Journal of Chromatography A最新文献_第10页

Sodium alginate-supramolecular solvent composite beads for green extraction of triazole fungicides in dried chili and tea leaves followed by ultra-performance liquid chromatography 海藻酸钠-超分子溶剂复合微球超高效液相色谱法提取辣椒干和茶叶中三唑类杀菌剂。

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-12-27 DOI: 10.1016/j.chroma.2025.466659

Rawikan Kachangoon , Yanawath Santaladchaiyakit , Jitlada Vichapong

A green and efficient analytical method was developed for the simultaneous determination of triazole fungicides using sodium alginate/supramolecular solvent composite beads (SA-SUPRAS beads) as an adsorbent in dispersive solid-phase extraction (dSPE), followed by ultra-performance liquid chromatography (UPLC). The supramolecular solvent was synthesized by the aggregation of 1-dodecanol and tetrahydrofuran in a molar ratio of 1:5 and incorporated into the alginate solution before a one-step formation process. Although THF is not an ideal green solvent, its use was minimized and handled under fume hood conditions. The nanoscale micelle-bead interactions enhanced the adsorption performance. The structural and physicochemical characteristics of the SA-SUPRAS beads were evaluated by FTIR, TGA, BET, XRD, ¹H-NMR, SEM, and the adsorption kinetics, and the impact of salt concentration was also investigated. Additionally, the parameters influencing the desorption process, such as the sorbent amount, type, and volume of the desorption solvent, sample concentration and volume, and extraction time, were optimized. The method demonstrated excellent linearity within a concentration range of 9–500 μg L^-1, with a correlation coefficient (R²) of 0.99. Detection and quantification limits ranged from 3.00 to 10.00 μg L⁻¹ and 9.00 to 30.00 μg L⁻¹, respectively. The precision of the method, expressed as relative standard deviation, was <7 %. Furthermore, enrichment factors ranged from 48.40 to 53.13, and extraction recoveries were between 96.00 and 106.25 %. However, the SA-SUPRAS beads exhibited limited reusability, and substantial matrix effects originating from UV-absorbing co-extractives in chili and tea necessitated matrix-matched calibration for reliable quantification. These findings highlight that the SA-SUPRAS beads-dSPE procedure is a rapid, sensitive, and reduced-solvent alternative to conventional sample preparation methods for the reliable determination of triazole fungicides in dried chili and tea leaves.

建立了以海藻酸钠/超分子溶剂复合微球（SA-SUPRAS微球）为吸附剂，采用分散固相萃取-超高效液相色谱法同时测定三唑类杀菌剂的绿色高效分析方法。该超分子溶剂由1-十二醇和四氢呋喃以1:5的摩尔比聚合而成，并加入到海藻酸盐溶液中，一步形成。虽然THF不是理想的绿色溶剂，但它的使用被最小化并在通风柜条件下处理。纳米级胶束-球的相互作用增强了吸附性能。采用FTIR、TGA、BET、XRD、1H-NMR、SEM、吸附动力学等手段对SA-SUPRAS微球的结构和理化性质进行了表征，并考察了盐浓度对其吸附性能的影响。并对吸附剂用量、解吸溶剂种类和体积、样品浓度和体积、萃取时间等影响解吸过程的参数进行了优化。方法在9 ~ 500 μg L-1的浓度范围内线性良好，相关系数（R²）为0.99。检测和定量范围分别为3.00 ~ 10.00 μg L⁻¹和9.00 ~ 30.00 μg L⁻¹。方法的精密度为，以相对标准偏差表示

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引用次数: 0

Self-consistent determination of hold-up volume in normal-phase liquid chromatography: A dividing-plane framework for adsorption isotherm interpretation 正相液相色谱中自一致的持率测定：吸附等温线解释的分隔板框架。

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-12-27 DOI: 10.1016/j.chroma.2025.466658

Hung-Wei Tsui

The determination of total adsorption isotherms in liquid chromatography is fundamentally sensitive to the definition of the hold-up volume (

