Journal of Chromatography A最新文献

Shared-autosampler parallel LC–MS/MS platform for high-throughput multi-analyte quantification in complex matrices 共享自动进样器并行LC-MS /MS平台，用于复杂矩阵中高通量多分析物定量

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2026-05-10 Epub Date: 2026-03-07 DOI: 10.1016/j.chroma.2026.466885

Shanshan Cai , Qisheng Zhong , Jiaqi Liu , Lisong Chen , Lingling Shen , Hongyuan Hao , Ting Zhou

Modern analytical tasks increasingly require the simultaneous quantification of large numbers of chemically diverse analytes in complex matrices, which remains challenging for a single LC–MS method. Here, we developed a shared-autosampler parallel LC–MS/MS strategy that enables two fully independent chromatographic methods to be executed sequentially within a single analytical cycle while generating one unified chromatogram-mass spectrum. The system employed two LC pump modules and two columns to form two independent LC pathways, which shared one autosampler and one MS detector for selective MRM acquisition and subsequent signal integration. Integration was performed exclusively at the MS detection and data-processing level, without inter-dimensional coupling or analyte transfer between columns. This avoided the mobile-phase compatibility and dead-volume limitations associated with 2D-LC, enabled modular recombination of chromatographic and MS conditions, and improved analytical throughput without additional MS detector or autosampler hardware. The performance of the strategy was demonstrated in two applications. An acidic/basic dual-method configuration enabled quantitative analysis of 394 emerging contaminants from 14 chemical classes in human serum within 28 min, exhibiting good linearity, limits of quantification not exceeding 0.20 ng/mL for >90 % of analytes, and peak-area RSDs generally below 10 %. A HILIC/RP parallel-column combination achieved simultaneous determination of 27 hypoglycemic agents spanning a log P range of −6.8 to 5.9 in a single 20 min run, reducing analysis time by >50 % compared with standard methods, with good precision and recoveries in spiked food samples. Overall, the shared-autosampler parallel LC–MS/MS strategy provided a flexible and efficient platform for high-throughput multi-analyte quantification in complex matrices.

现代分析任务越来越需要在复杂的矩阵中同时定量大量化学上不同的分析物，这对于单一的LC-MS方法来说仍然是一个挑战。在这里，我们开发了一种共享自动进样器并行LC-MS /MS策略，使两种完全独立的色谱方法在一个分析周期内依次执行，同时生成一个统一的色谱-质谱。该系统采用两个LC泵模块和两个色谱柱组成两个独立的LC通路，共享一个自动进样器和一个质谱检测器，用于选择性MRM采集和随后的信号集成。集成仅在质谱检测和数据处理级别进行，没有多维耦合或柱之间的分析物转移。这避免了2D-LC相关的移动相兼容性和死体积限制，实现了色谱和质谱条件的模块化重组，并提高了分析通量，而无需额外的质谱检测器或自动进样器硬件。在两个应用中验证了该策略的性能。酸性/碱性双方法配置能够在28分钟内对人血清中14种化学类别中的394种新出现的污染物进行定量分析，具有良好的线性，90%的分析物的定量限不超过0.20 ng/mL，峰面积rsd通常低于10%。HILIC/RP平行柱组合可在20分钟内同时测定27种降糖药，其logp范围为- 6.8至5.9，与标准方法相比，分析时间缩短了50%，在加标食品样品中具有良好的精密度和回收率。总体而言，共享自动进样器并行LC-MS /MS策略为复杂矩阵中的高通量多分析物定量提供了灵活高效的平台。

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引用次数: 0

Untargeted metabolomics and in-house database analysis reveal differences between elephantopus scaber L. and elephantopus tomentosus L. 非靶向代谢组学和内部数据库分析揭示了非洲象和毛象之间的差异。

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2026-05-10 Epub Date: 2026-03-06 DOI: 10.1016/j.chroma.2026.466881

Chang-Sheng Gao , Zhi-Kang Duan , Mei-Ya Lian, Run-Ze Yu, Ming Bai, Shu-Hui Dong, Shao-Jiang Song

