Journal of Chromatography A最新文献_第5页

Hybridization liquid chromatography-mass spectrometry for quantitative bioanalysis of oligonucleotides: The upcoming paradigm shift 杂交液相色谱-质谱法定量生物分析寡核苷酸：即将到来的范式转变。

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-11-26 DOI: 10.1016/j.chroma.2025.466575

Long Yuan

Therapeutic oligonucleotides, which are short, synthetic, single- or double-stranded oligonucleotides, have been rapidly growing in drug discovery and development as a new class of modality. Major types of approved oligonucleotide therapeutics include antisense oligonucleotide (ASO), small interfering RNA (siRNA), and aptamers. Various bioanalytical techniques, including hybridization immunoassay, liquid chromatography-mass spectrometry (LC-MS), liquid chromatography (LC)-fluorescence, and quantitative polymerase chain reaction (qPCR), have been used for the quantitative bioanalysis of oligonucleotides, but all have their own drawbacks on either specificity or sensitivity. Recently, hybridization LC-MS has been rapidly growing as a new bioanalytical technique for the quantification of oligonucleotides. This technique offers a unique advantage of achieving both high specificity and good sensitivity by integrating hybridization extraction with LC-MS. With the continued growing demands for sensitive, specific, accurate, and reliable bioanalytical methods, hybridization LC-MS has great potential to be more widely applied and to become the primary method for oligonucleotide bioanalysis. In this review, this technique will be reviewed and compared with the traditional techniques. The strategies and challenges of hybridization LC-MS for the quantification of oligonucleotides, including both single-stranded oligonucleotides (e.g., ASO) and double-stranded oligonucleotides (e.g., siRNA), will be discussed. Considerations, novel applications (e.g., microsampling, microflow LC), and future opportunities of this new technique will also be discussed.

治疗性寡核苷酸是一种短链、合成的单链或双链寡核苷酸，作为一类新的模式在药物发现和开发中得到了迅速发展。主要类型的批准寡核苷酸治疗包括反义寡核苷酸（ASO），小干扰RNA （siRNA）和适配体。各种生物分析技术，包括杂交免疫分析法、液相色谱-质谱法（LC- ms）、液相色谱-荧光法和定量聚合酶链反应（qPCR），已被用于寡核苷酸的定量生物分析，但它们在特异性或敏感性上都有各自的缺点。近年来，杂交LC-MS作为一种新的生物分析技术迅速发展起来。该技术将杂交提取与LC-MS相结合，具有高特异性和高灵敏度的独特优势。随着人们对灵敏、特异、准确、可靠的生物分析方法的要求不断提高，杂交LC-MS具有更广泛的应用前景，有望成为寡核苷酸生物分析的主要方法。本文将对该技术进行综述，并与传统技术进行比较。将讨论杂交LC-MS用于定量寡核苷酸的策略和挑战，包括单链寡核苷酸（如ASO）和双链寡核苷酸（如siRNA）。还将讨论该新技术的考虑因素、新应用（如微采样、微流LC）和未来机会。

{"title":"Hybridization liquid chromatography-mass spectrometry for quantitative bioanalysis of oligonucleotides: The upcoming paradigm shift","authors":"Long Yuan","doi":"10.1016/j.chroma.2025.466575","DOIUrl":"10.1016/j.chroma.2025.466575","url":null,"abstract":"<div><div>Therapeutic oligonucleotides, which are short, synthetic, single- or double-stranded oligonucleotides, have been rapidly growing in drug discovery and development as a new class of modality. Major types of approved oligonucleotide therapeutics include antisense oligonucleotide (ASO), small interfering RNA (siRNA), and aptamers. Various bioanalytical techniques, including hybridization immunoassay, liquid chromatography-mass spectrometry (LC-MS), liquid chromatography (LC)-fluorescence, and quantitative polymerase chain reaction (qPCR), have been used for the quantitative bioanalysis of oligonucleotides, but all have their own drawbacks on either specificity or sensitivity. Recently, hybridization LC-MS has been rapidly growing as a new bioanalytical technique for the quantification of oligonucleotides. This technique offers a unique advantage of achieving both high specificity and good sensitivity by integrating hybridization extraction with LC-MS. With the continued growing demands for sensitive, specific, accurate, and reliable bioanalytical methods, hybridization LC-MS has great potential to be more widely applied and to become the primary method for oligonucleotide bioanalysis. In this review, this technique will be reviewed and compared with the traditional techniques. The strategies and challenges of hybridization LC-MS for the quantification of oligonucleotides, including both single-stranded oligonucleotides (e.g., ASO) and double-stranded oligonucleotides (e.g., siRNA), will be discussed. Considerations, novel applications (e.g., microsampling, microflow LC), and future opportunities of this new technique will also be discussed.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1766 ","pages":"Article 466575"},"PeriodicalIF":4.0,"publicationDate":"2025-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145676138","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

Shilajit-analytical study to understand the phyto complex present in shilajit raw material, extract and resin by using hyphenated techniques 利用联用技术对石竹原料、提取物和树脂中存在的植物复合物进行了分析研究。

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-11-25 DOI: 10.1016/j.chroma.2025.466570

