 6.95 day, β^–_max = 593 keV), which can be produced using nuclear reactors through an indirect neutron capture reaction,

_{64}^{160} Gd (n, γ)_{64}^{161} Gd (t_{1 / 2} = 3.7 m i n, β^{-})_{65}^{161} Tb,

using enriched ¹⁶⁰Gd targets. A significant challenge in implementing ¹⁶¹Tb and new REE radionuclides into radiopharmaceutical agents is the efficient separation of the product and target materials to achieve a high specific activity. This study explored the use of synergic extractant combinations to enhance the extraction and separation efficiencies of Gd(III) and Tb(III). Three neutral organophosphorus extractants, octyl (phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO), dibutyl N,N-diethylcarbamylmethylenephosphonate (DBDECMP), and dihexyl N,N-diethylcarbamylmethylenephosphonate (DHDECMP), were investigated as synergic agents in solvent extraction (SX) when combined with one of two β-diketones, 2-thenoyltrifluoroacetone (HTTA) and 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one (HP). The separation factors (SF_Tb/Gd) of Tb(III) and Gd(III) for each system are reported as a function of extractant concentration. The system with the highest SF_Tb/Gd was found to be 0.1 M HTTA and 0.1 M DBDECMP at pH 2.00, which displayed a SF_Tb/Gd of 3.7 ± 0.1. This extractant combination was sorbed onto a macroporous support at various extractant ratios using rotary evaporator methods, and their Gd(III) and Tb(III) uptake behavior was characterized. The prepared EXC resins exhibited excellent metal retention in column experiments, demonstrating promising potential for separating Gd(III) and Tb(III), while recovering approximately 96.6 % of ¹⁶¹Tb with <5 % of the initial Gd(III) mass. Thermodynamic studies revealed an endothermic adsorption progress with increased uptake and decreased Gibbs free energy (ΔG) with rising temperature. Overall, this work successfully demonstrated the conversion and characterization of synergic SX systems into novel synergic EXC resins for adjacent REE separations.

一种对核医学非常感兴趣的稀土元素（REE）放射性核素是161Tb (t1/2= 6.95 day, β-max = 593 keV)，它可以通过核反应堆的间接中子俘获反应产生，64160Gd(n,γ)64161Gd(t1/2=3.7min,β-)65161Tb，使用富集的160Gd靶。将161Tb和新的REE放射性核素应用于放射性药物制剂的一个重大挑战是产品和目标材料的有效分离，以实现高比活性。本研究探索了使用协同萃取剂组合来提高Gd（III）和Tb（III）的萃取和分离效率。研究了三种中性有机磷萃取剂辛基（苯基）-N，N-二异丁基氨基甲酰甲基氧化膦（CMPO）、二丁基N，N-二乙基氨基甲酰亚膦酸二丁基（DBDECMP）和二己基N，N-二乙基氨基甲酰亚膦酸二己基（DHDECMP）与两种β-二酮，2-烯酰三氟丙酮（HTTA）和4-苯甲酰-3-甲基-1-苯基-2-吡唑啉-5-酮（HP）中的一种结合作为溶剂萃取（SX）的增效剂。每个体系中Tb（III）和Gd（III）的分离因子（SFTb/Gd）是萃取剂浓度的函数。在pH为2.00时，最高的SFTb/Gd为0.1 M hta和0.1 M DBDECMP，其SFTb/Gd为3.7±0.1。采用旋转蒸发器法将该萃取剂组合以不同萃取剂比例吸附在大孔载体上，并对其对Gd（III）和Tb（III）的吸附行为进行了表征。制备的EXC树脂在柱状实验中表现出良好的金属保留性，显示出分离Gd（III）和Tb（III）的良好潜力，同时回收约96.6%的161Tb

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引用次数: 0

Evaluation of hexamethyldisiloxane/ethyl isobutyrate/ethanol/water solvent system for liquid-liquid chromatography

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-03-13 DOI: 10.1016/j.chroma.2025.465873