In China, Elephantopus scaber L. and Elephantopus tomentosus L., two traditional Chinese medicinal herbs commonly known as "Ku-di-dan", are widely used. Moreover, they have demonstrated anti-hepatoma effects and hepatoprotective properties in experimental studies. Nonetheless, according to existing literature, E. scaber and E. tomentosus encompass compounds with similar but notably different chemical structures. Therefore, investigating the differences in secondary metabolites between E. scaber and E. tomentosus and elucidating their distinct anti-hepatocellular carcinoma activities is of great importance. This study employed an integrated approach combining untargeted metabolomics with bioactivity assays to effectively differentiate between the congeneric plant species E. scaber and E. tomentosus. To improve the accuracy of characterizing and identifying key metabolites, an in-house database and data screening methods were employed. The research findings revealed that thirty major secondary metabolites were detected in E. tomentosus and E. scaber extracts through untargeted metabolomics and data screening. Subsequently, eight significant differential metabolites were identified through multivariate statistical analyses. Thereafter, twelve compounds were isolated from these two plants and evaluated for their anti-hepatocellular activity, revealing that compounds 5—8 exhibited significant inhibitory effects on HepG2 and Hep3B cells. Consistent results were also observed in the tests conducted on the crude extracts of both E. scaber and E. tomentosus. This study demonstrates that E. scaber and E. tomentosus exhibit distinct secondary metabolite profiles and differential anti-hepatocellular carcinoma activities.

在中国，被广泛使用的两种传统中草药，俗称“苦地丹”，即是结痂象（Elephantopus scaber L.）和绒毛象（Elephantopus tomentosus L.）。此外，在实验研究中，它们已显示出抗肝癌和保护肝脏的作用。尽管如此，根据现有文献，E. scaber和E. tomentosus包含的化合物具有相似但明显不同的化学结构。因此，研究结痂荚膜荚膜荚膜荚膜荚膜菌和结痂荚膜荚膜荚膜菌次生代谢产物的差异，阐明其不同的抗肝癌活性具有重要意义。本研究采用非靶向代谢组学与生物活性检测相结合的综合方法，对属属植物剑麻和毛毛剑麻进行有效区分。为了提高表征和鉴定关键代谢物的准确性，采用了内部数据库和数据筛选方法。研究结果表明，通过非靶向代谢组学和数据筛选，在毛毛莲和剑麻提取物中检测到30种主要的次生代谢物。随后，通过多变量统计分析，确定了8种显著差异代谢物。随后，从这两种植物中分离得到12个化合物，并对其抗肝细胞活性进行了评价，发现化合物5 ~ 8对HepG2和Hep3B细胞有明显的抑制作用。在对剑麻和毛毛剑麻粗提取物进行的试验中也观察到一致的结果。本研究表明，结痂大肠杆菌和绒毛大肠杆菌具有不同的次级代谢物谱和不同的抗肝细胞癌活性。

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引用次数: 0

Computer vision–based augmented visualisation for coffee origins identitation using comprehensive two-dimensional gas chromatography 基于计算机视觉的增强可视化的咖啡原产地鉴定使用全面的二维气相色谱。

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2026-05-10 Epub Date: 2026-02-21 DOI: 10.1016/j.chroma.2026.466836

Giorgio Felizzato , Eloisa Bagnulo , Giulia Tapparo , Giorgia Botta , Qingping Tao , Stephen E. Reichenbach , Chiara Cordero , Luciano Navarini , Erica Liberto , Andrea Caratti

Coffee is a highly complex and variable matrix, with volatile profiles shaped by multiple factors including botanical origin, climatic and soil conditions, post-harvest treatments, and roasting parameters. This variability generates complex chemical patterns, encompassing hundreds of volatile compounds from diverse chemical classes including pyrazines, furans, aldehydes, ketones, and terpenes. The resulting chemical dimensionality poses significant analytical challenges, making the accurate identification of characteristic compounds and reliable discrimination of coffee origins particularly difficult.

In this study, we applied comprehensive two-dimensional gas chromatography (GC×GC) coupled with computer vision (CV) to address these challenges. The workflow begins with untargeted fingerprinting, capturing all detectable compounds in a feature template. Multiple sample chromatograms are then combined into composite class images, representing the typical chemical features of each origin while minimising individual variability, which enables rapid pairwise comparison of different origins.