Harsimran Kaur Kohli , Vanita Somasekhar , M. Devendra Reddy , N.S. Prakash

Shilajit is an astonishing sticky tar-like resinous substance obtained from the rocks of mountains at higher altitudes. In Ayurveda, shilajit is known for its rejuvenating and adaptogenic properties, mainly due to the presence of bioactive markers like fulvic acid, hippuric acid, urolithin A. The current study aimed to develop high performance liquid chromatography (HPLC) method for quantification of these markers. Both qualitative and quantitative analysis was performed on shilajit samples. The chromatographic separation was achieved on YMC-Triart C18 column using 0.1 % orthophosphoric acid (OPA) in water as mobile phase A and acetonitrile as mobile phase B. The flow rate was maintained at 1mL/min. Furthermore, high performance thin-layer chromatography (HPTLC) and liquid chromatography-mass spectrometry (LC-MS) methods were developed to identify and confirm the mass of bioactive markers. Gravimetric analysis was performed for the quantification of total fulvic acid content present in shilajit sample. Shilajit is known to be rich in wide range of minerals and trace elements. To investigate that, 14 elements were quantified using inductively coupled plasma mass spectrometry (ICP-MS). The minerals present in shilajit helps in its vitality and may improve nutrient absorption. The developed method resulted in good resolution of targeted compounds and will help in routine quality control and biomarker analysis. The research highlights the chemical complexity of shilajit, emphasizing its dual pharmacological significance through both organic phytochemicals and mineral content. The findings provide a foundation for reliable profiling and safety assessment, paving the way for future pharmaceutical applications of Shilajit.

Shilajit是一种惊人的粘稠焦油状树脂物质，从高海拔山区的岩石中提取。在阿育吠陀中，shilajit因其具有恢复活力和适应性的特性而闻名，主要是由于其存在的生物活性标记物，如黄腐酸、马尿酸、尿素a。目前的研究旨在建立高效液相色谱（HPLC）方法来定量这些标记物。对夏拉吉特样品进行了定性和定量分析。色谱柱为YMC-Triart C18，流动相为0.1%正磷酸（OPA），乙腈为流动相b，流速为1mL/min。此外，建立了高效薄层色谱（HPTLC）和液相色谱-质谱（LC-MS）方法来鉴定和确认生物活性标记物的质量。用重量分析法定量测定了石笋吉特样品中总黄腐酸的含量。希拉吉特富含多种矿物质和微量元素。为此，采用电感耦合等离子体质谱（ICP-MS）对14种元素进行了定量分析。shilajit中的矿物质有助于其活力，并可能改善营养吸收。该方法对目标化合物具有良好的分辨率，有助于常规的质量控制和生物标志物分析。该研究强调了石拉吉特的化学复杂性，强调其通过有机植物化学物质和矿物质含量的双重药理意义。这些发现为可靠的基因图谱和安全性评估奠定了基础，为Shilajit未来的制药应用铺平了道路。

{"title":"Shilajit-analytical study to understand the phyto complex present in shilajit raw material, extract and resin by using hyphenated techniques","authors":"Harsimran Kaur Kohli , Vanita Somasekhar , M. Devendra Reddy , N.S. Prakash","doi":"10.1016/j.chroma.2025.466570","DOIUrl":"10.1016/j.chroma.2025.466570","url":null,"abstract":"<div><div>Shilajit is an astonishing sticky tar-like resinous substance obtained from the rocks of mountains at higher altitudes. In Ayurveda, shilajit is known for its rejuvenating and adaptogenic properties, mainly due to the presence of bioactive markers like fulvic acid, hippuric acid, urolithin A. The current study aimed to develop high performance liquid chromatography (HPLC) method for quantification of these markers. Both qualitative and quantitative analysis was performed on shilajit samples. The chromatographic separation was achieved on YMC-Triart C18 column using 0.1 % orthophosphoric acid (OPA) in water as mobile phase A and acetonitrile as mobile phase B. The flow rate was maintained at 1mL/min. Furthermore, high performance thin-layer chromatography (HPTLC) and liquid chromatography-mass spectrometry (LC-MS) methods were developed to identify and confirm the mass of bioactive markers. Gravimetric analysis was performed for the quantification of total fulvic acid content present in shilajit sample. Shilajit is known to be rich in wide range of minerals and trace elements. To investigate that, 14 elements were quantified using inductively coupled plasma mass spectrometry (ICP-MS). The minerals present in shilajit helps in its vitality and may improve nutrient absorption. The developed method resulted in good resolution of targeted compounds and will help in routine quality control and biomarker analysis. The research highlights the chemical complexity of shilajit, emphasizing its dual pharmacological significance through both organic phytochemicals and mineral content. The findings provide a foundation for reliable profiling and safety assessment, paving the way for future pharmaceutical applications of Shilajit.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1766 ","pages":"Article 466570"},"PeriodicalIF":4.0,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145659825","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

Disaccharide/UiO-66(Zr) composites for selective dye adsorption: synergistic mechanisms 双糖/UiO-66（Zr）复合材料选择性染料吸附：协同机理

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-11-25 DOI: 10.1016/j.chroma.2025.466568

Jun Chen , Wenxiu Cao , Shuang Xu , Li Liu , Hui Tang , Ningyu Hu , Wei Zhang

The global water crisis demands the use of efficient adsorbents to remove carcinogenic synthetic dyes from industrial wastewater. This study developed composites of disaccharides (lactose, maltose, sucrose) with UiO-66(Zr) and systematically evaluated their adsorption performance towards both cationic (methylene blue, MB; malachite green, MG; rhodamine B, RhB) and anionic (methyl orange, MO; and Congo red, CR) dyes. Comprehensive characterization, including PXRD, FT-IR, BET, TGA, XPS and zeta potential, confirmed the successful formation of the disaccharide/UiO-66(Zr) composites. Compared to the removal of cationic dyes, the disaccharide/UiO-66 composites showed superior performance in adsorbing anionic dyes. Sucrose/UiO-66 showed particularly outstanding results, exhibiting adsorption capacities of 54, 56, 37, 154 and 287 mg/g for MB, MG, RhB, MO and CR, respectively. This is likely because lactose and maltose are reducing disaccharides, while sucrose is non-reducing. The reducing property governs the adsorption capacity for anionic dyes. Furthermore, based on adsorption kinetics data, the dye adsorption process of these materials follows the pseudo-second-order kinetic model, with adsorption mechanisms involving electrostatic interactions, π-π stacking, size-selective, and dual-mode regenerability. Thus, disaccharide/UiO-66(Zr) exhibits immense application potential in environmental pollutant removal and also provides a valuable reference for the preparation and application of other MOF composites.

