Journal of Chromatography A最新文献_第7页

A widely targeted analytical method for oxylipins including enantiomers using chiral liquid chromatography tandem mass spectrometry 应用手性液相色谱串联质谱法广泛分析包括对映体在内的氧脂类。

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-11-17 DOI: 10.1016/j.chroma.2025.466551

Yutaka Umakoshi , Yoshihiro Izumi , Tomomi Hashidate-Yoshida , Hideo Shindou , Takeshi Bamba

Oxylipins are lipids formed when polyunsaturated fatty acids are oxidized. Several oxylipins play important roles in the body, such as regulation of inflammatory responses. Although oxylipin measurement is commonly performed using reversed-phase liquid chromatography tandem mass spectrometry, conventional methods cannot resolve enantiomers. The aim of this study was to develop a widely targeted analysis method for oxylipins that could separate enantiomers. First, seven polysaccharide-derived chiral columns were screened, and the CHIRALPAK IG column, which achieved the highest resolution of eicosanoid isomers, was selected. Next, the set of targeted compounds was expanded, and the chromatographic separation of 151 compounds, including 40 pairs of enantiomers, was evaluated. The constructed method successfully separated 55 out of 59 pairs of isomers, including enantiomers. Finally, the established method was used to analyze mouse plasma and five types of tissues, and approximately 100 compounds exhibiting characteristic profiles were detected in each tissue. After evaluating hydroxyeicosatetraenoic acids (HETEs), monohydroxy compounds of arachidonic acid, it was found that the S-enantiomer of 12-HETE was more prevalent than the R-enantiomer in the lungs and spleens. Conversely, R-enantiomer of 9-HETE and 11-HETE was more abundant than the S-enantiomer. The amounts of R- and S-enantiomers of 5-HETE and 8-HETE were nearly equal in certain tissues. This analytical method is useful for biomarker discovery and accurately understanding the pathways of oxylipin formation because it can perform a widely targeted analysis of oxylipins, including enantiomers.

氧脂素是多不饱和脂肪酸氧化后形成的脂质。几种氧化脂素在体内发挥重要作用，如调节炎症反应。虽然通常使用反相液相色谱串联质谱法测量氧脂，但传统方法无法解决对映体。本研究的目的是建立一种具有广泛针对性的、可分离对映体的氧化脂类分析方法。首先，筛选了7个多糖源性手性色谱柱，选择了二十烷异构体分辨率最高的CHIRALPAK IG柱。下一步，扩大目标化合物集，并对151个化合物进行色谱分离，其中包括40对对映体。所构建的方法成功地分离了59对异构体中的55对，包括对映体。最后，将建立的方法用于分析小鼠血浆和五种类型的组织，在每种组织中检测到大约100种具有特征特征的化合物。对花生四烯酸的单羟基化合物羟基二十碳四烯酸（HETEs）进行评价后发现，在肺和脾脏中，12-HETE的s -对映体比r -对映体更普遍。相反，9-HETE和11-HETE的r -对映体比s -对映体更丰富。在某些组织中，5-HETE和8-HETE的R-和s -对映体的数量几乎相等。这种分析方法有助于发现生物标志物和准确理解氧脂质形成的途径，因为它可以对氧脂质进行广泛的靶向分析，包括对映体。

{"title":"A widely targeted analytical method for oxylipins including enantiomers using chiral liquid chromatography tandem mass spectrometry","authors":"Yutaka Umakoshi , Yoshihiro Izumi , Tomomi Hashidate-Yoshida , Hideo Shindou , Takeshi Bamba","doi":"10.1016/j.chroma.2025.466551","DOIUrl":"10.1016/j.chroma.2025.466551","url":null,"abstract":"<div><div>Oxylipins are lipids formed when polyunsaturated fatty acids are oxidized. Several oxylipins play important roles in the body, such as regulation of inflammatory responses. Although oxylipin measurement is commonly performed using reversed-phase liquid chromatography tandem mass spectrometry, conventional methods cannot resolve enantiomers. The aim of this study was to develop a widely targeted analysis method for oxylipins that could separate enantiomers. First, seven polysaccharide-derived chiral columns were screened, and the CHIRALPAK IG column, which achieved the highest resolution of eicosanoid isomers, was selected. Next, the set of targeted compounds was expanded, and the chromatographic separation of 151 compounds, including 40 pairs of enantiomers, was evaluated. The constructed method successfully separated 55 out of 59 pairs of isomers, including enantiomers. Finally, the established method was used to analyze mouse plasma and five types of tissues, and approximately 100 compounds exhibiting characteristic profiles were detected in each tissue. After evaluating hydroxyeicosatetraenoic acids (HETEs), monohydroxy compounds of arachidonic acid, it was found that the <em>S</em>-enantiomer of 12-HETE was more prevalent than the <em>R</em>-enantiomer in the lungs and spleens. Conversely, <em>R</em>-enantiomer of 9-HETE and 11-HETE was more abundant than the <em>S</em>-enantiomer. The amounts of <em>R</em>- and <em>S</em>-enantiomers of 5-HETE and 8-HETE were nearly equal in certain tissues. This analytical method is useful for biomarker discovery and accurately understanding the pathways of oxylipin formation because it can perform a widely targeted analysis of oxylipins, including enantiomers.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1765 ","pages":"Article 466551"},"PeriodicalIF":4.0,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145601517","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

High-speed characterization and quantification of polypropylene glycol based oligomeric mixtures by hydrophilic interaction liquid chromatography at critical conditions and mass spectrometry (LCCC/Q‑TOF MS) 临界条件下亲水相互作用液相色谱和质谱（LCCC/Q‑TOF MS）高速表征和定量聚丙烯-乙二醇基低聚物混合物

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-11-15 DOI: 10.1016/j.chroma.2025.466549

Sebastian Hagenhoff , Antje Wegener , Matthias Pursch

A rapid method for determination and characterization of polypropylene glycol diglycidylether and related oligomers (dGE-PPG) has been developed. The method is based on liquid chromatography at critical conditions coupled to high-resolution mass spectrometry (LCCC/MS). The LCCC method is operated in hydrophilic interaction liquid chromatography (HILIC) mode with acetonitrile/water at isocratic conditions using a core-shell silica column.

The developed method was found to be superior to conventional size exclusion chromatographic as well as reversed phase (RP) chromatographic techniques when coupled to mass spectrometry. Mass spectral overlap between different polypropylene glycol based compound classes that leads to over- and underestimation of such could be avoided by using the new method. In contrast to most published LCCC separations, this method is based on HILIC instead of RP or normal phase (NP) liquid chromatography. It provided higher chromatographic resolution between PPG based compound classes bearing different polar end groups. A run time of less than 2 minutes is achieved with high MS sensitivity at high organic modifier content, which facilitated compound identification and quantitation. Multiple compound classes could be identified, each having a distribution of propylene glycol oligomers. The methodology was straightforward to implement, and critical conditions could be maintained over the course of several months.