CV-based pairwise comparisons highlight differential peaks, which are integrated into a targeted template for subsequent peak extraction. Multivariate analyses then identify the key discriminant compounds driving origin differentiation. Post-processing strategies, such as ion-specific intensity mapping, further enhance interpretability, enabling visualisation of compositional differences across key chemical families. Overall, this GC×GC–CV workflow provides a robust, rapid, and visually intuitive platform for comprehensive chemical characterisation and origin classification of coffee, integrating untargeted and targeted analyses in a single framework.

咖啡是一种高度复杂和多变的基质，其挥发性特征受到多种因素的影响，包括植物来源、气候和土壤条件、收获后处理和烘焙参数。这种可变性产生了复杂的化学模式，包括来自不同化学类别的数百种挥发性化合物，包括吡嗪、呋喃、醛、酮和萜烯。由此产生的化学维度带来了重大的分析挑战，使得准确识别特征化合物和可靠地区分咖啡原产地尤其困难。在这项研究中，我们应用了全面的二维气相色谱（GC×GC）结合计算机视觉（CV）来解决这些挑战。工作流程从非目标指纹识别开始，在特征模板中捕获所有可检测的化合物。然后将多个样品色谱图组合成复合类图像，代表每个来源的典型化学特征，同时最大限度地减少个体差异，从而实现不同来源的快速两两比较。基于cv的两两比较突出了差异峰，并将其集成到目标模板中，用于后续的峰提取。然后通过多变量分析确定驱动起源分化的关键判别化合物。后处理策略，如离子特异性强度映射，进一步提高了可解释性，使关键化学家族的成分差异可视化。总的来说，这个GC×GC-CV工作流程提供了一个强大、快速、视觉直观的平台，用于全面的咖啡化学特征和原产地分类，将非目标和目标分析集成在一个框架中。

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引用次数: 0

Research advances in capillary gel electrophoresis for detecting biomacromolecules 毛细管凝胶电泳检测生物大分子的研究进展。

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2026-05-10 Epub Date: 2026-02-28 DOI: 10.1016/j.chroma.2026.466850

Wen-Jing Liu , Ying Zhang , Qiu-Yang Li , Rui-Ting Li , Long Zhao , Tharcisse Gatera , Qu-Huan Ma , Jun-Li Yang , Xiao-Feng Shi

Capillary gel electrophoresis (CGE) has been employed for the separation of biomacromolecules for over thirty years. Thanks to advances in gel materials and the ongoing development of electrophoresis instruments, the CGE method has now become one of the recognized gold standards for routine separation and analysis of biomacromolecules. This is due to its superior separation capabilities and the high robustness and reliability of its results. This paper reviews the research progress and applications of CGE in the separation and analysis of biomacromolecules, including proteins, nucleic acids, and polysaccharides, between 2015 and 2025, and offers a prospect on the future development of this technology.

毛细管凝胶电泳（CGE）用于生物大分子的分离已有三十多年的历史。由于凝胶材料的进步和电泳仪器的不断发展，CGE方法现已成为生物大分子常规分离和分析的公认金标准之一。这是由于其优越的分离能力和高鲁棒性和可靠性的结果。本文综述了2015 - 2025年CGE在生物大分子（蛋白质、核酸、多糖）分离分析方面的研究进展及应用，并对该技术的未来发展进行了展望。

引用次数: 0

A local predictive modelling approach for enhanced separation of critical volatile compounds with flow-modulated comprehensive two-dimensional gas chromatography 流动调制综合二维气相色谱法增强关键挥发性化合物分离的局部预测建模方法

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2026-05-10 Epub Date: 2026-03-07 DOI: 10.1016/j.chroma.2026.466886

Olga Vyviurska , Rocio Vidal Pellegrino , František Dugovič , Dominika Sklenárová , Ivan Špánik