V_{L}^{'}

), which implicitly fixes the Gibbs-like dividing plane between the mobile and stationary phases. Conventional approaches often rely on arbitrary dead-time markers, leading to inconsistencies between excess and total adsorption quantities and potentially inducing artificial saturation artifacts in model fitting. To resolve this ambiguity, this study establishes a self-consistent dividing-plane framework coupled with affinity energy distribution analysis. Using minor disturbance method data for homologous alcohols (ethanol to butanol) on a cyano-silica column, we propose an iterative approach that adjusts the dividing plane until the model-derived isotherm slope reconciles with experimental perturbation times. This approach robustly deconvolutes the adsorption landscape into two distinct contributions: a high-affinity family (sites B) governing specific hydrogen-bonding interactions at the ligand surface, and a low-affinity family (sites A) representing non-specific solute accumulation within the diffuse interfacial region. Thermodynamic analysis further validates this mechanism, revealing that sites B exhibit a strongly exothermic enthalpy of adsorption (

Δ H^{0} \approx

-35 kJ/mol for 2-propanol), whereas sites A are energetically weaker and geometrically sensitive to the choice of the dividing plane. By strictly defining the reference state, this framework offers a rigorous route to separate specific binding from interfacial accumulation, yielding adsorption parameters that are physically interpretable and thermodynamically consistent.

液相色谱法中总吸附等温线的测定从根本上对保持体积（VL’）的定义敏感，它隐含地固定了流动相和固定相之间的吉布斯样划分面。传统方法通常依赖于任意的死区时间标记，导致过量和总吸附量之间的不一致，并可能在模型拟合中引起人为饱和伪影。为了解决这一歧义，本研究建立了一个自一致的划分平面框架，并结合亲和能分布分析。利用氰化硅柱上同源醇（乙醇到丁醇）的小扰动法数据，我们提出了一种迭代方法，调整划分平面，直到模型推导的等温线斜率与实验扰动时间相一致。这种方法有力地将吸附景观分解为两个不同的贡献：一个高亲和家族（位点B）控制配体表面特定的氢键相互作用，一个低亲和家族（位点a）代表弥散界面区域内非特异性溶质积累。热力学分析进一步验证了这一机理，发现B位具有很强的放热吸附焓（2-丙醇为ΔH0≈-35 kJ/mol），而a位的放热吸附焓较弱，且对划分平面的选择具有几何敏感性。通过严格定义参考状态，该框架提供了一种严格的途径来分离特定结合和界面积累，从而产生物理可解释和热力学一致的吸附参数。

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引用次数: 0

Sustainable three-dimensional printed devices for thin-film solid-phase microextraction in green and efficient determination of isoflavones in environmental waters 绿色高效测定环境水体中异黄酮的薄膜固相微萃取可持续三维打印装置。

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-12-27 DOI: 10.1016/j.chroma.2025.466661

Francielle Crocetta Turazzi , Danay Manzo Jaime , Leonardo Santana , Luciane Effting , Eduardo Carasek , Guilherme Mariz de Oliveira Barra

This study reports an efficient sample preparation method based on fused filament fabrication (FFF) 3D printing technology for the production of thin-film solid-phase microextraction (TF-SPME) devices, applied to the determination of four isoflavones, daidzein (DA), glycitein (GLY), genistein (GEN), and formononetin (FOR), in water samples. Eleven different filaments were used for fabricating devices to assess their influence on extraction efficiency. In addition to the selection of the printed device, critical parameters, including desorption solvent, desorption and extraction time, sample pH, and salting-out effect were optimized using univariate and multivariate strategies. Among all tested filaments, polyamide 6 (PA6) was identified as the most suitable and selected due to its higher extraction efficiency for all analytes. The extraction step consisted of 1.5 mL of sample, pH adjusted to 6, and 15% of sodium chloride (NaCl), extraction time of 30 min, followed by liquid desorption with 300 μL of methanol (MeOH) and 30 min of desorption time. The analytical parameters of merit of the method were evaluated, showing coefficients of determination (R²) equal to or greater than 0.9930. LODs and LOQs were 1.5 and 5 μg L⁻¹ for all analytes. Precisions were equal to or below 12.3%. Recoveries ranged from 69% to 109% and no matrix effect was observed. Seven water samples collected from different points were analyzed though the method, and the analytes were not detected, or were present at concentrations below the method’s LOD. The reusability of the devices was confirmed for up to 10 consecutive uses following a cleaning procedure.