建立了一种快速测定和表征聚丙烯乙二醇二缩水甘油醚及其低聚物（dGE-PPG）的方法。该方法基于液相色谱-高分辨率质谱联用技术（LCCC/MS）。LCCC方法在亲水相互作用液相色谱（HILIC）模式下进行，乙腈/水在等压条件下使用核-壳硅胶柱。结果表明，该方法在与质谱联用时优于常规的粒径排除色谱法和反相色谱法。使用新方法可以避免不同的聚丙烯乙二醇基化合物类之间的质谱重叠导致的过高和过低的估计。与大多数已发表的LCCC分离相比，该方法基于HILIC而不是RP或正相（NP）液相色谱。该方法在具有不同极性端基的PPG基化合物类别之间提供了更高的色谱分辨率。在高有机改性剂含量下，运行时间小于2分钟，质谱灵敏度高，有利于化合物的鉴定和定量。可以确定多种化合物类别，每种化合物都具有丙二醇低聚物的分布。该方法易于实施，关键条件可以维持几个月。

{"title":"High-speed characterization and quantification of polypropylene glycol based oligomeric mixtures by hydrophilic interaction liquid chromatography at critical conditions and mass spectrometry (LCCC/Q‑TOF MS)","authors":"Sebastian Hagenhoff , Antje Wegener , Matthias Pursch","doi":"10.1016/j.chroma.2025.466549","DOIUrl":"10.1016/j.chroma.2025.466549","url":null,"abstract":"<div><div>A rapid method for determination and characterization of polypropylene glycol diglycidylether and related oligomers (dGE-PPG) has been developed. The method is based on liquid chromatography at critical conditions coupled to high-resolution mass spectrometry (LCCC/MS). The LCCC method is operated in hydrophilic interaction liquid chromatography (HILIC) mode with acetonitrile/water at isocratic conditions using a core-shell silica column.</div><div>The developed method was found to be superior to conventional size exclusion chromatographic as well as reversed phase (RP) chromatographic techniques when coupled to mass spectrometry. Mass spectral overlap between different polypropylene glycol based compound classes that leads to over- and underestimation of such could be avoided by using the new method. In contrast to most published LCCC separations, this method is based on HILIC instead of RP or normal phase (NP) liquid chromatography. It provided higher chromatographic resolution between PPG based compound classes bearing different polar end groups. A run time of less than 2 minutes is achieved with high MS sensitivity at high organic modifier content, which facilitated compound identification and quantitation. Multiple compound classes could be identified, each having a distribution of propylene glycol oligomers. The methodology was straightforward to implement, and critical conditions could be maintained over the course of several months.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1766 ","pages":"Article 466549"},"PeriodicalIF":4.0,"publicationDate":"2025-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145546937","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

Ethanol/ethyl acetate azeotropic mixture gas-phase separation using MOF-801-modified monolithic columns mof -801改性整体柱分离乙醇/乙酸乙酯共沸混合物气相

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-11-15 DOI: 10.1016/j.chroma.2025.466548

Alaa Bin Shuqayr , Sadeem Bin Tuwaym , Mostafa Zeama , Rawan AL Natour , Osama Shekhah , Mohamed Eddaoudi , Zeid A. ALOthman , Kareem Y. Mahmoud

Organic monolithic columns have traditionally been used for macromolecule separations; however, enhancing their performance for small molecule and azeotrope separations remains challenging. Incorporating particles into monolithic matrices has emerged as a promising strategy to overcome these limitations, particularly in gas chromatography (GC). In this work, a composite monolithic column comprising a minimal loading (0.2 wt%) of zirconium-based MOF-801 particles embedded within a divinylbenzene (DVB) polymer framework was successfully fabricated and evaluated under low operating pressure (0.2 MPa). The short 15 cm × 0.25 mm i.d. MOF-801@DVB columns enabled rapid, high-efficiency separation of light hydrocarbons, achieving sub-minute separation of linear alkane mixtures with excellent repeatability (RSD% 0.38–1.16 %) over ten injections and operational stability across >2000 runs.

Thermodynamic characterization revealed that MOF-801 incorporation enhanced the dispersive surface energy of the monolith while maintaining high permeability. McReynolds constants confirmed a polar interaction character, and a clear enthalpy–entropy compensation behavior was observed during adsorption. The monolith demonstrated successful separation of ethanol/ethyl acetate azeotropic mixtures, achieving a selectivity of 8.3 at 120 °C, surpassing benchmark materials like ZIF-8. Zero-coverage enthalpy analysis indicated stronger guest–host interactions in the MOF-801@DVB system, attributed to enhanced dispersion forces and hydrophilic framework effects.

In addition, inter-batch reproducibility across three independently prepared columns was confirmed (RSD% 1.41–6.29 %), demonstrating the reliability of the fabrication approach. This study underscores the potential of integrating MOF particles into organic monolithic matrices to expand their application in small molecule GC separations, providing a cost-effective, high-stability platform for rapid gas-phase separations driven by thermodynamic control.

有机整体柱传统上用于大分子分离；然而，提高它们在小分子和共沸物分离中的性能仍然具有挑战性。将颗粒整合到整体矩阵中已经成为克服这些限制的一种有前途的策略，特别是在气相色谱（GC）中。在这项工作中，成功地制造了一种复合整体柱，该整体柱包含了嵌入在二乙烯苯（DVB）聚合物框架中的锆基MOF-801颗粒的最小负载（0.2 wt%），并在低操作压力（0.2 MPa）下进行了评估。短的15 cm × 0.25 mm id MOF-801@DVB色谱柱能够快速、高效地分离轻烃，在10次进样中实现线性烷烃混合物的亚分钟分离，具有出色的重复性（RSD% 0.38 - 1.16%）和2000次运行的操作稳定性。热力学表征表明，MOF-801的掺入增强了整体体的弥散表面能，同时保持了高渗透率。McReynolds常数证实了极性相互作用的特征，并且在吸附过程中观察到明显的焓熵补偿行为。该单体成功分离了乙醇/乙酸乙酯共沸混合物，在120°C下达到8.3的选择性，超过了ZIF-8等基准材料。零覆盖焓分析表明，在MOF-801@DVB体系中，由于增强的分散力和亲水框架效应，主客体相互作用更强。此外，确认了三个独立制备柱的批间重现性（RSD% 1.41 - 6.29%），证明了制备方法的可靠性。该研究强调了将MOF颗粒整合到有机单片基质中的潜力，以扩大其在小分子气相色谱分离中的应用，为热力学控制驱动的快速气相分离提供了一个经济高效、高稳定性的平台。