全球水危机要求使用高效吸附剂来去除工业废水中的致癌合成染料。本研究开发了二糖（乳糖、麦芽糖、蔗糖）与uuo -66（Zr）的复合材料，并系统地评价了其对阳离子（亚甲基蓝，MB；孔孔石绿，MG；罗丹明B， RhB）和阴离子（甲基橙，MO；刚果红，CR）染料的吸附性能。综合表征，包括PXRD、FT-IR、BET、TGA、XPS和zeta电位，证实了双糖/UiO-66（Zr）复合材料的成功形成。与阳离子染料的去除效果相比，双糖/UiO-66复合材料对阴离子染料的吸附效果更好。蔗糖/UiO-66对MB、mg、RhB、MO和CR的吸附量分别为54、56、37、154和287 mg/g。这可能是因为乳糖和麦芽糖是还原双糖，而蔗糖是不还原的。还原性决定了阴离子染料的吸附能力。此外，基于吸附动力学数据，这些材料的染料吸附过程遵循伪二级动力学模型，其吸附机制包括静电相互作用、π-π堆积、尺寸选择性和双模式再生。因此，双糖/UiO-66（Zr）在环境污染物去除方面具有巨大的应用潜力，也为其他MOF复合材料的制备和应用提供了有价值的参考。

{"title":"Disaccharide/UiO-66(Zr) composites for selective dye adsorption: synergistic mechanisms","authors":"Jun Chen , Wenxiu Cao , Shuang Xu , Li Liu , Hui Tang , Ningyu Hu , Wei Zhang","doi":"10.1016/j.chroma.2025.466568","DOIUrl":"10.1016/j.chroma.2025.466568","url":null,"abstract":"<div><div>The global water crisis demands the use of efficient adsorbents to remove carcinogenic synthetic dyes from industrial wastewater. This study developed composites of disaccharides (lactose, maltose, sucrose) with UiO-66(Zr) and systematically evaluated their adsorption performance towards both cationic (methylene blue, MB; malachite green, MG; rhodamine B, RhB) and anionic (methyl orange, MO; and Congo red, CR) dyes. Comprehensive characterization, including PXRD, FT-IR, BET, TGA, XPS and zeta potential, confirmed the successful formation of the disaccharide/UiO-66(Zr) composites. Compared to the removal of cationic dyes, the disaccharide/UiO-66 composites showed superior performance in adsorbing anionic dyes. Sucrose/UiO-66 showed particularly outstanding results, exhibiting adsorption capacities of 54, 56, 37, 154 and 287 mg/g for MB, MG, RhB, MO and CR, respectively. This is likely because lactose and maltose are reducing disaccharides, while sucrose is non-reducing. The reducing property governs the adsorption capacity for anionic dyes. Furthermore, based on adsorption kinetics data, the dye adsorption process of these materials follows the pseudo-second-order kinetic model, with adsorption mechanisms involving electrostatic interactions, π-π stacking, size-selective, and dual-mode regenerability. Thus, disaccharide/UiO-66(Zr) exhibits immense application potential in environmental pollutant removal and also provides a valuable reference for the preparation and application of other MOF composites.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1765 ","pages":"Article 466568"},"PeriodicalIF":4.0,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145620979","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

Surface engineering of cell membrane biomimetic nanocomposites for enhanced drug lead discovery and evaluation 细胞膜仿生纳米复合材料的表面工程，增强药物先导物的发现和评价

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-11-25 DOI: 10.1016/j.chroma.2025.466571

Xu Jiang , Chenning Zhang , Yi Qin , Haiwei Wang , Yang Liu , Zhili Xiong , Longshan Zhao

Cell membrane-coated nanoparticles (CMNPs) have garnered significant attention in drug lead discovery due to their superior biochemical properties and distinctive ability to target biological interfaces. However, designing nanocarriers that can expand the applicability of these emerging nanomaterials while preserving the biological functionality of the cell membrane remains a significant challenge. Herein, nucleus pulposus (NP) cell membrane biomimetic FITC-loaded poly-amidoamine (PAMAM) modified NiFe₂O₄-GO (NFGPFPs-NP) nanocomposites were prepared by purposeful surface engineering to facilitate the efficient screening of drug leads from Yaobitong capsule (YBTC) that target membrane receptors. By employing NFGPFPs magnetic fluorescent nanoparticles as cell membrane carrier materials, the synthesized NFGPFPs-NP were endowed with capabilities for magnetic separation and fluorescence in-situ imaging, thereby realizing the rapid screening of active compounds and the visual evaluation of their pharmacological activities. Meanwhile, the validation including adsorption capacity, selectivity and stability of this biomimetic screening platform had been evaluated, and demonstrated satisfactory results. Notably, the platform exhibited a high adsorption capacity, reaching up to 12.88 mg·g^-1 for the target bioactive compounds. Eventually, eight potentially bioactive compounds were screened out from YBTC, and their proliferative activity on NP cells were subsequently validated by pharmacological experiments and cell morphology fluorescence imaging assays. In conclusion, this purposeful surface engineering endowed CMNPs with significantly enhanced versatility, thereby expanding the application scope of cell membrane biomimetic platform.