本研究报告了一种基于熔丝制造（FFF） 3D打印技术的高效样品制备方法，用于生产薄膜固相微萃取（TF-SPME）装置，用于测定水样中的四种异黄酮，大豆苷元（DA）、glycitein （GLY）、染料木素（GEN）和刺芒柄花素（for）。采用11种不同的灯丝制作装置，评估其对萃取效率的影响。除了印刷装置的选择外，还对解吸溶剂、解吸萃取时间、样品pH、盐析效果等关键参数进行了单因素和多因素优化。在所有测试的长丝中，聚酰胺6 （PA6）被认为是最合适的，因为它对所有分析物的提取效率都很高。提取步骤为：样品1.5 mL， pH调至6，氯化钠（NaCl）用量为15%，提取时间30 min，甲醇（MeOH）浓度为300 μL，解吸时间30 min。对方法的分析参数进行评价，其决定系数（R2）等于或大于0.9930。所有分析物的lod和loq分别为1.5和5 μg L-1。精度等于或低于12.3%。加样回收率为69% ~ 109%，无基质效应。从不同地点采集的7个水样通过该方法进行了分析，分析物未被检测到，或者浓度低于该方法的LOD。在清洁程序后，设备的可重复使用性被确认为长达10次连续使用。

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引用次数: 0

Scouting of different separation strategies for phenolic compounds in comprehensive two-dimensional liquid chromatography 综合二维液相色谱法中酚类化合物不同分离策略的探索

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-12-25 DOI: 10.1016/j.chroma.2025.466654

Roberto Laganà Vinci , Carmelo Coppolino , Katia Arena , Francesco Cacciola , Patrik Appelblad , Paola Dugo , Luigi Mondello

Comprehensive two-dimensional liquid chromatography (LC × LC) offers unique opportunities to resolve structurally diverse analytes that cannot be fully characterized by conventional one-dimensional methods. In this work, different LC × LC configurations combining reversed-phase liquid chromatography (RP-LC) and hydrophilic interaction chromatography (HILIC) were systematically investigated for the separation of a 48-compound phenolic standard mixture. Special attention was devoted to the discussion of key method parameters affecting retention behaviour and selectivity in the different LC × LC configurations. Three setups, namely, HILIC × RP-LC, RP-LC × RP-LC, and RP-LC × HILIC were optimized using focusing modulation with active trapping and evaluated in terms of orthogonality, peak capacity, resolution, dilution factor, analysis time, and solvent consumption. Among the tested configurations, HILIC × RP-LC provided the best results in terms of both separation efficiency and operational sustainability with higher corrected peak capacity, reduced dilution, and enhanced throughput. On the one hand, RP-LC × RP-LC offered robust performance with broad applicability due to stationary-phase availability, whereas, RP-LC × HILIC showed complementary selectivity but lower eco-sustainability. The Red, Green, Blue (RGB) additive colour model was applied to integrate analytical, environmental, and productivity metrics, identifying HILIC × RP-LC as the most effective configuration. Finally, the optimized method was applied to the characterization of phenolic profiles in herbal liqueurs, enabling detailed fingerprinting of complex natural matrices. These findings highlight the importance of rationally selecting LC × LC configurations and demonstrate the potential of HILIC × RP-LC with focusing modulation for efficient, sustainable, and information-rich profiling of phenolic compounds.

综合二维液相色谱（LC × LC）提供了独特的机会来解决结构多样的分析物，不能完全表征传统的一维方法。本研究系统地研究了不同的LC × LC构型结合反相液相色谱（RP-LC）和亲水性相互作用色谱（HILIC）对48种化合物酚类标准混合物的分离。重点讨论了在不同LC × LC构型下影响保留行为和选择性的关键方法参数。采用主动捕集的聚焦调制技术对HILIC × RP-LC、RP-LC × RP-LC、RP-LC × HILIC三种方法进行了优化，并对正交性、峰容量、分辨率、稀释系数、分析时间和溶剂消耗进行了评价。在测试的配置中，HILIC × RP-LC在分离效率和操作可持续性方面均取得了最佳结果，具有更高的校正峰容量，降低稀释度，提高了吞吐量。一方面，RP-LC × RP-LC由于具有稳定期可用性，具有广泛的适用性，而RP-LC × HILIC具有互补选择性，但生态可持续性较低。采用红、绿、蓝（RGB）加色模型来整合分析、环境和生产率指标，确定HILIC × RP-LC是最有效的配置。最后，将优化后的方法应用于草药利口酒中酚类成分的表征，实现了复杂天然基质的精细指纹图谱。这些发现强调了合理选择LC × LC结构的重要性，并展示了HILIC × RP-LC在聚焦调制下高效、可持续和信息丰富的酚类化合物分析中的潜力。