{"title":"Ethanol/ethyl acetate azeotropic mixture gas-phase separation using MOF-801-modified monolithic columns","authors":"Alaa Bin Shuqayr , Sadeem Bin Tuwaym , Mostafa Zeama , Rawan AL Natour , Osama Shekhah , Mohamed Eddaoudi , Zeid A. ALOthman , Kareem Y. Mahmoud","doi":"10.1016/j.chroma.2025.466548","DOIUrl":"10.1016/j.chroma.2025.466548","url":null,"abstract":"<div><div>Organic monolithic columns have traditionally been used for macromolecule separations; however, enhancing their performance for small molecule and azeotrope separations remains challenging. Incorporating particles into monolithic matrices has emerged as a promising strategy to overcome these limitations, particularly in gas chromatography (GC). In this work, a composite monolithic column comprising a minimal loading (0.2 wt%) of zirconium-based MOF-801 particles embedded within a divinylbenzene (DVB) polymer framework was successfully fabricated and evaluated under low operating pressure (0.2 MPa). The short 15 cm × 0.25 mm i.d. MOF-801@DVB columns enabled rapid, high-efficiency separation of light hydrocarbons, achieving sub-minute separation of linear alkane mixtures with excellent repeatability (RSD% 0.38–1.16 %) over ten injections and operational stability across >2000 runs.</div><div>Thermodynamic characterization revealed that MOF-801 incorporation enhanced the dispersive surface energy of the monolith while maintaining high permeability. McReynolds constants confirmed a polar interaction character, and a clear enthalpy–entropy compensation behavior was observed during adsorption. The monolith demonstrated successful separation of ethanol/ethyl acetate azeotropic mixtures, achieving a selectivity of 8.3 at 120 °C, surpassing benchmark materials like ZIF-8. Zero-coverage enthalpy analysis indicated stronger guest–host interactions in the MOF-801@DVB system, attributed to enhanced dispersion forces and hydrophilic framework effects.</div><div>In addition, inter-batch reproducibility across three independently prepared columns was confirmed (RSD% 1.41–6.29 %), demonstrating the reliability of the fabrication approach. This study underscores the potential of integrating MOF particles into organic monolithic matrices to expand their application in small molecule GC separations, providing a cost-effective, high-stability platform for rapid gas-phase separations driven by thermodynamic control.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1766 ","pages":"Article 466548"},"PeriodicalIF":4.0,"publicationDate":"2025-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145571030","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

Adsorption and separation of RNA and protein on imidazolium-type ionic liquids-based chromatographic media: influence of counterions RNA和蛋白质在咪唑型离子液体色谱介质上的吸附和分离：反离子的影响

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-11-15 DOI: 10.1016/j.chroma.2025.466547

Ziang Yan , Jingyang Zhao , Xuan Lin , Zhengjun Li , Weiqing Zhou , Xiangming Na , Zhiguo Su , Songping Zhang

Imidazolium-based ionic liquids (ILs) as ligand have shown great potentials in biomacromolecule separation by chemically coupling the cationic functional group of the ILs to solid supports. Whether and how the counterions affect the adsorption of biomacromolecule, however remains unclear. In this work, GigaMIm chromatographic media was prepared by coupling an ionizable 1-methylimidazole (MIm) to giga-porous microspheres and paired with four different counterions including Cl⁻, H₂PO₄⁻, benzoate ion (BZA⁻), and 4-hydroxybenzenesulfonate (HBS⁻). The types of the counterions on GigaMIm was found to significantly influence the adsorption kinetics and isotherms of yeast RNA and BSA, as well as the chromatographic separation of RNA-BSA mixture. Compared to the media paired with inorganic ions (Cl⁻ and H₂PO₄⁻), those paired with benzene ring-containing counterions (HBS⁻ and BZA⁻) exhibited slightly slower pore diffusion kinetics and lower adsorption capacities for both RNA and BSA, but provided better separation resolution for their mixture. Molecular docking suggested that enhanced hydrogen bonding between MIm⁺/HBS⁻ or MIm⁺/BZA⁻ and biomolecules contributed to improved resolution. The counterion-tuning strategy was further validated by separation of eGFP mRNA from in vitro transcription system. Compared to GigaMIm-Cl, purification using GigaMIm-HBS obtained higher mRNA recovery (38.42 % vs. 30.94 %) with high mRNA purity and lower T7 polymerase residual (0.16 % vs. 0.21 %). These findings demonstrate that modulating counterions in ILs-based media may offer a promising strategy for optimizing nucleic acid and protein separation.

咪唑类离子液体作为配体，通过将离子液体的阳离子官能团与固体载体进行化学偶联，在生物大分子分离中显示出巨大的潜力。然而，反离子是否以及如何影响生物大分子的吸附尚不清楚。在这项工作中，通过将可电离的1-甲基咪唑（MIm）偶联到千兆孔微球上制备了GigaMIm色谱介质，并与四种不同的反离子配对，包括Cl−，H2PO4−，苯甲酸盐离子（BZA−）和4-羟基苯磺酸盐（HBS−）。研究发现，GigaMIm上反离子的类型显著影响酵母RNA和牛血清白蛋白的吸附动力学和等温线，以及RNA-牛血清白蛋白混合物的色谱分离。与无机离子（Cl−和H2PO4−）配对的介质相比，含苯环反离子（HBS−和BZA−）配对的介质对RNA和BSA的孔扩散动力学稍慢，吸附能力较低，但对其混合物具有更好的分离分辨率。分子对接表明，MIm⁺/HBS⁻或MIm⁺/BZA⁻与生物分子之间的氢键增强有助于提高分辨率。通过从体外转录系统中分离eGFP mRNA，进一步验证了反调谐策略。与GigaMIm-Cl相比，使用GigaMIm-HBS纯化获得更高的mRNA回收率（38.42%比30.94%），mRNA纯度高，T7聚合酶残留量低（0.16%比0.21%）。这些发现表明，在基于il的培养基中调节反离子可能为优化核酸和蛋白质分离提供了一种有前途的策略。