细胞膜包被纳米颗粒（CMNPs）由于其优越的生化特性和靶向生物界面的独特能力，在药物先导物的发现中引起了极大的关注。然而，设计纳米载体，既能扩大这些新兴纳米材料的适用性，又能保持细胞膜的生物功能，仍然是一个重大挑战。本文采用有目的的表面工程技术，制备了髓核（NP）细胞膜仿生fitc负载的聚胺胺（PAMAM）修饰的NiFe2O4-GO （nfgfpps -NP）纳米复合材料，以促进药痹通胶囊（YBTC）中靶向膜受体的药物先导物的高效筛选。利用NFGPFPs磁性荧光纳米颗粒作为细胞膜载体材料，合成的nfgfpps - np具有磁分离和荧光原位成像能力，从而实现了活性化合物的快速筛选和药理活性的可视化评价。同时，对该仿生筛选平台的吸附量、选择性和稳定性进行了验证，取得了满意的效果。值得注意的是，该平台对目标生物活性化合物的吸附量高达12.88 mg·g-1。最终，从YBTC中筛选出8个潜在的生物活性化合物，并通过药理实验和细胞形态荧光成像分析验证了它们对NP细胞的增殖活性。综上所述，这种有目的的表面工程赋予了CMNPs显著增强的通用性，从而扩大了细胞膜仿生平台的应用范围。

{"title":"Surface engineering of cell membrane biomimetic nanocomposites for enhanced drug lead discovery and evaluation","authors":"Xu Jiang , Chenning Zhang , Yi Qin , Haiwei Wang , Yang Liu , Zhili Xiong , Longshan Zhao","doi":"10.1016/j.chroma.2025.466571","DOIUrl":"10.1016/j.chroma.2025.466571","url":null,"abstract":"<div><div>Cell membrane-coated nanoparticles (CMNPs) have garnered significant attention in drug lead discovery due to their superior biochemical properties and distinctive ability to target biological interfaces. However, designing nanocarriers that can expand the applicability of these emerging nanomaterials while preserving the biological functionality of the cell membrane remains a significant challenge. Herein, nucleus pulposus (NP) cell membrane biomimetic FITC-loaded poly-amidoamine (PAMAM) modified NiFe<sub>2</sub>O<sub>4</sub>-GO (NFGPFPs-NP) nanocomposites were prepared by purposeful surface engineering to facilitate the efficient screening of drug leads from Yaobitong capsule (YBTC) that target membrane receptors. By employing NFGPFPs magnetic fluorescent nanoparticles as cell membrane carrier materials, the synthesized NFGPFPs-NP were endowed with capabilities for magnetic separation and fluorescence in-situ imaging, thereby realizing the rapid screening of active compounds and the visual evaluation of their pharmacological activities. Meanwhile, the validation including adsorption capacity, selectivity and stability of this biomimetic screening platform had been evaluated, and demonstrated satisfactory results. Notably, the platform exhibited a high adsorption capacity, reaching up to 12.88 mg·g<sup>-1</sup> for the target bioactive compounds. Eventually, eight potentially bioactive compounds were screened out from YBTC, and their proliferative activity on NP cells were subsequently validated by pharmacological experiments and cell morphology fluorescence imaging assays. In conclusion, this purposeful surface engineering endowed CMNPs with significantly enhanced versatility, thereby expanding the application scope of cell membrane biomimetic platform.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1765 ","pages":"Article 466571"},"PeriodicalIF":4.0,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145620982","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

Application of design of experiments to optimize the separation of lipid-related compounds in supercritical fluid chromatography-mass spectrometry 应用实验设计优化超临界流体色谱-质谱法分离脂类相关化合物

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-11-25 DOI: 10.1016/j.chroma.2025.466567

Muhamad Yahia Kazmouz , Mátyás Mayer , Attila Felinger

The response surface methodology (RSM) was used to optimize the separation conditions in a supercritical fluid chromatography-mass spectrometry (SFC/MS) analysis. This optimization was applied on data obtained from a central composite design (CCD). The target compounds were two fatty acids – arachidonic acid (AA) and docosahexaenoic acid (DHA) – along with various lipid classes, including phosphatidylcholines (PC), phosphatidylglycerols (PG), and phosphatidylethanolamines (PE). Three operational variables – gradient time, pressure, and modifier percentage – were investigated to evaluate their influence on the resolution between AA and DHA and the symmetry factor of their respective peaks.

The CCD included 3 levels for each variable within a range of gradient time between 1 and 2 min, the pressure between 125 and 225 bar, and the modifier percentage from 2 to 5 %.

The data of RSM for the critical pair of acids indicated that pressure and modifier percentage were the parameters that most influenced both the resolution and symmetry factor, whereas gradient time was not a significant variable.

The importance of this study lies in the capability of the response surface to show not only a linear interaction (relationship) but also a non-linear interaction between the significant variables – pressure and modifier percentage. Consequently, small changes in one of the significant variables affected the resolution AA/DHA and symmetry factors of their respective peaks significantly. This type of interaction between variables can only be elucidated by the design of experiments (DOE) approach employed in this work, which is not demonstrated in similar work of lipid anbalysis.

采用响应面法（RSM）对超临界液相色谱-质谱（SFC/MS）分离条件进行优化。该优化应用于中心复合设计（CCD）获得的数据。目标化合物是两种脂肪酸——花生四烯酸（AA）和二十二碳六烯酸（DHA）——以及各种脂类，包括磷脂酰胆碱（PC）、磷脂酰甘油（PG）和磷脂酰乙醇胺（PE）。考察了梯度时间、压力和改良剂百分比三个操作变量对AA和DHA的分辨及各自峰对称系数的影响。CCD在梯度时间为1 ~ 2min，压力为125 ~ 225 bar，调节剂百分比为2% ~ 5%的范围内对每个变量进行3级调节。关键对酸的RSM数据表明，压力和改良剂百分比是影响分辨率和对称系数最大的参数，而梯度时间不是显著变量。本研究的重要性在于响应面不仅能够显示显著变量-压力和修改剂百分比之间的线性相互作用（关系），而且能够显示非线性相互作用。因此，其中一个重要变量的微小变化会显著影响各自峰的分辨率AA/DHA和对称性因子。这种变量之间的相互作用只能通过本研究中采用的实验设计（DOE）方法来阐明，这在类似的脂质分析工作中没有得到证实。