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引用次数: 0

A rapid and sensitive method for the determination of vitamin E and carotenoids in vegetables and fruits using deep eutectic solvent-based dispersive liquid-liquid microextraction 深共晶溶剂基分散液液微萃取法测定蔬菜水果中维生素E和类胡萝卜素的快速灵敏方法

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-12-24 DOI: 10.1016/j.chroma.2025.466656

Mengting Cui , Qingpeng Gao , Jinling Bai , Mengting Fu , Zhiyu Liu , Zhixin Ouyang , Liyun Kong , Le Ma

Conventional extraction techniques for fat-soluble nutrient analysis in foods may present certain limitations, including variable or limited efficiency, high solvent consumption, lengthy procedures, and potential environmental and health concerns. This study evaluates deep eutectic solvents (DESs) as a green and efficient alternative for extracting vitamin E and carotenoids from vegetables and fruits. Conductor-like screening model for real solvents (COSMO-RS) simulation and experimental screening identified the menthol-thymol (1:2) DES as optimal due to the balanced distribution of polar and nonpolar sites within its components. A novel dispersive liquid-liquid microextraction method based on this DES (DES-DLLME) was developed and integrated with HPLC for the simultaneous quantitation of vitamin E and carotenoids. The optimized method demonstrated excellent analytical performance with low detection limits (0.01–0.18 µg/mL), satisfactory recovery rates (80.04–111.95 %), and high reproducibility (relative standard deviation, RSD < 16.83 %). When applied to a range of Chinese food samples, the obtained nutrient profiles were largely consistent with USDA reference data, with observed variations likely due to factors such as geographic origin, cultivation practices, and post-harvest processing. This DES-based approach offers an efficient, reproducible, and environmentally friendly method for determining fat-soluble vitamins and carotenoids in complex food matrices, offering significant value for food quality assessment and nutritional research.

用于食品中脂溶性营养素分析的传统提取技术可能存在某些局限性，包括效率可变或有限、溶剂消耗高、程序冗长以及潜在的环境和健康问题。本研究评价了深共晶溶剂（DESs）作为一种绿色高效的从蔬菜和水果中提取维生素E和类胡萝卜素的替代方法。真实溶剂类导体筛选模型（cosmos - rs）模拟和实验筛选表明，薄荷-百里香酚（1:2）DES是最佳的，因为其组分中极性和非极性位点分布平衡。建立了一种基于DES （DES- dllme）的分散液液微萃取方法，并将其与高效液相色谱相结合，用于同时测定维生素E和类胡萝卜素的含量。优化后的方法检出限低（0.01 ~ 0.18µg/mL），回收率高（80.04 ~ 111.95%），重现性好（相对标准偏差，RSD < 16.83%）。当应用于一系列中国食品样品时，所获得的营养概况与美国农业部的参考数据基本一致，观察到的变化可能是由于地理来源、种植方法和收获后加工等因素造成的。该方法为复杂食品基质中脂溶性维生素和类胡萝卜素的测定提供了一种高效、可重复、环保的方法，为食品质量评估和营养研究提供了重要价值。

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引用次数: 0

Efficient analysis of sodium chromate by combining phase-transfer headspace strategy and GC-TCD 相转移顶空策略与GC-TCD相结合的高效分析铬酸钠

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-12-24 DOI: 10.1016/j.chroma.2025.466657

Wei-Qi Xie, Ya-Yun Wang, Yi-Xan Gong

This study developed a gas-evolving phase-transfer strategy for precise sodium chromate quantification. The analytical approach utilized the chemical reaction between sodium chromate and oxalic acid to generate measurable carbon dioxide, which was subsequently quantified via headspace gas chromatography equipped with thermal conductivity detector (HS-GC-TCD). Experimental validation confirmed the method's exceptional analytical performance in sodium chromate determination. The developed phase transformation technique established a robust and efficient protocol for sodium chromate assessment while simultaneously creating a framework for extending this analytical paradigm to other gas-evolving compounds.