In recent years, the application of flow-modulated comprehensive two-dimensional gas chromatography (FM-GC × GC) has significantly increased, particularly for profiling complex food volatilomes. However, the full potential of this technique is often hindered by the complexity of instrumental optimisation, which is critical for achieving high-resolution separation across a wide variety of analytes in diverse samples. This work addresses this challenge by developing a predictive strategy to optimise FM-GC × GC conditions for the separation of a wide variety of volatile compounds. The efficiency of a local model based on peak parameters was tested across four different column setups, monitoring its correlation to the separation of 22 critical coeluting pairs. Using a Doehlert experimental design and a General Linear Model (GLM) approach, robust predictive models (R² > 0.80) were established and validated. Although the predictive models are confined to the tested experimental space, the underlying strategy and observed general behaviours provide a transferable framework for other setups. The use of a multiresponse optimisation strategy coupled to a global resolution metric, the Fraction of Resolved Peaks (FRP), successfully improved the separation of coelutions, particularly for specific column configurations. The effectiveness of this workflow was ultimately demonstrated by its successful application to the complex volatilomes of wine, honey, cascara coffee tea, and masala tea.

近年来，流量调制综合二维气相色谱法（FM-GC × GC）在分析复杂食品挥发物方面的应用显著增加。然而，该技术的全部潜力往往受到仪器优化的复杂性的阻碍，这对于在不同样品中实现各种分析物的高分辨率分离至关重要。这项工作通过开发一种预测策略来优化各种挥发性化合物分离的FM-GC × GC条件，从而解决了这一挑战。基于峰值参数的局部模型的效率在四种不同的柱设置中进行了测试，并监测了其与22个关键coeloling对分离的相关性。采用Doehlert实验设计和一般线性模型（GLM）方法，建立并验证了鲁棒预测模型（R²> 0.80）。虽然预测模型仅限于测试的实验空间，但潜在策略和观察到的一般行为为其他设置提供了可转移的框架。使用多响应优化策略与全局分辨率度量相结合，即分解峰的分数（FRP），成功地提高了分离度，特别是对于特定的柱配置。该工作流程的有效性最终通过其成功应用于葡萄酒，蜂蜜，卡斯卡拉咖啡茶和马沙拉茶的复杂挥发物而得到证明。

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引用次数: 0

Archaea synthesize heterochiral phospholipid membranes as revealed by chiral analysis of archaeols 古菌的手性分析表明，古菌可合成杂手性磷脂膜。

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2026-05-10 Epub Date: 2026-03-01 DOI: 10.1016/j.chroma.2026.466853

Walter Hofmann , Andrea Palyzová , Jan Jansa , Nika Pende , Simon K.-M.R. Rittmann , Tomáš Řezanka

This study comprehensively characterizes structural diversity of archaeol lipids in selected archaeal genera, integrating available genomic information with advanced lipidomic and stereochemical analyzes. Study of genomes from six archaeal genera revealed the presence of key enzymes involved in glycerophosphate biosynthesis, namely glycerol-1-phosphate dehydrogenase and glycerol-3-phosphate dehydrogenase. Their coexistence in some of the studied strains suggests the ability of these organisms to synthesize both enantiomeric forms of glycerol phosphates. Shotgun lipidomic profiling confirmed the presence of saturated and unsaturated archaeols, including extended forms (C20–C25), hydroxyarchaeols, and tetraether lipids, especially in the species Haloferax volcanii, Methanopyrus kandleri, and Sulfolobus acidocaldarius. Using on-line 2D LC-MS/MS, a specific molecular species of archaeol (20:3–25:4-AR) with seven double bonds was identified in H. volcanii, while bis-extended archaeol (C25–C25) was not detected. Chiral HPLC of a commercial archaeol standard resolved four isomers, with the (R)-2,3-di-O-phytanyl-sn-glycerol stereoisomer being the most abundant (> 80 %). In four of our archaeal strains a minor S enantiomer was present at concentrations of 6.8–13.9 % relative to the main R isomer, and its presence coincided with the presence of both glycerol phosphate dehydrogenases in the respective genomes. The distribution of these isomers across the studied strains supports the coexistence of both R- and S- enantiomers of archaeols in some, but not all, archaeal lineages. These findings highlight the stereochemical and structural complexity of archaeal membrane lipids and provide new insights into their biosynthetic diversity.