Kai Wang, Simon Vlad Luca, Mirjana Minceva

The most commonly used solvent systems in liquid-liquid chromatography (LLC), such as heptane/ethyl acetate/methanol/water (ARIZONA) or its variant hexane/ethyl acetate/methanol/water (HEMWat), contain toxic petroleum-based solvents that raise serious risks to human health and environment. Therefore, there is a great need to find alternative, greener, and safer solvent systems for LLC applications. This work comprehensively evaluated an alternative biphasic solvent system, hexamethyldisiloxane/ethyl isobutyrate/ethanol/water (HMDSO/EIB/ethanol/water), by considering its thermodynamic properties, physical properties, and suitability for LLC applications. Compared with the HEMWat system, the HMDSO/EIB/ethanol/water system had a similar phase density difference, higher phase viscosity, and longer settling times. The distribution constants (

K_{i}

) of 12 test compounds with different polarities and chemical structural features representative of various classes of natural products were assessed in 16 compositions of the HMDSO/EIB/ethanol/water and HEMWat systems. System compositions with similar

K_{i}

values were identified for the two solvent systems. Since COSMO-RS provided good predictions of the

K_{i}

of the test compounds, its use can significantly reduce the process of finding an HMDSO/EIB/ethanol/water system composition for separating other components, using only their molecular structures as input. The results of countercurrent chromatography and centrifugal partition chromatography experiments showed comparable separation behaviors of selected compounds in both solvent systems, demonstrating that the HMDSO/EIB/ethanol/water system could be a viable, safer replacement for HEMWat and ARIZONA solvent systems in LLC.

液-液色谱（LLC）中最常用的溶剂体系，如庚烷/乙酸乙酯/甲醇/水（ARIZONA）或其变体己烷/乙酸乙酯/甲醇/水（HEMWat），含有有毒的石油基溶剂，对人类健康和环境构成严重风险。因此，迫切需要为LLC应用寻找更环保、更安全的替代溶剂系统。本研究综合评价了一种替代双相溶剂体系——六甲基二硅氧烷/异丁酸乙酯/乙醇/水（HMDSO/EIB/乙醇/水），考虑了其热力学性质、物理性质和LLC应用的适用性。与HEMWat体系相比，HMDSO/EIB/乙醇/水体系具有相似的相密度差、更高的相粘度和更长的沉淀时间。在HMDSO/EIB/乙醇/水和HEMWat体系的16种组成中，测定了具有不同极性和不同化学结构特征的12种测试化合物的分布常数（Ki）。两种溶剂体系的组分具有相似的Ki值。由于cosmos - rs能够很好地预测测试化合物的Ki值，因此使用它可以大大减少寻找HMDSO/EIB/乙醇/水体系组成物来分离其他组分的过程，而只使用它们的分子结构作为输入。逆流色谱和离心分配色谱实验结果表明，两种溶剂体系中所选化合物的分离行为相当，表明HMDSO/EIB/乙醇/水体系可以作为LLC中HEMWat和ARIZONA溶剂体系的可行且更安全的替代品。

{"title":"Evaluation of hexamethyldisiloxane/ethyl isobutyrate/ethanol/water solvent system for liquid-liquid chromatography","authors":"Kai Wang, Simon Vlad Luca, Mirjana Minceva","doi":"10.1016/j.chroma.2025.465873","DOIUrl":"10.1016/j.chroma.2025.465873","url":null,"abstract":"<div><div>The most commonly used solvent systems in liquid-liquid chromatography (LLC), such as heptane/ethyl acetate/methanol/water (ARIZONA) or its variant hexane/ethyl acetate/methanol/water (HEMWat), contain toxic petroleum-based solvents that raise serious risks to human health and environment. Therefore, there is a great need to find alternative, greener, and safer solvent systems for LLC applications. This work comprehensively evaluated an alternative biphasic solvent system, hexamethyldisiloxane/ethyl isobutyrate/ethanol/water (HMDSO/EIB/ethanol/water), by considering its thermodynamic properties, physical properties, and suitability for LLC applications. Compared with the HEMWat system, the HMDSO/EIB/ethanol/water system had a similar phase density difference, higher phase viscosity, and longer settling times. The distribution constants (<span><math><msub><mi>K</mi><mi>i</mi></msub></math></span>) of 12 test compounds with different polarities and chemical structural features representative of various classes of natural products were assessed in 16 compositions of the HMDSO/EIB/ethanol/water and HEMWat systems. System compositions with similar <span><math><msub><mi>K</mi><mi>i</mi></msub></math></span> values were identified for the two solvent systems. Since COSMO-RS provided good predictions of the <span><math><msub><mi>K</mi><mi>i</mi></msub></math></span> of the test compounds, its use can significantly reduce the process of finding an HMDSO/EIB/ethanol/water system composition for separating other components, using only their molecular structures as input. The results of countercurrent chromatography and centrifugal partition chromatography experiments showed comparable separation behaviors of selected compounds in both solvent systems, demonstrating that the HMDSO/EIB/ethanol/water system could be a viable, safer replacement for HEMWat and ARIZONA solvent systems in LLC.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1748 ","pages":"Article 465873"},"PeriodicalIF":3.8,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143637280","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}