本研究开发了一种用于精确定量铬酸钠的气相转移策略。分析方法利用铬酸钠和草酸之间的化学反应产生可测量的二氧化碳，随后通过配备热导检测器的顶空气相色谱（HS-GC-TCD）进行定量。实验验证了该方法在铬酸钠测定中具有优异的分析性能。开发的相变技术为铬酸钠的评估建立了一个强大而有效的协议，同时创建了一个框架，将这种分析范式扩展到其他气态化合物。

引用次数: 0

Development and validation of a multi-class solid-phase extraction and liquid chromatography tandem mass spectrometry method for emerging contaminants in water 多类固相萃取-液相色谱串联质谱法用于水中新出现污染物的开发与验证。

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-12-24 DOI: 10.1016/j.chroma.2025.466655

Madara Weerasooriyagedara , Jordan M. Partington , Wejdan Alghamdi , Mulugeta Legesse Akele , Stefano Freguia , Bradley O. Clarke

A robust and sensitive liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed for the simultaneous quantification of 39 multi-class emerging contaminants (ECs), encompassing diverse groups including industrial chemicals (n = 6), pharmaceuticals (n = 19), personal care products (n = 4), and pesticides (n = 10). LC-MS/MS parameters were systematically optimized, including compound-specific transitions, source conditions, mobile phase composition, injection volumes, and chromatographic flow rates, to maximize signal intensity and ensure reproducible detection. Solid-phase extraction (SPE) was further optimized through evaluation of reconstitution solvent composition, evaporation settings, washing solvents, and elution strategies to improve recoveries and minimize matrix effects. The final method achieved instrument detection limits as low as 0.01 fg on-column, with method detection and quantitation limits of 0.01–1.32 ng/L and 0.03–3.96 ng/L, respectively. Calibration linearity (R² >0.99), recoveries within 70–130%, and intra-/inter-day precision (RSD ≤20%) confirmed the robustness and reproducibility of the protocol. Application to six real water matrices, bottled water, tap water, surface water, seawater, wastewater effluent, and influent, revealed the highest concentrations and widest range of analytes in influent, lower but quantifiable levels of persistent compounds in effluent, and predominantly trace-level detections or non-detects in natural and potable waters. Complementary greenness and applicability assessments using AGREE, MoGAPI, and BAGI highlighted moderate environmental sustainability and strong practical utility, reinforcing the suitability of the method for routine monitoring, source tracking, regulatory compliance, and risk assessment applications requiring ultra-trace sensitivity, high selectivity, and broad chemical coverage.

建立了一种高效灵敏的液相色谱-串联质谱（LC-MS/MS）方法，用于同时定量39种多类别新兴污染物（ECs），包括工业化学品（n = 6）、药品（n = 19）、个人护理产品（n = 4）和农药（n = 10）。系统优化了LC-MS/MS参数，包括化合物特异性过渡、源条件、流动相组成、进样量和色谱流速，以最大限度地提高信号强度并确保检测的重复性。通过评价固相萃取（SPE）的重构溶剂组成、蒸发设置、洗涤溶剂和洗脱策略，进一步优化固相萃取（SPE），以提高回收率并最大限度地减少基质效应。最终方法柱上检出限低至0.01 fg，方法检出限为0.01 ~ 1.32 ng/L，定量限为0.03 ~ 3.96 ng/L。校准线性（R²>0.99），回收率在70-130%范围内，日内/日间精密度（RSD≤20%）证实了该方案的稳健性和重复性。对六种实际水基质（瓶装水、自来水、地表水、海水、废水排放和进水）的应用显示，进水中分析物的浓度最高，范围最广，污水中持久性化合物的含量较低，但可量化，在自然和饮用水中主要检测到痕量水平或未检测到痕量水平。使用AGREE、MoGAPI和BAGI的互补绿色和适用性评估强调了适度的环境可持续性和强大的实用性，加强了常规监测、来源跟踪、法规遵从性和风险评估应用的适用性，这些应用需要超痕量灵敏度、高选择性和广泛的化学覆盖。