本研究综合了已有的基因组信息和先进的脂质组学和立体化学分析，全面表征了选定古菌属中古醇脂质的结构多样性。对6个古细菌属基因组的研究发现，存在参与甘油磷酸生物合成的关键酶，即甘油-1-磷酸脱氢酶和甘油-3-磷酸脱氢酶。它们在某些研究菌株中的共存表明这些生物有能力合成两种对映体形式的甘油磷酸。散弹枪脂质组学分析证实了饱和古醇和不饱和古醇的存在，包括扩展形式（C20-C25），羟基古醇和四醚类脂质，特别是在Haloferax volcanii， Methanopyrus kandleri和Sulfolobus acidocalarius物种中。利用在线二维LC-MS/MS，在H. volcanii中鉴定出具有7个双键的古酚（20:3-25:4-AR），而未检测到双延伸古酚（C25-C25）。手性高效液相色谱法测定了4种异构体的含量，其中(R)-2,3-二- o -植烷- n-甘油立体异构体含量最多（约80%）。在我们的四株古细菌菌株中，相对于主要的R异构体，存在一个次要的S对映体，其浓度为6.8- 13.9%，其存在与各自基因组中磷酸甘油脱氢酶的存在一致。这些异构体在研究菌株中的分布支持了古菌R-和S-对映体在一些（但不是全部）古菌谱系中共存。这些发现突出了古细菌膜脂的立体化学和结构复杂性，并为其生物合成多样性提供了新的见解。

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引用次数: 0

Chiral derivatization reagents for enantioselective LC-MS/MS analysis of amino acids with analyte-specific fragmentation 用于氨基酸对映选择性LC-MS/MS分析的手性衍生化试剂

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2026-05-10 Epub Date: 2026-02-28 DOI: 10.1016/j.chroma.2026.466851

Tatsuya Sakamoto, Kana Ishikura, Mayu Onozato, Takeshi Fukushima

Accurate enantioselective analysis of amino acids by liquid chromatography-tandem mass spectrometry (LC–MS/MS) remains challenging, as existing derivatization strategies often compromise either chromatographic resolution or structural discrimination in tandem mass spectrometry. In this study, we developed novel chiral derivatization reagents, (R)- and (S)-Oqic, based on a 1,3-oxazinoquinoline-4-one scaffold, for the simultaneous determination of amino acid enantiomers via LC–MS/MS. The reagents reacted rapidly with amino acids under mild basic conditions to form their chiral derivatives, enabling the simultaneous separation of 37 amino acids (18 pairs of amino acid enantiomers and Gly) on a conventional ODS column within 16 min. The resulting derivatives exhibited unique fragmentation patterns, yielding characteristic fragment ions at m/z 190 and [M + H − 171], with intensity ratios dependent on the tagged amino acid, thereby facilitating reliable analyte discrimination. The method was validated and subsequently applied to the analysis of commercially available fermented dairy products, revealing the presence of d-Ala, d-Ser, d-Asp, d-Glu, and d-Arg in yogurt and a probiotic beverage. The detection of sweet-tasting d-amino acids (d-Ala, d-Ser, and d-Arg) suggests their potential contribution to the sensory properties of fermented foods. Overall, the developed Oqic-based method provides a powerful tool for elucidating bacterial metabolism and food flavor profiles.

液相色谱-串联质谱（LC-MS /MS）对氨基酸进行精确的对映选择性分析仍然具有挑战性，因为现有的衍生化策略通常会损害串联质谱的色谱分辨率或结构辨别。在这项研究中，我们开发了新的手性衍生试剂(R)-和(S)- oqic，基于1,3-恶嗪喹啉-4- 1支架，用于通过LC-MS /MS同时测定氨基酸对映体。该试剂与氨基酸在温和的碱性条件下快速反应形成手性衍生物，在常规ODS色谱柱上可在16 min内同时分离37种氨基酸（18对氨基酸对映体和Gly）。所得到的衍生物显示出独特的碎片模式，在m/z 190和[m + H−171]处产生特征碎片离子，其强度比取决于所标记的氨基酸，从而促进了可靠的分析物鉴别。该方法经过验证并随后应用于市售发酵乳制品的分析，揭示了酸奶和益生菌饮料中d-Ala， d-Ser, d-Asp， d-Glu和d-Arg的存在。甜味d-氨基酸（d-Ala， d-Ser和d-Arg）的检测表明它们对发酵食品的感官特性有潜在的贡献。总之，开发的基于oqic的方法为阐明细菌代谢和食物风味谱提供了一个强大的工具。