{"title":"Adsorption and separation of RNA and protein on imidazolium-type ionic liquids-based chromatographic media: influence of counterions","authors":"Ziang Yan , Jingyang Zhao , Xuan Lin , Zhengjun Li , Weiqing Zhou , Xiangming Na , Zhiguo Su , Songping Zhang","doi":"10.1016/j.chroma.2025.466547","DOIUrl":"10.1016/j.chroma.2025.466547","url":null,"abstract":"<div><div>Imidazolium-based ionic liquids (ILs) as ligand have shown great potentials in biomacromolecule separation by chemically coupling the cationic functional group of the ILs to solid supports. Whether and how the counterions affect the adsorption of biomacromolecule, however remains unclear. In this work, GigaMIm chromatographic media was prepared by coupling an ionizable 1-methylimidazole (MIm) to giga-porous microspheres and paired with four different counterions including Cl<sup>−</sup>, H<sub>2</sub>PO<sub>4</sub><sup>−</sup>, benzoate ion (BZA<sup>−</sup>), and 4-hydroxybenzenesulfonate (HBS<sup>−</sup>). The types of the counterions on GigaMIm was found to significantly influence the adsorption kinetics and isotherms of yeast RNA and BSA, as well as the chromatographic separation of RNA-BSA mixture. Compared to the media paired with inorganic ions (Cl<sup>−</sup> and H<sub>2</sub>PO<sub>4</sub><sup>−</sup>), those paired with benzene ring-containing counterions (HBS<sup>−</sup> and BZA<sup>−</sup>) exhibited slightly slower pore diffusion kinetics and lower adsorption capacities for both RNA and BSA, but provided better separation resolution for their mixture. Molecular docking suggested that enhanced hydrogen bonding between MIm⁺/HBS⁻ or MIm⁺/BZA⁻ and biomolecules contributed to improved resolution. The counterion-tuning strategy was further validated by separation of eGFP mRNA from <em>in vitro</em> transcription system. Compared to GigaMIm-Cl, purification using GigaMIm-HBS obtained higher mRNA recovery (38.42 % <em>vs.</em> 30.94 %) with high mRNA purity and lower T7 polymerase residual (0.16 % <em>vs.</em> 0.21 %). These findings demonstrate that modulating counterions in ILs-based media may offer a promising strategy for optimizing nucleic acid and protein separation.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1766 ","pages":"Article 466547"},"PeriodicalIF":4.0,"publicationDate":"2025-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145571029","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

Comprehensive quality analysis strategy for Qizhi Yishen Capsule based on mass spectrometry profiling and tandem fingerprinting technology 基于质谱分析和串联指纹图谱技术的芪脂益神胶囊质量综合分析策略。

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-11-15 DOI: 10.1016/j.chroma.2025.466527

Jirui Wang , Baolian Wan , Fuxia He , Guichun Shang , Weihan Qin , Xiaomei Zhang , Yong Yang , Hongyi Qi

The Qizhi Yishen Capsule (QYC) is a traditional Chinese medicine (TCM) used for the treatment of patients exhibiting syndromes of both qi and yin deficiency in early diabetic nephropathy. However, due to its relatively recent market introduction, no research has yet been reported on the characterization of its chemical constituents. This study presents a reliable and systematic approach for characterizing the chemical constituents present in QYC, establishing its dual-detector mode fingerprint, and quantifying ten components using ultra-performance liquid chromatography coupled with quadrupole-time-of-flight tandem mass spectrometry (UPLC-Q-TOF-MS/MS) and high-performance liquid chromatography with photodiode array and evaporative light scattering detectors (HPLC-PDA-ELSD). Multivariate analysis was also employed to screen characteristic peaks and identify differences across different production years. A total of 103 compounds, including phenolic acids, alkaloids, flavonoids, quinones, terpenoids, and other phytochemicals, were successfully characterized. Moreover, 35 common peaks were matched in the HPLC-PDA mode and 29 in the HPLC-ELSD mode, among which 12 and 6 peaks were identified, respectively. Subsequently, the contents of sinomenine, calycosin-7-O-glucoside, acteoside, specnuezhenide, isoacteoside, aloe-emodin, rhein, emodin, chrysophanol, and physcion in 19 batch samples were determined, ranging from 9.516 to 17.571 mg/g, 0.485 to 0.811 mg/g, 0.853 to 1.750 mg/g, 11.037 to 17.834 mg/g, 1.575 to 11.522 mg/g, 0.342 to 0.664 mg/g, 0.729 to 0.962 mg/g, 0.318 to 0.566 mg/g, 0.835 to 1.391 mg/g, and 0.424 to 0.727 mg/g, respectively. Overall, the findings of this study may support future investigations into the active chemical constituents and quality evaluation of QYC.

芪脂益肾胶囊（QYC）是一种用于治疗早期糖尿病肾病气阴两虚证的中药。然而，由于其相对较新的市场引入，尚未有研究报告其化学成分的表征。本研究提出了一种可靠、系统的方法来表征青青中存在的化学成分，建立其双检测器模式指纹图谱，并使用超高效液相色谱-四极杆飞行时间串联质谱（UPLC-Q-TOF-MS/MS）和高效液相色谱-光电二极管阵列和蒸发光散射检测器（HPLC-PDA-ELSD）对10种成分进行定量分析。采用多变量分析筛选特征峰，确定不同生产年份间的差异。共鉴定了103个化合物，包括酚酸、生物碱、黄酮类、醌类、萜类和其他植物化学物质。在HPLC-PDA模式和HPLC-ELSD模式下分别匹配了35个和29个共同峰，其中分别鉴定出12个和6个。测定了19批样品中青藤碱、毛蕊花苷-7- o -葡萄糖苷、毛蕊花苷、specnuezhenide、异毛蕊花苷、芦荟大黄素、大黄素、大黄素、大黄酚、白藜芦醇的含量，分别为9.516 ~ 17.571 mg/g、0.485 ~ 0.811 mg/g、0.853 ~ 1.750 mg/g、11.037 ~ 17.834 mg/g、1.575 ~ 11.522 mg/g、0.342 ~ 0.664 mg/g、0.729 ~ 0.962 mg/g、0.318 ~ 0.566 mg/g、0.835 ~ 1.391 mg/g、0.424 ~ 0.727 mg/g。综上所述，本研究结果可为今后对青花草有效化学成分的研究和质量评价提供支持。

{"title":"Comprehensive quality analysis strategy for Qizhi Yishen Capsule based on mass spectrometry profiling and tandem fingerprinting technology","authors":"Jirui Wang , Baolian Wan , Fuxia He , Guichun Shang , Weihan Qin , Xiaomei Zhang , Yong Yang , Hongyi Qi","doi":"10.1016/j.chroma.2025.466527","DOIUrl":"10.1016/j.chroma.2025.466527","url":null,"abstract":"<div><div>The Qizhi Yishen Capsule (QYC) is a traditional Chinese medicine (TCM) used for the treatment of patients exhibiting syndromes of both qi and yin deficiency in early diabetic nephropathy. However, due to its relatively recent market introduction, no research has yet been reported on the characterization of its chemical constituents. This study presents a reliable and systematic approach for characterizing the chemical constituents present in QYC, establishing its dual-detector mode fingerprint, and quantifying ten components using ultra-performance liquid chromatography coupled with quadrupole-time-of-flight tandem mass spectrometry (UPLC-Q-TOF-MS/MS) and high-performance liquid chromatography with photodiode array and evaporative light scattering detectors (HPLC-PDA-ELSD). Multivariate analysis was also employed to screen characteristic peaks and identify differences across different production years. A total of 103 compounds, including phenolic acids, alkaloids, flavonoids, quinones, terpenoids, and other phytochemicals, were successfully characterized. Moreover, 35 common peaks were matched in the HPLC-PDA mode and 29 in the HPLC-ELSD mode, among which 12 and 6 peaks were identified, respectively. Subsequently, the contents of sinomenine, calycosin-7-O-glucoside, acteoside, specnuezhenide, isoacteoside, aloe-emodin, rhein, emodin, chrysophanol, and physcion in 19 batch samples were determined, ranging from 9.516 to 17.571 mg/g, 0.485 to 0.811 mg/g, 0.853 to 1.750 mg/g, 11.037 to 17.834 mg/g, 1.575 to 11.522 mg/g, 0.342 to 0.664 mg/g, 0.729 to 0.962 mg/g, 0.318 to 0.566 mg/g, 0.835 to 1.391 mg/g, and 0.424 to 0.727 mg/g, respectively. Overall, the findings of this study may support future investigations into the active chemical constituents and quality evaluation of QYC.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1766 ","pages":"Article 466527"},"PeriodicalIF":4.0,"publicationDate":"2025-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145585655","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