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引用次数: 0

Analysis of mRNA multimerisation (aggregation) using non-denaturing ion-pair reversed-phase liquid chromatography 使用非变性离子对反相液相色谱分析mRNA多聚（聚集）。

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-12-24 DOI: 10.1016/j.chroma.2025.466653

Alexandra L.J. Webb , Emma N. Welbourne , Thomas C. Minshull , Kate A. Loveday , Prerna Bora , Zoltán Kis , Gunilla A. Nilsson , Andal Murthy , Eivor Örnskov , Mark J. Dickman

mRNA-based technology has emerged as a new class of medicines with a wide range of applications, including viral vaccines, cancer vaccines, and therapeutics for the treatment of metabolic diseases and cardiovascular conditions. Impurities, including double-stranded RNA (dsRNA), mRNA fragments, and mRNA multimers (aggregates) that result from the manufacturing of mRNA, as well as from subsequent purification, formulation, and storage, can potentially impact the safety and efficacy of mRNA medicines.

mRNA higher-order structures and mRNA multimers (aggregates) can affect translational efficiency and also impact the efficiency of formulation into lipid nanoparticles. mRNA purity is typically analysed using denaturing or partially denaturing methods, precluding the detection of mRNA multimers (aggregates). In this study, we developed and utilised ion-pair reversed-phase HPLC (IP-RP HPLC) under non-denaturing conditions to analyse mRNA multimers. The inclusion of 1 mM Mg²⁺ in the mobile phase stabilises mRNA higher-order structures, RNA:RNA interactions, and the formation of mRNA dimers/multimers, which can be readily separated from the mRNA monomers.

The ability to resolve mRNA monomers from mRNA dimers/multimers was demonstrated for a range of mRNA sequences and lengths. Moreover, we have shown that the relative abundance of mRNA dimers/multimers is concentration dependent. Using the relative percentage of dimer vs concentration of monomer, we were able to determine that the K_d of the interaction between two eGFP mRNA monomers was 82.93 nM. Characterisation and sizing of the mRNA multimers was performed using mass photometry analysis following the purification of mRNA monomer and dimer/multimer peaks using IP-RP HPLC.

Thus, non-denaturing IP-RP demonstrates significant advantages over current approaches for the analysis of mRNA multimers (aggregates). The high-throughput, temperature-dependent profiling of mRNA multimerisation using IP-RP HPLC will enable further comparative studies on the stability of mRNA multimers and provide important insights into potential factors influencing mRNA multimerisation.

基于mrna的技术已成为一类具有广泛应用的新型药物，包括病毒疫苗、癌症疫苗以及用于治疗代谢疾病和心血管疾病的疗法。杂质，包括双链RNA （dsRNA）、mRNA片段和mRNA多聚体（聚集体），这些杂质来自mRNA的制造以及随后的纯化、配方和储存，可能会影响mRNA药物的安全性和有效性。mRNA高阶结构和mRNA多聚体（聚集体）可以影响翻译效率，也影响脂质纳米颗粒配方的效率。mRNA纯度通常使用变性或部分变性方法进行分析，排除了mRNA多聚体（聚集体）的检测。在这项研究中，我们在非变性条件下开发并使用了离子对反相高效液相色谱（IP-RP HPLC）来分析mRNA多聚体。在流动相中加入1mm Mg²⁺可以稳定mRNA的高阶结构、RNA:RNA的相互作用，以及mRNA二聚体/多聚体的形成，这些二聚体/多聚体可以很容易地从mRNA单体中分离出来。从mRNA二聚体/多聚体中分离mRNA单体的能力在mRNA序列和长度范围内得到了证明。此外，我们已经证明mRNA二聚体/多聚体的相对丰度与浓度有关。利用二聚体相对于单体浓度的相对百分比，我们可以确定两个eGFP mRNA单体相互作用的Kd为82.93 nM。在使用IP-RP高效液相色谱纯化mRNA单体和二聚体/多聚体峰后，使用质谱分析对mRNA多聚体进行表征和分级。因此，非变性IP-RP在分析mRNA多聚体（聚合体）方面比目前的方法具有显著的优势。利用IP-RP高效液相色谱对mRNA多聚合进行高通量、温度依赖性分析，将有助于对mRNA多聚合体的稳定性进行进一步比较研究，并为影响mRNA多聚合的潜在因素提供重要见解。