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引用次数: 0

Metal-organic framework MIL-101(Cr) functionalized β-cyclodextrin-modified magnetic multi-walled carbon nanotubes for efficient extraction of amphenicol antibiotics 金属有机骨架MIL-101（Cr）功能化β-环糊精修饰磁性多壁碳纳米管高效提取抗生素

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2026-05-10 Epub Date: 2026-03-06 DOI: 10.1016/j.chroma.2026.466882

Lin Lv , Hongmei Liu , Tao Song , Yan Zhao

Given the extensive use of amphenicol antibiotics and their potential adverse effects on human health, the development of simple and highly sensitive detection methods is essential to ensure food safety. In this work, a novel and highly efficient magnetic sorbent based on β-cyclodextrin-modified magnetic multi-walled carbon nanotubes functionalized with MIL-101(Cr) (Fe₃O₄@β-CD@MWCNTs@MIL-101(Cr)) was developed and combined with ultra-high-performance liquid chromatography-mass spectrometry (UHPLC-MS/MS) to achieve highly sensitive detection of three amphenicol antibiotics (chloramphenicol, thiamphenicol, and florfenicol) in honey samples. The key factors influencing extraction efficiency in the magnetic solid-phase extraction process were identified using the Plackett-Burman experimental design, whereas the optimal experimental conditions were determined through Box-Behnken design-based response surface methodology optimization. Under these optimized conditions, favorable linear relationships for amphenicol antibiotics were observed within the concentration range of 0.5–250 ng mL⁻¹ (R² ≥ 0.9951). The method exhibited detection limits of 0.04–0.07 μg kg⁻¹. Recovery rates ranged from 83.2% to 97.9%, with intra-day and inter-day precisions both below 7.2%. This method provides an efficient tool for monitoring amphenicol antibiotics in complex matrices.

鉴于氨霉素抗生素的广泛使用及其对人类健康的潜在不利影响，开发简单和高度敏感的检测方法对于确保食品安全至关重要。本研究基于MIL-101（Cr）功能化的β-环糊精修饰磁性多壁碳纳米管（Fe3O4@β-CD@MWCNTs@MIL-101(Cr)）制备了一种新型高效磁性吸附剂，并结合超高效液相色谱-质谱联用（UHPLC-MS/MS），实现了蜂蜜样品中氯霉素、硫霉素和氟苯尼考三种抗生素的高灵敏度检测。采用Plackett-Burman实验设计确定了磁固相萃取过程中影响萃取效率的关键因素，并采用基于Box-Behnken设计的响应面法优化确定了最佳实验条件。在此优化条件下，在0.5 ~ 250 ng mL−1的浓度范围内，抗生素用量呈良好的线性关系（R2≥0.9951）。方法检出限为0.04 ~ 0.07 μg kg−1。回收率为83.2% ~ 97.9%，日内、日间精密度均低于7.2%。该方法为复杂基质中抗生素的监测提供了一种有效的工具。

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引用次数: 0

Revisiting the definition and measurement of total accessible and hold-up volumes in liquid chromatography: Current understanding and advances 重新审视液相色谱中总可接近体积和持有体积的定义和测量：当前的理解和进展。

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2026-05-10 Epub Date: 2026-02-27 DOI: 10.1016/j.chroma.2026.466849

Judith Mollen , Gert Desmet , Deirdre Cabooter

The accurate determination of the retention factor, and particularly, the determination of the mobile phase volume that is needed for its computation, remains a fundamental, yet highly-debated topic in liquid chromatography. Two main approaches currently co-exist in literature: i) one based on the total accessible volume (= the total column volume accessible for solvent molecules after bonded phase coating) and ii) one based on the mobile phase volume that is accessible to unretained analytes (the hold-up volume). This review provides a clear graphical definition for both volumes and subsequently critically examines their use in current literature and reviews their methods of determination, emphasizing the need for careful experimental practice and standardized, universally accepted definitions. By comparing traditional experimental methods with findings from molecular dynamics simulations and Monte Carlo method studies, this review furthermore aims to clarify ambiguities and recommend best practices for future research. In addition, a comprehensive table linking the different names, symbols and definitions that have been used throughout literature to denote the different mobile phase volumes is provided, to help researchers navigate literature more easily.