{"title":"Application of design of experiments to optimize the separation of lipid-related compounds in supercritical fluid chromatography-mass spectrometry","authors":"Muhamad Yahia Kazmouz , Mátyás Mayer , Attila Felinger","doi":"10.1016/j.chroma.2025.466567","DOIUrl":"10.1016/j.chroma.2025.466567","url":null,"abstract":"<div><div>The response surface methodology (RSM) was used to optimize the separation conditions in a supercritical fluid chromatography-mass spectrometry (SFC/MS) analysis. This optimization was applied on data obtained from a central composite design (CCD). The target compounds were two fatty acids – arachidonic acid (AA) and docosahexaenoic acid (DHA) – along with various lipid classes, including phosphatidylcholines (PC), phosphatidylglycerols (PG), and phosphatidylethanolamines (PE). Three operational variables – gradient time, pressure, and modifier percentage – were investigated to evaluate their influence on the resolution between AA and DHA and the symmetry factor of their respective peaks.</div><div>The CCD included 3 levels for each variable within a range of gradient time between 1 and 2 min, the pressure between 125 and 225 bar, and the modifier percentage from 2 to 5 %.</div><div>The data of RSM for the critical pair of acids indicated that pressure and modifier percentage were the parameters that most influenced both the resolution and symmetry factor, whereas gradient time was not a significant variable.</div><div>The importance of this study lies in the capability of the response surface to show not only a linear interaction (relationship) but also a non-linear interaction between the significant variables – pressure and modifier percentage. Consequently, small changes in one of the significant variables affected the resolution AA/DHA and symmetry factors of their respective peaks significantly. This type of interaction between variables can only be elucidated by the design of experiments (DOE) approach employed in this work, which is not demonstrated in similar work of lipid anbalysis.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1766 ","pages":"Article 466567"},"PeriodicalIF":4.0,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145616111","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

Computational study and synthesis of multi-template molecularly imprinted polymer for isolating ethyl p-methoxycinnamate and ethyl cinnamate using bulk methods 体块法分离对甲氧基肉桂酸乙酯和肉桂酸乙酯的多模板分子印迹聚合物的计算研究与合成

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-11-24 DOI: 10.1016/j.chroma.2025.466566

Ike Susanti , Aliya Nur Hasanah , Rimadani Pratiwi , Yudi Rosandi

In recent years, research into molecularly imprinted polymers (MIPs) has expanded significantly, particularly for separation or isolation of analytes from extracts. MIPs designed for the simultaneous isolation of ethyl p-methoxycinnamate (EPMC) and ethyl cinnamate (EC) from Kaempferia galanga L. extract or multi-template molecularly imprinted polymer (MT-MIP) have been developed. However, the percentage recovery and purity have remained low. In this study, molecular modelling of MT-MIP for EPMC and EC was conducted using the semi-empirical Parametric Method 3 (PM3) to select functional monomers and determine the ratio of template molecule (TM) to functional monomer (FM). Geometry optimisation revealed that the HEMA formed a stable complex with the template molecule (ΔE of –92.33 kcal/mol). MT-MIPs were synthesised using HEMA at TM:FM molar ratios of 1:4 (MT-MIP-1) and 1:13 (MT-MIP-2), with an EPMC to EC ratio of 3:2, via bulk polymerisation. These polymers were employed as solid-phase extraction (SPE) adsorbents to isolate EPMC and EC from Kaempferia galanga L. extract. MT-MIP-2 exhibited a higher imprinting factor (IF) for both EPMC and EC compared to MT-MIP-1. The percentage recovery of EPMC using MT-MIP-2 for n-hexane, ethanol, and ethyl acetate extract were 65.89 %, 71.31 %, and 71.97 %. In addition, the percentage recovery of EC for n-hexane, ethanol, and ethyl acetate extract were 52.27 %, 60.79 %, and 63.36 % for the ethyl acetate extract. The purity of both EPMC and EC isolated using MT-MIP-2 exceeded 90 %. These findings demonstrate that MT-MIP-2 offers improved efficiency in the simultaneous isolation of EPMC and EC, making it a promising SPE adsorbent for natural product analysis. The separation step using MT-MIP-2 as SPE sorbent can replace the fractionation and sub-fractionation stages in EPMC and EC conventional isolation methods with high purity.

近年来，对分子印迹聚合物（MIPs）的研究有了显著的扩展，特别是在萃取物的分离或分离分析物方面。建立了同时分离山柰提取物中对甲氧基肉桂酸乙酯（EPMC）和肉桂酸乙酯（EC）的多模板分子印迹聚合物（MT-MIP）。然而，回收率和纯度仍然很低。本研究采用半经验参数化方法3 （PM3）对MT-MIP进行EPMC和EC的分子建模，选择功能单体，确定模板分子（TM）与功能单体（FM）的比例。几何优化表明，HEMA与模板分子形成稳定的配合物（ΔE -92.33 kcal/mol）。采用HEMA合成MT-MIPs， TM:FM摩尔比为1:4 （MT-MIP-1）和1:13 (MT-MIP-2)， EPMC与EC的比例为3:2，通过本体聚合。利用这些聚合物作为固相萃取（SPE）吸附剂，从山柰提取物中分离出EPMC和EC。与MT-MIP-1相比，MT-MIP-2对EPMC和EC均表现出更高的印迹因子（IF）。MT-MIP-2对正己烷、乙醇和乙酸乙酯萃取物的EPMC回收率分别为65.89%、71.31%和71.97%。正己烷、乙醇和乙酸乙酯提取物的EC回收率分别为52.27%、60.79%和63.36%。用MT-MIP-2分离得到的EPMC和EC的纯度均超过90%。这些发现表明，MT-MIP-2可以提高同时分离EPMC和EC的效率，使其成为天然产物分析中有前途的SPE吸附剂。以MT-MIP-2作为SPE吸附剂的分离步骤可取代EPMC和EC传统分离方法中的分馏和亚分馏阶段，具有较高的纯度。