引用次数: 0

Compressed chromatographic fingerprint of Artemisiae argyi Folium empowered by 1D-CNN: Reduce mobile phase consumption using chemometric algorithm

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-03-13 DOI: 10.1016/j.chroma.2025.465874

Wennan Nie , Jiahe Qian , Cunhao Li , Shule Zhang , Wenlong Li

Introduction

High-Performance Liquid Chromatography (HPLC) is widely used for its high sensitivity, stability, and accuracy. Nonetheless, it often involves lengthy analysis times and considerable solvent consumption, especially when dealing with complex systems and quality control, posing challenges to green and eco-friendly analytical practices.

Objective

This study proposes a compressed fingerprint chromatogram analysis technique that combines a one-dimensional convolutional neural network (1D-CNN) with HPLC, aiming to improve the analytical efficiency of various compounds in complex systems while reducing the use of organic solvents.

Materials and Methods

The natural product Artemisiae argyi Folium (AAF) was selected as the experimental subject. Firstly, HPLC fingerprints of AAF were developed based on conventional programs. Next, a compressed fingerprint was obtained without losing compound information. Finally, a 1D-CNN deep learning model was used to analyze and identify the compressed chromatograms, enabling quantitative analysis of 10 compounds in complex systems.

Results

The results indicate that the 1D-CNN model can effectively extract features from complex data, reducing the analysis time for each sample by about 40 min. In addition, the consumption of mobile phase has significantly decreased by 78 % compared to before. Among the ten compounds to be analyzed, nine of them achieved good results, with the highest correlation coefficient reaching above 0.95, indicating that the model has strong explanatory power.

Conclusion

The proposed compressed fingerprint chromatograms recognition technique enhances the environmental sustainability and efficiency of traditional HPLC methods, offering valuable insights for future advancements in analytical methodologies and equipment development.

高效液相色谱法（HPLC）因其高灵敏度、稳定性和准确性而被广泛应用。然而，它通常涉及较长的分析时间和相当大的溶剂消耗，特别是在处理复杂的系统和质量控制时，对绿色和环保的分析实践提出了挑战。目的提出一种将一维卷积神经网络（1D-CNN）与高效液相色谱（HPLC）相结合的压缩指纹图谱分析技术，旨在提高复杂体系中各种化合物的分析效率，同时减少有机溶剂的使用。材料与方法以天然产物艾叶蒿（artemisisiae argyi Folium， AAF）为实验对象。首先，在常规程序的基础上建立了AAF的HPLC指纹图谱。然后，在不丢失复合信息的情况下获得压缩指纹。最后，利用1D-CNN深度学习模型对压缩色谱图进行分析和识别，实现了对复杂体系中10种化合物的定量分析。结果1D-CNN模型可以有效地从复杂数据中提取特征，每个样本的分析时间缩短约40 min，流动相的消耗比之前显著降低了78%。在待分析的10种化合物中，有9种获得了较好的结果，最高相关系数达到0.95以上，说明该模型具有较强的解释力。结论所建立的压缩指纹图谱识别技术提高了传统HPLC方法的环境可持续性和效率，为未来分析方法和设备的发展提供了有价值的见解。