Encapsulated nanomaterials: Exploring Cutting-edge horizons for sustainable approach in extraction processes: A review 封装纳米材料：探索提取过程中可持续方法的前沿视野：综述。

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-11-14 DOI: 10.1016/j.chroma.2025.466545

Muhammad Saqaf Jagirani , Mustafa Soylak

The integration of nanotechnology into extraction methods has revolutionized separation and purification approaches by offering high selectivity, sensitivity, efficiency, and environmental sustainability. Among several nanomaterials, encapsulated nanomaterials have emerged as a promising class due to their excellent morphology, high surface area, tunable porosity, and controllable surface functionalities. Encapsulation stabilizes nanomaterials, improves reproducibility, enhances stability during extraction, and minimizes waste. Furthermore, encapsulated nanomaterials have high potential for achieving high extraction efficiency in real-time applications and eliminating various analytes. Encapsulation stabilizes nanomaterials, improves reproducibility, enhances stability during extraction, and minimizes waste. This review explores cutting-edge developments in encapsulated nanomaterials for extraction techniques (solid-phase extraction and solid-phase microextraction), offering insights into their potential to reduce ecological footprints, enhance resource recovery efficiency, and facilitate the pretreatment of organic and inorganic contaminants. This review examines the encapsulation methods and mechanisms that govern host-guest interactions, supporting excellent performance. The ecological benefits of exploring sustainable materials, such as metal-organic frameworks, biodegradable polymers, covalent organic frameworks, and hybrid nanocomposites, as well as encapsulating materials, are also highlighted. Conclusively, key challenges, emerging trends, and future directions are outlined to guide the development of next-generation encapsulated nanomaterials, aiming to achieve highly efficient, sustainable, and economically extracted technologies. The continuous evolution in this field promises to revolutionize industrial extraction methods.

将纳米技术整合到提取方法中，通过提供高选择性、灵敏度、效率和环境可持续性，彻底改变了分离和纯化方法。在众多纳米材料中，封装纳米材料因其优异的形貌、高表面积、可调节的孔隙率和可控制的表面功能而成为一种很有前途的纳米材料。封装稳定纳米材料，提高可重复性，提高提取过程中的稳定性，并最大限度地减少浪费。此外，封装纳米材料在实时应用中具有很高的萃取效率和去除各种分析物的潜力。封装稳定纳米材料，提高可重复性，提高提取过程中的稳定性，并最大限度地减少浪费。本文综述了用于萃取技术（固相萃取和固相微萃取）的封装纳米材料的最新进展，并对其在减少生态足迹、提高资源回收效率和促进有机和无机污染物预处理方面的潜力进行了深入研究。这篇综述研究了控制主-客交互的封装方法和机制，以支持出色的性能。探索可持续材料的生态效益，如金属有机框架、可生物降解聚合物、共价有机框架、杂化纳米复合材料以及封装材料，也得到了强调。最后，概述了关键挑战，新兴趋势和未来方向，以指导下一代封装纳米材料的发展，旨在实现高效，可持续和经济的提取技术。该领域的不断发展有望彻底改变工业提取方法。

{"title":"Encapsulated nanomaterials: Exploring Cutting-edge horizons for sustainable approach in extraction processes: A review","authors":"Muhammad Saqaf Jagirani , Mustafa Soylak","doi":"10.1016/j.chroma.2025.466545","DOIUrl":"10.1016/j.chroma.2025.466545","url":null,"abstract":"<div><div>The integration of nanotechnology into extraction methods has revolutionized separation and purification approaches by offering high selectivity, sensitivity, efficiency, and environmental sustainability. Among several nanomaterials, encapsulated nanomaterials have emerged as a promising class due to their excellent morphology, high surface area, tunable porosity, and controllable surface functionalities. Encapsulation stabilizes nanomaterials, improves reproducibility, enhances stability during extraction, and minimizes waste. Furthermore, encapsulated nanomaterials have high potential for achieving high extraction efficiency in real-time applications and eliminating various analytes. Encapsulation stabilizes nanomaterials, improves reproducibility, enhances stability during extraction, and minimizes waste. This review explores cutting-edge developments in encapsulated nanomaterials for extraction techniques (solid-phase extraction and solid-phase microextraction), offering insights into their potential to reduce ecological footprints, enhance resource recovery efficiency, and facilitate the pretreatment of organic and inorganic contaminants. This review examines the encapsulation methods and mechanisms that govern host-guest interactions, supporting excellent performance. The ecological benefits of exploring sustainable materials, such as metal-organic frameworks, biodegradable polymers, covalent organic frameworks, and hybrid nanocomposites, as well as encapsulating materials, are also highlighted. Conclusively, key challenges, emerging trends, and future directions are outlined to guide the development of next-generation encapsulated nanomaterials, aiming to achieve highly efficient, sustainable, and economically extracted technologies. The continuous evolution in this field promises to revolutionize industrial extraction methods.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1765 ","pages":"Article 466545"},"PeriodicalIF":4.0,"publicationDate":"2025-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145556058","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

Construction of porous adsorbent for selective enrichment of cis-diol-containing flavonoids and evaluation of green performance based on life cycle analysis 含顺式二醇类黄酮选择性富集多孔吸附剂的构建及基于生命周期分析的绿色性能评价。

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-11-14 DOI: 10.1016/j.chroma.2025.466546

Hui Wang , Anrui Gu , Mingyuan Gao , Yuqing Zhang , Houle Xiang , Jingwei Kou , Hanjie Ying , Jinglan Wu