{"title":"Computational study and synthesis of multi-template molecularly imprinted polymer for isolating ethyl p-methoxycinnamate and ethyl cinnamate using bulk methods","authors":"Ike Susanti , Aliya Nur Hasanah , Rimadani Pratiwi , Yudi Rosandi","doi":"10.1016/j.chroma.2025.466566","DOIUrl":"10.1016/j.chroma.2025.466566","url":null,"abstract":"<div><div>In recent years, research into molecularly imprinted polymers (MIPs) has expanded significantly, particularly for separation or isolation of analytes from extracts. MIPs designed for the simultaneous isolation of ethyl p-methoxycinnamate (EPMC) and ethyl cinnamate (EC) from <em>Kaempferia galanga</em> L. extract or multi-template molecularly imprinted polymer (MT-MIP) have been developed. However, the percentage recovery and purity have remained low. In this study, molecular modelling of MT-MIP for EPMC and EC was conducted using the semi-empirical Parametric Method 3 (PM3) to select functional monomers and determine the ratio of template molecule (TM) to functional monomer (FM). Geometry optimisation revealed that the HEMA formed a stable complex with the template molecule (ΔE of –92.33 kcal/mol). MT-MIPs were synthesised using HEMA at TM:FM molar ratios of 1:4 (MT-MIP-1) and 1:13 (MT-MIP-2), with an EPMC to EC ratio of 3:2, via bulk polymerisation. These polymers were employed as solid-phase extraction (SPE) adsorbents to isolate EPMC and EC from <em>Kaempferia galanga</em> L. extract. MT-MIP-2 exhibited a higher imprinting factor (IF) for both EPMC and EC compared to MT-MIP-1. The percentage recovery of EPMC using MT-MIP-2 for n-hexane, ethanol, and ethyl acetate extract were 65.89 %, 71.31 %, and 71.97 %. In addition, the percentage recovery of EC for n-hexane, ethanol, and ethyl acetate extract were 52.27 %, 60.79 %, and 63.36 % for the ethyl acetate extract. The purity of both EPMC and EC isolated using MT-MIP-2 exceeded 90 %. These findings demonstrate that MT-MIP-2 offers improved efficiency in the simultaneous isolation of EPMC and EC, making it a promising SPE adsorbent for natural product analysis. The separation step using MT-MIP-2 as SPE sorbent can replace the fractionation and sub-fractionation stages in EPMC and EC conventional isolation methods with high purity.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1765 ","pages":"Article 466566"},"PeriodicalIF":4.0,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145620981","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

Evolution of chromatographic modeling: From mechanistic models to hybrid models with physics-based deep learning 色谱建模的演变：从机械模型到基于物理的深度学习混合模型

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-11-22 DOI: 10.1016/j.chroma.2025.466565

Yu-Cheng Chen , Zhiyuan Chen , Shi-Peng Dai , Youping Xie , Shan-Jing Yao , Dong-Qiang Lin

Hybrid modeling based on physics-based deep learning (PBDL) represents a transformative approach that unifies mechanistic understanding and data-driven learning, offering a pathway beyond the limitations of traditional chromatographic models. This review systematically summarizes the evolution of PBDL methods for chromatography across three generations. The first generation, surrogate-model-based solvers, accelerates simulations through mechanistic up-sampling and fast inference but remains constrained by indirect physical coupling, reflecting “data-assisted physics”. The second generation, physics-informed neural networks, embeds governing equations into the loss function, enabling simultaneous learning from physics and data, while facing challenges in loss balancing and numerical integration, representing “physics-constrained data”. The third generation, differentiable numerical simulations of physical systems, integrates neural networks within numerical solvers, achieving high-fidelity modeling and gradient-based optimization, achieving “mutual feedback between physics and data”. Collectively, these advances empower chromatographic models with the ability to self-learn complex adsorption behaviors under physical constraints, paving the way toward real-time digital twins and intelligent bioprocess modeling for the next generation of chromatographic engineering.

基于物理深度学习（PBDL）的混合建模代表了一种将机制理解和数据驱动学习相结合的变革性方法，提供了超越传统色谱模型限制的途径。本文系统地总结了PBDL色谱方法在三代色谱中的发展。第一代，基于代理模型的求解器，通过机械上采样和快速推理来加速模拟，但仍然受到间接物理耦合的限制，反映了“数据辅助物理”。第二代，物理信息神经网络，将控制方程嵌入到损失函数中，能够同时从物理和数据中学习，同时面临损失平衡和数值积分的挑战，代表“物理约束数据”。第三代是物理系统的可微数值模拟，将神经网络集成到数值求解器中，实现了高保真建模和基于梯度的优化，实现了“物理和数据之间的相互反馈”。总的来说，这些进步使色谱模型能够在物理约束下自我学习复杂的吸附行为，为下一代色谱工程的实时数字双胞胎和智能生物过程建模铺平了道路。