保留因子的准确测定，特别是计算其所需的流动相体积的测定，仍然是液相色谱中一个基本的，但又备受争议的话题。目前文献中存在两种主要方法：i)一种基于总可接触体积（=键合相涂层后溶剂分子可接触的总柱体积），ii)一种基于未保留分析物可接触的流动相体积（保持体积）。这篇综述为这两卷提供了一个清晰的图形定义，随后批判性地检查了它们在当前文献中的使用，并回顾了它们的测定方法，强调需要仔细的实验实践和标准化，普遍接受的定义。通过比较传统的实验方法与分子动力学模拟和蒙特卡罗方法的研究结果，进一步澄清歧义，并为未来的研究提供最佳实践建议。此外，还提供了一个综合表，链接了整个文献中用于表示不同流动相卷的不同名称、符号和定义，以帮助研究人员更容易地浏览文献。

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引用次数: 0

Integrating natural deep eutectic solvents and ionic liquids as green mobile phase additives for enhanced selenium speciation analysis in food samples by liquid chromatography-atomic fluorescence spectrometry 结合天然深共晶溶剂和离子液体作为绿色流动相添加剂，液相色谱-原子荧光光谱法增强食品样品中硒的形态分析。

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2026-05-10 Epub Date: 2026-02-28 DOI: 10.1016/j.chroma.2026.466844

María B. Botella , María N. Oviedo , Rodolfo G. Wuilloud

A study to evaluate the effects of natural deep eutectic solvent (NADES) and ionic liquids (ILs) on the separation of selenium (Se) species by reversed phase high performance liquid chromatography and detection by hydride generation atomic fluorescence spectrometry (RP-HPLC-HG-AFS) was performed in this work. The NADESs choline chloride:ethylene glycol and choline chloride:glycerol were applied as mobile phase additives for the separation of Se(IV), Se(VI), selenomethionine (SeMet) and Se-methylselenocysteine (SeMetSeCys). The effects of NADES composition, molar ratio, and concentration on chromatographic performance were systematically investigated, along with the influence of pH, buffer strength, and flow rate. The combined use of NADESs with the IL 1-hexyl-3-methylimidazolium chloride ([C₆mim]Cl) significantly enhanced the resolution of inorganic Se species. In addition, the effects of NADES and IL on the Se fluorescence signals obtained with the HG-AFS techniques were also studied using a multivariate technique for sensitivity optimization. The method achieved limits of detection of 1.59–2.78 µg L^-1, with relative standard deviations of 0.53–1.86 % for retention times and 1.23–1.72 % for peak areas. Finally, the proposed analytical method was successfully applied to Se speciation analysis in complex food samples, including nuts and Se-enriched garlic, yielding recoveries of 93.4–106 %.

本文研究了天然深共晶溶剂（NADES）和离子液体（ILs）对反相高效液相色谱法分离硒（Se）和氢化物发生原子荧光光谱法（RP-HPLC-HG-AFS）检测的影响。采用NADESs氯化胆碱：乙二醇和氯化胆碱：甘油作为流动相添加剂分别分离硒（IV）、硒（VI）、硒代蛋氨酸（SeMet）和硒甲基硒半胱氨酸（SeMetSeCys）。系统地研究了NADES的组成、摩尔比和浓度对色谱性能的影响，以及pH、缓冲液强度和流速的影响。NADESs与IL - 1-己基-3-甲基咪唑氯（[C6mim]Cl）的联合使用显著提高了无机硒的分辨率。此外，还利用多元灵敏度优化技术研究了NADES和IL对HG-AFS技术获得的Se荧光信号的影响。方法的检出限为1.59 ~ 2.78µg L-1，保留时间的相对标准偏差为0.53 ~ 1.86%，峰面积的相对标准偏差为1.23 ~ 1.72%。最后，该方法成功地应用于坚果和富硒大蒜等复杂食品样品的硒形态分析，回收率为93.4 ~ 106%。

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引用次数: 0