{"title":"Compressed chromatographic fingerprint of Artemisiae argyi Folium empowered by 1D-CNN: Reduce mobile phase consumption using chemometric algorithm","authors":"Wennan Nie , Jiahe Qian , Cunhao Li , Shule Zhang , Wenlong Li","doi":"10.1016/j.chroma.2025.465874","DOIUrl":"10.1016/j.chroma.2025.465874","url":null,"abstract":"<div><h3>Introduction</h3><div>High-Performance Liquid Chromatography (HPLC) is widely used for its high sensitivity, stability, and accuracy. Nonetheless, it often involves lengthy analysis times and considerable solvent consumption, especially when dealing with complex systems and quality control, posing challenges to green and eco-friendly analytical practices.</div></div><div><h3>Objective</h3><div>This study proposes a compressed fingerprint chromatogram analysis technique that combines a one-dimensional convolutional neural network (1D-CNN) with HPLC, aiming to improve the analytical efficiency of various compounds in complex systems while reducing the use of organic solvents.</div></div><div><h3>Materials and Methods</h3><div>The natural product <em>Artemisiae argyi Folium</em> (AAF) was selected as the experimental subject. Firstly, HPLC fingerprints of AAF were developed based on conventional programs. Next, a compressed fingerprint was obtained without losing compound information. Finally, a 1D-CNN deep learning model was used to analyze and identify the compressed chromatograms, enabling quantitative analysis of 10 compounds in complex systems.</div></div><div><h3>Results</h3><div>The results indicate that the 1D-CNN model can effectively extract features from complex data, reducing the analysis time for each sample by about 40 min. In addition, the consumption of mobile phase has significantly decreased by 78 % compared to before. Among the ten compounds to be analyzed, nine of them achieved good results, with the highest correlation coefficient reaching above 0.95, indicating that the model has strong explanatory power.</div></div><div><h3>Conclusion</h3><div>The proposed compressed fingerprint chromatograms recognition technique enhances the environmental sustainability and efficiency of traditional HPLC methods, offering valuable insights for future advancements in analytical methodologies and equipment development.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1748 ","pages":"Article 465874"},"PeriodicalIF":3.8,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143642738","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Influence of zwitterionic liquid chemical structure on separation of volatile carboxylic acids when used as stationary phases in gas chromatography 两性离子液体化学结构对气相色谱中挥发性羧酸分离的影响。

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-03-12 DOI: 10.1016/j.chroma.2025.465872

Victoria R. Zeger , Jessica F. DeLair , Bhawana Thapa , Daniel Shollenberger , Moubani Chakraborty , Jason S. Herrington , David S. Bell , Jared L. Anderson

Volatile carboxylic acids (VCAs) are important chemicals and synthetic building blocks in various industrial fields ranging from foods to polymers and pharmaceuticals. The analysis of VCAs using gas chromatography (GC) is challenging due to poor peak shapes on many traditional polar stationary phases. Zwitterionic liquids (ZILs) are promising GC stationary phase materials, featuring improved inertness for acidic molecules. In this study, imidazolium-based ZILs with sulfonate and triflimide anions are evaluated to understand the influence of ZIL chemical structure on the separation of polar analytes. Five VCAs were used as probe molecules to evaluate chromatographic retention, peak shapes, and selectivity. Higher VCA retention was observed on imidazolium sulfonate ZIL stationary phases compared to a commercially available wax-type or polyethylene glycol-based columns. ZILs containing either octyl or decyl substituents provided higher VCA retention than oligoether functionalized ZILs, but incorporation of a phenyl moiety to the imidazolium ring increased retention of oligoether functionalized ZILs. VCA retention also decreased when either the anion was exchanged or linker length connecting the cation and anion groups was decreased. The chemical nature of substituent groups and chain length appears to play important roles in controlling VCA selectivity, where alkyl-substituted ZILs offered higher selectivity than the oligoether ZILs. Excellent peak asymmetry factors (< 2) were observed for most ZIL stationary phases; however, oligoether functionalized ZILs exhibited limited analyte loading capacity for less polar VCAs. When ZIL stationary phases were coated on a salt-deactivated capillary, an increase in VCA retention was observed along with slightly higher peak asymmetry factors. For an oligoether ZIL stationary phase on salt-deactivated capillary, more prominent fronting peak shapes were observed due to reduced solubility of less polar VCAs in the stationary phase.