{"title":"Evolution of chromatographic modeling: From mechanistic models to hybrid models with physics-based deep learning","authors":"Yu-Cheng Chen , Zhiyuan Chen , Shi-Peng Dai , Youping Xie , Shan-Jing Yao , Dong-Qiang Lin","doi":"10.1016/j.chroma.2025.466565","DOIUrl":"10.1016/j.chroma.2025.466565","url":null,"abstract":"<div><div>Hybrid modeling based on physics-based deep learning (PBDL) represents a transformative approach that unifies mechanistic understanding and data-driven learning, offering a pathway beyond the limitations of traditional chromatographic models. This review systematically summarizes the evolution of PBDL methods for chromatography across three generations. The first generation, surrogate-model-based solvers, accelerates simulations through mechanistic up-sampling and fast inference but remains constrained by indirect physical coupling, reflecting “data-assisted physics”. The second generation, physics-informed neural networks, embeds governing equations into the loss function, enabling simultaneous learning from physics and data, while facing challenges in loss balancing and numerical integration, representing “physics-constrained data”. The third generation, differentiable numerical simulations of physical systems, integrates neural networks within numerical solvers, achieving high-fidelity modeling and gradient-based optimization, achieving “mutual feedback between physics and data”. Collectively, these advances empower chromatographic models with the ability to self-learn complex adsorption behaviors under physical constraints, paving the way toward real-time digital twins and intelligent bioprocess modeling for the next generation of chromatographic engineering.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1765 ","pages":"Article 466565"},"PeriodicalIF":4.0,"publicationDate":"2025-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145620983","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

A review of pretreatment and analytical methods for H2 receptor antagonists: An update since 2019 H2受体拮抗剂的预处理和分析方法综述：自2019年以来的更新

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-11-22 DOI: 10.1016/j.chroma.2025.466564

Yun-Qi Ning , Yuan Zhang , Wen-hao Shao , Mei-di Wang , Yi Zhai , Xue-song Feng

H₂ receptor antagonists (H₂RAs) are widely used anti-secretory drugs that require careful therapeutic drug monitoring because of their dose-dependent hepatorenal toxicity risks. This review systematically examines recent advances (2019–present) in H₂RA analysis, covering modern sample-preparation strategies such as on-chip dispersive liquid–liquid microextraction, ultrasound-assisted emulsification microextraction, novel materials-based solid-phase extraction, and modified QuEChERS techniques. In addition, cutting-edge detection platforms, including HPLC coupled with high-resolution mass detectors and various sensor-based methods, are discussed. Each method is assessed in terms of analytical performance, environmental impact, and practical applicability, while current limitations and future developmental needs are also highlighted. Taken together, this comprehensive comparison provides valuable insights for selecting suitable analytical approaches tailored to specific clinical or research requirements.

H2受体拮抗剂（H2RAs）是广泛使用的抗分泌药物，由于其剂量依赖性的肝肾毒性风险，需要仔细的治疗药物监测。本文系统回顾了H2RA分析的最新进展（2019年至今），涵盖了现代样品制备策略，如片上分散液液微萃取、超声辅助乳化微萃取、新型材料固相萃取和改进的QuEChERS技术。此外，还讨论了尖端的检测平台，包括HPLC与高分辨率质量检测器和各种基于传感器的方法。每种方法在分析性能、环境影响和实际适用性方面进行了评估，同时也强调了当前的局限性和未来的发展需求。总的来说，这种全面的比较为选择适合特定临床或研究要求的分析方法提供了有价值的见解。

{"title":"A review of pretreatment and analytical methods for H2 receptor antagonists: An update since 2019","authors":"Yun-Qi Ning , Yuan Zhang , Wen-hao Shao , Mei-di Wang , Yi Zhai , Xue-song Feng","doi":"10.1016/j.chroma.2025.466564","DOIUrl":"10.1016/j.chroma.2025.466564","url":null,"abstract":"<div><div>H<sub>2</sub> receptor antagonists (H<sub>2</sub>RAs) are widely used anti-secretory drugs that require careful therapeutic drug monitoring because of their dose-dependent hepatorenal toxicity risks. This review systematically examines recent advances (2019–present) in H<sub>2</sub>RA analysis, covering modern sample-preparation strategies such as on-chip dispersive liquid–liquid microextraction, ultrasound-assisted emulsification microextraction, novel materials-based solid-phase extraction, and modified QuEChERS techniques. In addition, cutting-edge detection platforms, including HPLC coupled with high-resolution mass detectors and various sensor-based methods, are discussed. Each method is assessed in terms of analytical performance, environmental impact, and practical applicability, while current limitations and future developmental needs are also highlighted. Taken together, this comprehensive comparison provides valuable insights for selecting suitable analytical approaches tailored to specific clinical or research requirements.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1765 ","pages":"Article 466564"},"PeriodicalIF":4.0,"publicationDate":"2025-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145601483","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

A high-throughput determination method of chlorate and perchlorate in commercially available tea beverages 市售茶饮料中氯酸盐和高氯酸盐的高通量测定方法

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-11-21 DOI: 10.1016/j.chroma.2025.466563

Hao Zhang, Juan Wei, Wenliang Ji, Run Yang

Chlorate and perchlorate are two widely distributed contaminants, and there is a lack of research on their distribution in tea-related beverages. A new high-throughput analytical method has been developed to obtain detailed distribution data for chlorate and perchlorate. An anion-polar pesticide column and 96-well plates were applied in the chromatographic separation and sample pretreatment. The method was then used to investigate the occurrence of two compounds in 288 commercial tea-related products. The results showed that perchlorate and chlorate were widely distributed in various tea beverages, indicating that tea leaves, the processing procedure, and other flavor additives could introduce contamination into the liquor. According to the risk assessment, perchlorate and chlorate are unlikely to cause significant adverse effects from long-term consumption of tea beverages and infusions. Meanwhile, effective ways to reduce the contaminants in tea leaf consumption include using purified water for the tea brewing process, rinsing the tea leaves before brewing, and controlling the brewing time.