Flavonoids exhibit anti-inflammatory, anti-cancer, antibacterial and anti-aging properties. However, their complex structures make the separation and purification of flavonoids pharmacologically significant. The study employed a one-pot synthesis method to prepare the adsorbent (Pectin/Carboxymethyl starch sodium/Polyethylenimine/4-Formylphenylboronic acid, PCPF), using pectin, sodium carboxymethyl starch, polyethyleneimine and 4-formylbenzeneboronic acid as raw materials. Under the same adsorption conditions, the adsorption capacity of PCPF reached 40.87 mg/g, which was significantly higher than those of the commercial macroporous resins AB-8 (33.56 mg/g), HPD100 (34.19 mg/g) and HP20 (34.42 mg/g). PCPF selectively adsorbed flavonoids containing cis-diol structures (quercetin, rutin and luteolin). At 318.15 K, its maximum adsorption capacity for quercetin reached 214.93 mg/g. The content of quercetin in Cordyceps militaris was significantly enhanced by 20.49-fold through the use of this adsorbent for enrichment. Fourier transform infrared spectroscopy further confirmed that the adsorption mechanism primarily resulted from cyclization reactions between boronic acid groups and flavonoids containing cis-diol structures at pH 8, along with π–π interactions, hydrophobic interaction and hydrogen bonding. Furthermore, this adsorbent demonstrated excellent recyclability, with adsorption capacity decreasing by only 5 mg/g after five cycles. Finally, Life Cycle Analysis (LCA) comparing PCPF with conventional macroporous resin adsorbents across seven evaluation metrics (abiotic depletion, abiotic depletion (fossil fuels), acidification, freshwater aquatic ecotoxicity, global warming (GWP 100 a), human toxicity and marine aquatic ecotoxicity) confirmed PCPF as the more environmentally sustainable choice. In summary, PCPF held significant potential as an adsorbent for flavonoid compounds containing cis-diol structures.

黄酮类化合物具有抗炎、抗癌、抗菌和抗衰老的特性。然而，黄酮类化合物的复杂结构使得其分离纯化具有重要的药理意义。本研究以果胶、羧甲基淀粉钠、聚乙烯亚胺和4-甲酰苯硼酸为原料，采用一锅法合成了吸附剂（果胶/羧甲基淀粉钠/聚乙烯亚胺/4-甲酰苯硼酸，PCPF）。在相同的吸附条件下，PCPF的吸附量达到40.87 mg/g，显著高于商用大孔树脂AB-8 （33.56 mg/g）、HPD100 （34.19 mg/g）和HP20 （34.42 mg/g）。PCPF选择性吸附含有顺式二醇结构的黄酮类化合物（槲皮素、芦丁和木犀草素）。在318.15 K时，其对槲皮素的最大吸附量为214.93 mg/g。用该吸附剂富集后，蛹虫草中槲皮素的含量显著提高20.49倍。傅里叶红外光谱进一步证实了吸附机理主要是硼酸基团与含顺式二醇结构的黄酮类化合物在pH为8时发生环化反应，并伴有π-π相互作用、疏水相互作用和氢键作用。此外，该吸附剂具有良好的可回收性，经过5次循环后，吸附量仅下降5 mg/g。最后，生命周期分析（LCA）通过7个评价指标（非生物耗竭、非生物耗竭（化石燃料）、酸化、淡水水生生态毒性、全球变暖（GWP 100 a）、人类毒性和海洋水生生态毒性）将PCPF与传统大孔树脂吸附剂进行了比较，证实了PCPF是更具环境可持续性的选择。综上所述，PCPF作为含有顺式二醇结构的类黄酮化合物的吸附剂具有很大的潜力。

{"title":"Construction of porous adsorbent for selective enrichment of cis-diol-containing flavonoids and evaluation of green performance based on life cycle analysis","authors":"Hui Wang , Anrui Gu , Mingyuan Gao , Yuqing Zhang , Houle Xiang , Jingwei Kou , Hanjie Ying , Jinglan Wu","doi":"10.1016/j.chroma.2025.466546","DOIUrl":"10.1016/j.chroma.2025.466546","url":null,"abstract":"<div><div>Flavonoids exhibit anti-inflammatory, anti-cancer, antibacterial and anti-aging properties. However, their complex structures make the separation and purification of flavonoids pharmacologically significant. The study employed a one-pot synthesis method to prepare the adsorbent (Pectin/Carboxymethyl starch sodium/Polyethylenimine/4-Formylphenylboronic acid, PCPF), using pectin, sodium carboxymethyl starch, polyethyleneimine and 4-formylbenzeneboronic acid as raw materials. Under the same adsorption conditions, the adsorption capacity of PCPF reached 40.87 mg/g, which was significantly higher than those of the commercial macroporous resins AB-8 (33.56 mg/g), HPD100 (34.19 mg/g) and HP20 (34.42 mg/g). PCPF selectively adsorbed flavonoids containing cis-diol structures (quercetin, rutin and luteolin). At 318.15 K, its maximum adsorption capacity for quercetin reached 214.93 mg/g. The content of quercetin in <em>Cordyceps militaris</em> was significantly enhanced by 20.49-fold through the use of this adsorbent for enrichment. Fourier transform infrared spectroscopy further confirmed that the adsorption mechanism primarily resulted from cyclization reactions between boronic acid groups and flavonoids containing cis-diol structures at pH 8, along with π–π interactions, hydrophobic interaction and hydrogen bonding. Furthermore, this adsorbent demonstrated excellent recyclability, with adsorption capacity decreasing by only 5 mg/g after five cycles. Finally, Life Cycle Analysis (LCA) comparing PCPF with conventional macroporous resin adsorbents across seven evaluation metrics (abiotic depletion, abiotic depletion (fossil fuels), acidification, freshwater aquatic ecotoxicity, global warming (GWP 100 a), human toxicity and marine aquatic ecotoxicity) confirmed PCPF as the more environmentally sustainable choice. In summary, PCPF held significant potential as an adsorbent for flavonoid compounds containing cis-diol structures.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1765 ","pages":"Article 466546"},"PeriodicalIF":4.0,"publicationDate":"2025-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145556048","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

Optimization of gas chromatography-isotope ratio mass spectrometry oxygen isotope analysis method and recommendations for precision control 气相色谱-同位素比质谱法氧同位素分析方法的优化及精密度控制建议。

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-11-13 DOI: 10.1016/j.chroma.2025.466544

Zhi-Hao Zhang , Yu-Shan Luo , Jie Jin , Zhuo-Yi Zhu

Accurate measurement of oxygen isotope composition (δ¹⁸O) in dissolved oxygen (DO) is critical for quantifying oxygen dynamics in aquatic systems, yet traditional methods such as dual-inlet isotope ratio mass spectrometry (DI-IRMS) require labor-intensive offline preparation. The continuous-flow gas chromatography-IRMS (GC-IRMS) technique improves throughput but faces limitations in precision calibration and simultaneously O₂/Ar detection. This study addresses these challenges by optimizing GC-IRMS protocols for gas-phase δ¹⁸O analysis, with a focus on applications in DO studies. A semi-automated O₂-Ar purification system was developed for δ¹⁸O analysis, integrating a modified Precon unit, a GC, and an IRMS. DO was converted to gaseous O₂ via headspace equilibration and calibrated using synthetic air. A total of three injections were sequentially conducted in a single run and our results showed that at peak intensities >6.0 × 10³, δ¹⁸O precision reached <0.15 ‰. This study's breakthrough involves enhancing δ¹⁸O measurement accuracy via Baseline drift correction (BDC) and Argon interference correction (AIC), with Helium (He) blank correction (HBC) additionally required when using ambient air as reference, as well as the acquisition of the O₂/Ar ratio, which facilitates the geochemical application of oxygen isotopes in aquatic sciences. Analysis of East China Sea profiles revealed that the δ¹⁸O corrected using synthetic air as the reference were higher than those corrected based on ambient air, with HBC contributing the most to the final δ¹⁸O, up to 0.3 ‰. Our results indicate that employing a He-mixed air method for daily calibration is crucial for enhancing δ¹⁸O precision in continuous-flow DO isotope analysis.