挥发性羧酸（VCAs）是重要的化学物质和各种工业领域的合成基石，从食品到聚合物和药品。由于许多传统极性固定相的峰形较差，使用气相色谱（GC）分析VCAs具有挑战性。两性离子液体（ZILs）是一种很有前途的气相色谱固定相材料，对酸性分子具有良好的惰性。本研究通过对咪唑基磺酸盐和三酰亚胺阴离子ZIL进行评价，以了解ZIL的化学结构对极性分析物分离的影响。5种vca作为探针分子来评价色谱保留、峰形和选择性。与市售的蜡型或聚乙二醇基柱相比，在咪唑磺酸ZIL固定相上观察到更高的VCA保留。含有辛基或癸基取代基的ZILs比低聚醚功能化的ZILs具有更高的VCA保留率，但在咪唑环中加入苯基片段增加了低聚醚功能化ZILs的保留率。当阴离子交换或连接正离子和阴离子基团的连接剂长度减少时，VCA保留率也降低。取代基的化学性质和链长似乎在控制VCA选择性中起重要作用，其中烷基取代的ZILs比低聚醚ZILs具有更高的选择性。大多数ZIL固定相的峰不对称系数均< 2；然而，低聚醚功能化的ZILs对低极性vca的分析物负载能力有限。当ZIL固定相涂覆在盐失活毛细管上时，观察到VCA保留率增加，峰不对称因子略高。对于盐失活毛细管上的低聚ZIL固定相，由于极性较低的VCAs在固定相中的溶解度降低，观察到更突出的前峰形状。

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引用次数: 0

Corrigendum to “Magnetic molecular imprinted covalent organic framework composite for the magnetic solid-phase extraction of bisphenol AF” [Journal of Chromatography A 1717 (2024) 464693]

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-03-12 DOI: 10.1016/j.chroma.2025.465847

Luchun Wang, Qiuyi Liu, Yuemeng Zou, Shaochi Liu, Yulian Yang, Yongqing Tao, Mingyue Wang, Lingling Li, Dandan Wang, Die Gao

引用次数: 0

Adaptable 3D printed detector for absorbance monitoring of column chromatography separations using deep-UV LED at 280 nm 用于280 nm深紫外LED柱色谱分离吸光度监测的适应性3D打印检测器。

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-03-12 DOI: 10.1016/j.chroma.2025.465870

Diego Godina Prado, Débora Machado de Lima, Karinne Teixeira Gonçalves, Alberto de Oliveira, Raquel Maria Ferreira de Sousa, João Flávio da Silveira Petruci

Column chromatography has been extensively used in the field of chemistry for a variety of applications, from the purification of synthesized compounds for pharmaceutical products to the isolation of natural products. Typically, the separated compounds are collected at the end of the column based on elution time, mobile phase volume, or colored markers. However, many target substances exhibit absorption in the ultraviolet range, making it challenging to monitor the elution process without an expensive instrumental detection system. In this study, we describe a flow-through absorbance-based detector for column chromatography using a deep-UV light-emitting diode with peak emission centered at 280 nm as light source for the first time. A 3D-printed holder was designed to house the LED and a UV-sensitive photodiode, positioned at 180° to measure radiation through a quartz tube with a diameter of 5 mm. The current generated by the photodiode was converted to absorbance using a log-ratio amplifier circuit and monitored via a USB data recorder. A noise level of 2.1 mAU was achieved, suitable for qualitative analysis. As a proof of concept, this detector was coupled with column chromatography to monitor the elution of (i) caffeine, (ii) a caffeine-hesperetin mixture, and a (iii) coffee extract sample. Absorbance spectra and thin-layer chromatography (TLC) experiments were performed to confirm the detector's capability to evaluate the efficiency of identifying UV-absorbing compounds. With this approach and the potential use of various deep-UV LEDs, we anticipate a cost-effective and efficient solution for monitoring the elution of non-colored compounds in column chromatography.

柱层析法已广泛应用于化学领域的各种应用，从纯化合成化合物的药物产品到天然产物的分离。通常，根据洗脱时间、流动相体积或彩色标记在色谱柱的末端收集分离的化合物。然而，许多目标物质在紫外线范围内表现出吸收，这使得在没有昂贵的仪器检测系统的情况下监测洗脱过程具有挑战性。在这项研究中，我们首次使用深紫外发光二极管作为光源，以280 nm为中心，描述了一种用于柱层析的基于吸光度的流动检测器。设计了一个3d打印支架来容纳LED和一个紫外线敏感的光电二极管，定位在180°，通过直径为5毫米的石英管测量辐射。光电二极管产生的电流通过对数比放大电路转换为吸光度，并通过USB数据记录器进行监测。达到2.1 mAU的噪声水平，适合定性分析。作为概念验证，该检测器与柱层析相结合，以监测(i)咖啡因，（ii）咖啡因-橙皮素混合物，以及（iii）咖啡提取物样品的洗脱。通过吸光度光谱和薄层色谱（TLC）实验验证了该检测器对紫外吸收化合物鉴别效率的评价。通过这种方法和各种深紫外led的潜在使用，我们期望一种具有成本效益和高效的解决方案来监测柱层析中非彩色化合物的洗脱。