氯酸盐和高氯酸盐是两种广泛分布的污染物，对其在茶类饮料中的分布研究较少。建立了一种新的高通量分析方法，以获得氯酸盐和高氯酸盐的详细分布数据。采用阴离子极性农药柱和96孔板进行色谱分离和样品前处理。然后用该方法调查了288种商业茶相关产品中两种化合物的出现。结果表明，高氯酸盐和氯酸盐在各种茶饮料中广泛分布，表明茶叶、加工过程和其他风味添加剂可能会将污染引入酒中。根据风险评估，高氯酸盐和氯酸盐不太可能因长期饮用茶饮料和冲剂而造成重大不良影响。同时，茶叶冲泡过程中使用纯净水，冲泡前将茶叶冲洗干净，控制冲泡时间是减少茶叶中污染物消耗的有效途径。

{"title":"A high-throughput determination method of chlorate and perchlorate in commercially available tea beverages","authors":"Hao Zhang, Juan Wei, Wenliang Ji, Run Yang","doi":"10.1016/j.chroma.2025.466563","DOIUrl":"10.1016/j.chroma.2025.466563","url":null,"abstract":"<div><div>Chlorate and perchlorate are two widely distributed contaminants, and there is a lack of research on their distribution in tea-related beverages. A new high-throughput analytical method has been developed to obtain detailed distribution data for chlorate and perchlorate. An anion-polar pesticide column and 96-well plates were applied in the chromatographic separation and sample pretreatment. The method was then used to investigate the occurrence of two compounds in 288 commercial tea-related products. The results showed that perchlorate and chlorate were widely distributed in various tea beverages, indicating that tea leaves, the processing procedure, and other flavor additives could introduce contamination into the liquor. According to the risk assessment, perchlorate and chlorate are unlikely to cause significant adverse effects from long-term consumption of tea beverages and infusions. Meanwhile, effective ways to reduce the contaminants in tea leaf consumption include using purified water for the tea brewing process, rinsing the tea leaves before brewing, and controlling the brewing time.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1765 ","pages":"Article 466563"},"PeriodicalIF":4.0,"publicationDate":"2025-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145621022","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

Synthesis and characterization of triple acid stationary phases for cation exchange chromatography using click chemistry and atom transfer radical polymerization 用点击化学和原子转移自由基聚合合成及表征阳离子交换色谱用三酸固定相

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-11-20 DOI: 10.1016/j.chroma.2025.466561

Luca Schipplick, Andreas Seubert

Triple acid cation exchangers were synthesized by a combination of atom transfer radical polymerization (ATRP) and alkyne azide click chemistry. Oxidized uniform PS/DVB particles were functionalized stepwise with carboxylic, phosphonic and sulfonic acid groups to prepare stationary phases with unique selectivity.

The amount of sulfonic acid groups was varied while the amount of carboxylic and phosphonic acid groups remained constant, resulting in a set of stationary phases for trend analysis. The presence of sulfonic acid groups gives a good selectivity for the monovalent standard cations, while stationary phases without sulfonic acid groups show a coelution of monovalent ions. Furthermore, the presence of sulfonic acid groups results in a retention gap between mono and divalent ions, which can be used to separate target analytes inside the gap between these mono and divalent matrix ions.

The relevant inorganic matrix cations Li⁺, Na⁺, NH₄⁺, K⁺, Mg²⁺ and Ca²⁺ were separated together with mono-, di-, trimethylamine and tetramethylammonium in 45 min using a nitric acid gradient elution and suppressed conductivity detection. The retention gap between the monovalent and divalent ions was used to elute the analytes together with these ubiquitous matrix ions.

采用原子转移自由基聚合（ATRP）和炔叠氮化反应相结合的方法合成了三酸型阳离子交换剂。将氧化均匀的PS/DVB颗粒与羧基、膦基和磺酸基逐步官能化，制备出具有独特选择性的固定相。磺酸基的数量变化，羧酸和膦酸的数量保持不变，形成一组固定相用于趋势分析。磺酸基的存在对一价标准阳离子有很好的选择性，而不含磺酸基的固定相则显示出一价离子的共洗脱。此外，磺酸基团的存在导致一价和二价离子之间的保留间隙，这可以用来分离这些一价和二价基质离子之间的间隙内的目标分析物。采用硝酸梯度洗脱和抑制电导率检测，在45 min内将相关无机基质阳离子Li+、Na+、NH4+、K+、Mg2+和Ca2+与一、二、三甲胺和四甲胺一起分离。利用一价离子和二价离子之间的保留间隙与这些普遍存在的基质离子一起洗脱分析物。

{"title":"Synthesis and characterization of triple acid stationary phases for cation exchange chromatography using click chemistry and atom transfer radical polymerization","authors":"Luca Schipplick, Andreas Seubert","doi":"10.1016/j.chroma.2025.466561","DOIUrl":"10.1016/j.chroma.2025.466561","url":null,"abstract":"<div><div>Triple acid cation exchangers were synthesized by a combination of atom transfer radical polymerization (ATRP) and alkyne azide click chemistry. Oxidized uniform PS/DVB particles were functionalized stepwise with carboxylic, phosphonic and sulfonic acid groups to prepare stationary phases with unique selectivity.</div><div>The amount of sulfonic acid groups was varied while the amount of carboxylic and phosphonic acid groups remained constant, resulting in a set of stationary phases for trend analysis. The presence of sulfonic acid groups gives a good selectivity for the monovalent standard cations, while stationary phases without sulfonic acid groups show a coelution of monovalent ions. Furthermore, the presence of sulfonic acid groups results in a retention gap between mono and divalent ions, which can be used to separate target analytes inside the gap between these mono and divalent matrix ions.</div><div>The relevant inorganic matrix cations Li<sup>+</sup>, Na<sup>+</sup>, NH<sub>4</sub><sup>+</sup>, K<sup>+</sup>, Mg<sup>2+</sup> and Ca<sup>2+</sup> were separated together with mono-, di-, trimethylamine and tetramethylammonium in 45 min using a nitric acid gradient elution and suppressed conductivity detection. The retention gap between the monovalent and divalent ions was used to elute the analytes together with these ubiquitous matrix ions.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1765 ","pages":"Article 466561"},"PeriodicalIF":4.0,"publicationDate":"2025-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145620980","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