准确测量溶解氧（DO）中的氧同位素组成（δ¹⁸O）对于定量水生系统中的氧动力学至关重要，然而传统的方法，如双入口同位素比质谱法（DI-IRMS）需要劳动密集型的离线准备。连续流气相色谱- irms （GC-IRMS）技术提高了通量，但在精度校准和同时检测O₂/Ar方面存在局限性。本研究通过优化气相δ¹⁸O分析的GC-IRMS方案来解决这些挑战，重点关注在DO研究中的应用。开发了一套用于δ¹⁸O分析的半自动O₂-Ar净化系统，该系统集成了改良的Precon单元、气相色谱和IRMS。通过顶空平衡将DO转化为气态O₂，并使用合成空气进行校准。结果表明，在峰值强度>6.0 × 10³时，δ¹⁸O的精密度达到了峰值

{"title":"Optimization of gas chromatography-isotope ratio mass spectrometry oxygen isotope analysis method and recommendations for precision control","authors":"Zhi-Hao Zhang , Yu-Shan Luo , Jie Jin , Zhuo-Yi Zhu","doi":"10.1016/j.chroma.2025.466544","DOIUrl":"10.1016/j.chroma.2025.466544","url":null,"abstract":"<div><div>Accurate measurement of oxygen isotope composition (δ¹⁸O) in dissolved oxygen (DO) is critical for quantifying oxygen dynamics in aquatic systems, yet traditional methods such as dual-inlet isotope ratio mass spectrometry (DI-IRMS) require labor-intensive offline preparation. The continuous-flow gas chromatography-IRMS (GC-IRMS) technique improves throughput but faces limitations in precision calibration and simultaneously O₂/Ar detection. This study addresses these challenges by optimizing GC-IRMS protocols for gas-phase δ¹⁸O analysis, with a focus on applications in DO studies. A semi-automated O₂-Ar purification system was developed for δ¹⁸O analysis, integrating a modified Precon unit, a GC, and an IRMS. DO was converted to gaseous O₂ via headspace equilibration and calibrated using synthetic air. A total of three injections were sequentially conducted in a single run and our results showed that at peak intensities >6.0 × 10³, δ¹⁸O precision reached <0.15 ‰. This study's breakthrough involves enhancing δ¹⁸O measurement accuracy via Baseline drift correction (BDC) and Argon interference correction (AIC), with Helium (He) blank correction (HBC) additionally required when using ambient air as reference, as well as the acquisition of the O₂/Ar ratio, which facilitates the geochemical application of oxygen isotopes in aquatic sciences. Analysis of East China Sea profiles revealed that the δ¹⁸O corrected using synthetic air as the reference were higher than those corrected based on ambient air, with HBC contributing the most to the final δ¹⁸O, up to 0.3 ‰. Our results indicate that employing a He-mixed air method for daily calibration is crucial for enhancing δ¹⁸O precision in continuous-flow DO isotope analysis.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1765 ","pages":"Article 466544"},"PeriodicalIF":4.0,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145547739","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

Separation of homologues and positional isomers of secondary alcohol ethoxylates via supercritical fluid chromatography 超临界流体色谱法分离仲醇乙氧基醚的同系物和位置异构体。

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-11-13 DOI: 10.1016/j.chroma.2025.466543

Akihiro Moriuchi , Yoshihiro Izumi , Toshiyuki Yamashita , Masatomo Takahashi , Takeshi Bamba

Non-ionic surfactants consist of hydrophobic alkyl chains and hydrophilic polyethylene oxide (EO), whose distributions significantly influence properties such as hydrophilic–lipophilic balance and critical micelle concentration. In particular, secondary alcohol ethoxylates (AEOs), in which EO units are inserted within the alkyl chain, are complex mixtures that include multiple positional isomers in addition to homologous EO and alkyl‑chain distributions, making them difficult to separate via conventional liquid chromatography (LC) or gas chromatography (GC). Therefore, we evaluated supercritical fluid chromatography (SFC) for high-resolution analysis of these nonvolatile mixtures. Using an octadecylsilane (ODS) column without end‑capping (Inertsil ODS‑4 noEC, 2.1 mm inner diameter (i.d.) × 150 mm, 3 μm) connected in series (five columns, total length 750 mm), with a flow rate of 0.8 mL/min, column oven at 40 °C, and back pressure regulator set at 10 MPa, we achieved separation of positional isomers of secondary AEOs that had been previously unresolved. For example, five positional isomers of the C14 alkyl chain with EO6 were resolved (five peaks) in a single analysis (total run time 200 min), and the measured peak capacity was 67. This separation was due to differences in the molecular shapes of the positional isomers of secondary AEOs, which resulted in varying degrees of steric hindrance from the ODS group on the stationary phase surface and differences in polar interactions with the residual silanol groups. SFC is useful for separation and composition analysis of complex mixtures that are difficult to separate via GC or LC and is expected to be utilized for the precise analysis of components such as surfactants and synthetic polymers whose composition significantly affects performance and quality.