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引用次数: 0

Chromatographic interferences potentially inflating the levels of Δ9-THC in Cannabis Sativa plant samples and possible solutions 色谱干扰可能会使大麻植物样品和可能的溶液中Δ9-THC的水平升高。

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-03-12 DOI: 10.1016/j.chroma.2025.465871

Walter B. Wilson , Andrea J. Yarberry , Stephen Goldman

Researchers in the Chemical Sciences Division (CSD) at the National Institute of Standards and Technology (NIST) have been evaluating existing and developing new analytical methods for the differentiation of hemp and marijuana since the passage of the Agriculture Improvement Act of 2018. This legislation defined hemp as a Cannabis sativa plant containing 0.3 % or less Δ⁹-tetrahydrocannabinol (Δ⁹-THC) and removed hemp from the United States Drug Enforcement Agency controlled substances list. The United States Department of Agriculture later clarified that this threshold must be representative of the total Δ⁹-THC, which includes the Δ⁹-THC acidic precursor Δ⁹-tetrahydrocannabinolic acid (Δ⁹-THCA). As a result, the burden of making these distinctions fell to forensic and Cannabis testing laboratories. NIST CSD has previously demonstrated accurate and precise analytical measurements for Δ⁹-THC, Δ⁹-THCA, and nine other related cannabinoids in well-characterized samples from interlaboratory studies at NIST by liquid chromatography with photodiode array detection (LC-PDA) following a methanolic extraction. This publication expands this method for the first time to include 16 commercial hemp samples and 20 seized Cannabis samples, simulating the types of samples typically analyzed by forensic and Cannabis testing laboratories. The results presented here highlight chromatographic interferences from CBNA and synthetic Δ⁸-THC by-products for Δ⁹-THC that can inflate its mass fraction levels and lead to the misidentification of Cannabis plant samples as marijuana when they are actually hemp. Data collected for 7448 plant samples in 2023 by a Cannabis testing laboratory were used to demonstrate the prevalence of these chromatographic interferences for the first time in a large sample population. Examples are included to demonstrate the resolution of chromatographic interferences through modification of the chromatographic method, selective detection methods, and peak deconvolution.

自2018年《农业改进法案》通过以来，美国国家标准与技术研究院（NIST）化学科学部（CSD）的研究人员一直在评估现有的大麻和大麻区分分析方法，并开发新的分析方法。该立法将大麻定义为含有0.3%或更少Δ9-tetrahydrocannabinol （Δ9-THC）的大麻植物，并将大麻从美国缉毒局控制物质清单中删除。美国农业部后来澄清说，这一阈值必须代表总量Δ9-THC，其中包括Δ9-THC酸性前体Δ9-tetrahydrocannabinolic酸（Δ9-THCA）。因此，作出这些区分的重担落在了法医和大麻检测实验室身上。NIST CSD先前通过甲醇提取后的液相色谱与光电二极管阵列检测（LC-PDA），在NIST的实验室间研究中，对Δ9-THC， Δ9-THCA和其他九种相关大麻素进行了准确和精确的分析测量。本出版物首次扩展了这种方法，包括16个商业大麻样本和20个缉获大麻样本，模拟了法医和大麻测试实验室通常分析的样本类型。本文的结果强调了来自CBNA和Δ9-THC合成Δ8-THC副产物的色谱干扰，这些干扰会使其质量分数水平膨胀，导致大麻植物样品被误认为是大麻，而实际上它们是大麻。大麻检测实验室于2023年收集了7448份植物样本的数据，首次在大样本群体中证明了这些色谱干扰的普遍性。示例包括通过改进色谱方法、选择性检测方法和峰反褶积来演示色谱干扰的解决。

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引用次数: 0

Corrigendum to “Evaluating orthogonality between ion-pair reversed phase, anion exchange, and hydrophilic interaction liquid chromatography for the separation of synthetic oligonucleotides” [Journal of Chromatography A 1705 (2023) 464184]

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-03-11 DOI: 10.1016/j.chroma.2025.465848

Matthew J. Sorensen, Mellie June Paulines, Todd D. Maloney

引用次数: 0