非离子表面活性剂由疏水烷基链和亲水聚氧乙烯（EO）组成，它们的分布对表面活性剂的亲水-亲脂平衡和临界胶束浓度等性能有显著影响。特别是，在烷基链内插入EO单元的二级醇乙氧基酸酯（AEOs）是复杂的混合物，除了同源EO和烷基链分布外，还包括多个位置异构体，这使得它们难以通过传统的液相色谱（LC）或气相色谱（GC）分离。因此，我们评估了超临界流体色谱（SFC）对这些非挥发性混合物的高分辨率分析。使用无端盖的十八烷基硅烷（ODS）色谱柱（Inertsil ODS - 4 noEC，内径2.1 mm）。× 150mm, 3 μm)串联（5个柱，全长750mm），流速0.8 mL/min，柱箱温度40℃，背压调节器温度10 MPa，实现了二级AEOs位置异构体的分离。例如，C14烷基链与EO6的5个位置异构体在一次分析（总运行时间200 min）中被分解（5个峰），测得的峰容量为67。这种分离是由于二级AEOs的位置异构体的分子形状不同，导致固定相表面ODS基团的空间位阻程度不同，与剩余硅烷醇基团的极性相互作用也不同。SFC可用于GC或LC难以分离的复杂混合物的分离和组成分析，有望用于表面活性剂和合成聚合物等成分对性能和质量有显著影响的成分的精确分析。

{"title":"Separation of homologues and positional isomers of secondary alcohol ethoxylates via supercritical fluid chromatography","authors":"Akihiro Moriuchi , Yoshihiro Izumi , Toshiyuki Yamashita , Masatomo Takahashi , Takeshi Bamba","doi":"10.1016/j.chroma.2025.466543","DOIUrl":"10.1016/j.chroma.2025.466543","url":null,"abstract":"<div><div>Non-ionic surfactants consist of hydrophobic alkyl chains and hydrophilic polyethylene oxide (EO), whose distributions significantly influence properties such as hydrophilic–lipophilic balance and critical micelle concentration. In particular, secondary alcohol ethoxylates (AEOs), in which EO units are inserted within the alkyl chain, are complex mixtures that include multiple positional isomers in addition to homologous EO and alkyl‑chain distributions, making them difficult to separate via conventional liquid chromatography (LC) or gas chromatography (GC). Therefore, we evaluated supercritical fluid chromatography (SFC) for high-resolution analysis of these nonvolatile mixtures. Using an octadecylsilane (ODS) column without end‑capping (Inertsil ODS‑4 noEC, 2.1 mm inner diameter (i.d.) × 150 mm, 3 μm) connected in series (five columns, total length 750 mm), with a flow rate of 0.8 mL/min, column oven at 40 °C, and back pressure regulator set at 10 MPa, we achieved separation of positional isomers of secondary AEOs that had been previously unresolved. For example, five positional isomers of the C14 alkyl chain with EO6 were resolved (five peaks) in a single analysis (total run time 200 min), and the measured peak capacity was 67. This separation was due to differences in the molecular shapes of the positional isomers of secondary AEOs, which resulted in varying degrees of steric hindrance from the ODS group on the stationary phase surface and differences in polar interactions with the residual silanol groups. SFC is useful for separation and composition analysis of complex mixtures that are difficult to separate via GC or LC and is expected to be utilized for the precise analysis of components such as surfactants and synthetic polymers whose composition significantly affects performance and quality.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1765 ","pages":"Article 466543"},"PeriodicalIF":4.0,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145556050","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

New breakthrough in interfacial characterization: concept of molecular surface area of molecules from a static geometric constant into a dynamic thermodynamic property using inverse gas chromatography 界面表征的新突破：利用反相色谱法将分子表面积从静态几何常数转化为动态热力学性质。

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-11-12 DOI: 10.1016/j.chroma.2025.466542

Tayssir Hamieh

The accurate determination of the London dispersive surface energy (

γ_{s}^{d}

) of solids is a fundamental challenge in interfacial science, with implications for adhesion, wetting, catalysis, and material design. Conventional approaches to estimate

γ_{s}^{d}

rely on molecular models that approximate the surface area of probe molecules, yet these models treat molecular surface area as a fixed, geometry-based parameter, ignoring its thermodynamic dependence on temperature and the nature of the solid substrate. In this study, we introduce a new method to determine the temperature-dependent molecular surface area of n-alkanes and polar solvents adsorbed on solid oxides. The approach combines the Hamaker constant formalism with the London dispersive interaction equation, as we recently reformulated, to separate dispersive and polar contributions to the adsorption free energy. By integrating molecular polarizability and ionization energy with experimentally derived

γ_{s}^{d}

, we obtain, for the first time, a consistent thermodynamic expression of the molecular surface area as a function of temperature. This method resolves long-standing discrepancies among classical molecular models, provides unprecedented accuracy in

γ_{s}^{d}

determination, and opens pathways to extend the analysis to polymers, fibers, and nanostructured materials.

固体的伦敦色散表面能（γ - sd）的准确测定是界面科学的一个基本挑战，对粘附、润湿、催化和材料设计具有重要意义。传统的估算γ - sd的方法依赖于近似探针分子表面积的分子模型，然而这些模型将分子表面积作为一个固定的、基于几何的参数，忽略了它对温度和固体基质性质的热力学依赖。在这项研究中，我们介绍了一种新的方法来测定正构烷烃和极性溶剂吸附在固体氧化物上的温度依赖的分子表面积。该方法结合了Hamaker常数形式和我们最近重新表述的伦敦色散相互作用方程，以分离色散和极性对吸附自由能的贡献。通过将分子极化率和电离能与实验导出的γ - sd积分，我们首次得到了分子表面积随温度变化的一致热力学表达式。该方法解决了经典分子模型之间长期存在的差异，提供了前所未有的γ - sd测定精度，并开辟了将分析扩展到聚合物，纤维和纳米结构材料的途径。

{"title":"New breakthrough in interfacial characterization: concept of molecular surface area of molecules from a static geometric constant into a dynamic thermodynamic property using inverse gas chromatography","authors":"Tayssir Hamieh","doi":"10.1016/j.chroma.2025.466542","DOIUrl":"10.1016/j.chroma.2025.466542","url":null,"abstract":"<div><div>The accurate determination of the London dispersive surface energy (<span><math><msubsup><mi>γ</mi><mi>s</mi><mi>d</mi></msubsup></math></span>) of solids is a fundamental challenge in interfacial science, with implications for adhesion, wetting, catalysis, and material design. Conventional approaches to estimate <span><math><msubsup><mi>γ</mi><mi>s</mi><mi>d</mi></msubsup></math></span> rely on molecular models that approximate the surface area of probe molecules, yet these models treat molecular surface area as a fixed, geometry-based parameter, ignoring its thermodynamic dependence on temperature and the nature of the solid substrate. In this study, we introduce a new method to determine the temperature-dependent molecular surface area of n-alkanes and polar solvents adsorbed on solid oxides. The approach combines the Hamaker constant formalism with the London dispersive interaction equation, as we recently reformulated, to separate dispersive and polar contributions to the adsorption free energy. By integrating molecular polarizability and ionization energy with experimentally derived <span><math><msubsup><mi>γ</mi><mi>s</mi><mi>d</mi></msubsup></math></span>, we obtain, for the first time, a consistent thermodynamic expression of the molecular surface area as a function of temperature. This method resolves long-standing discrepancies among classical molecular models, provides unprecedented accuracy in <span><math><msubsup><mi>γ</mi><mi>s</mi><mi>d</mi></msubsup></math></span> determination, and opens pathways to extend the analysis to polymers, fibers, and nanostructured materials.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1765 ","pages":"Article 466542"},"PeriodicalIF":4.0,"publicationDate":"2025-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145547676","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