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引用次数: 0

Molecularly imprinted polymer-based HPLC column and smart syringe for selective extraction of quercetin from complex plant extracts: A sustainable and green approach 分子印迹聚合物高效液相色谱柱和智能注射器从复杂植物提取物中选择性提取槲皮素：一种可持续和绿色的方法

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-12-24 DOI: 10.1016/j.chroma.2025.466651

Sumera Shezadi , Muhammad Ali Minhas , Muhammad Shaiq Ali , Muhammad Imran Malik

Quercetin (QR) is a bioactive flavonoid naturally present in various fruits and vegetables, known for its potent antioxidant, antidiabetic, and anti-inflammatory activities. Efficient and sustainable extraction of QR is essential for its wide-ranging applications as a nutraceutical; however, conventional extraction techniques are often time-consuming, solvent-intensive, and environmentally unfriendly. In this study, a quercetin-imprinted polymer (QR-MIP) was synthesized via bulk polymerization using 2-hydroxyethyl methacrylate (HEMA) as the functional monomer and ethylene glycol dimethacrylate (EGDMA) as the crosslinker. The resulting polymer was characterized by SEM, FT-IR, BET, and TGA to confirm its morphological, structural, and thermal properties. Batch rebinding experiments revealed that the QR-MIP exhibited a high binding capacity of 26.7 mg/g, markedly exceeding that of the non-imprinted polymer (6.9 mg/g), with an imprinting factor of 3.8. The adsorption behavior was well-described by the Langmuir isotherm and pseudo-second-order kinetic model, indicating homogeneous and specific binding interactions. Selectivity assessments demonstrated the superior molecular recognition of QR-MIP toward quercetin compared to structurally similar analogs, confirming the presence of specific imprinting sites. The developed MIP was successfully integrated into an HPLC column and a smart syringe system for selective extraction and preconcentration of quercetin from complex matrices utilizing a low volume of less toxic tetrahydrofuran The proposed approach enables sustainable multi-cycle purification while consuming only a few milliliters of organic solvent, in contrast to the liters typically required in conventional protocols. This work presents a novel, green, and cost-effective approach for targeted enrichment of quercetin, offering promising potential for the selective isolation of other nutraceuticals and natural bioactive compounds.

槲皮素（QR）是一种天然存在于各种水果和蔬菜中的生物活性类黄酮，以其有效的抗氧化、抗糖尿病和抗炎活性而闻名。有效和可持续地提取QR对于其作为营养保健品的广泛应用至关重要；然而，传统的提取技术往往耗时，溶剂密集，环境不友好。本研究以甲基丙烯酸2-羟乙酯（HEMA）为功能单体，乙二醇二甲基丙烯酸酯（EGDMA）为交联剂，通过体聚法制备了槲皮素印迹聚合物（QR-MIP）。通过SEM、FT-IR、BET和TGA等手段对聚合物进行了表征，确定了聚合物的形态、结构和热性能。批量重结合实验表明，QR-MIP具有26.7 mg/g的高结合能力，明显超过非印迹聚合物（6.9 mg/g），印迹因子为3.8。Langmuir等温线和拟二级动力学模型很好地描述了吸附行为，表明了均匀和特异性的结合相互作用。选择性评估表明，与结构相似的类似物相比，QR-MIP对槲皮素具有优越的分子识别能力，证实了特定印迹位点的存在。开发的MIP成功地集成到高效液相色谱柱和智能注射器系统中，利用小体积毒性较小的四氢呋喃从复杂基质中选择性提取和预浓缩槲皮素。所提出的方法可以实现可持续的多循环纯化，同时仅消耗几毫升有机溶剂，而传统方案通常需要升。这项工作提出了一种新颖、绿色、经济的靶向富集槲皮素的方法，为其他营养药品和天然生物活性化合物的选择性分离提供了广阔的前景。

{"title":"Molecularly imprinted polymer-based HPLC column and smart syringe for selective extraction of quercetin from complex plant extracts: A sustainable and green approach","authors":"Sumera Shezadi , Muhammad Ali Minhas , Muhammad Shaiq Ali , Muhammad Imran Malik","doi":"10.1016/j.chroma.2025.466651","DOIUrl":"10.1016/j.chroma.2025.466651","url":null,"abstract":"<div><div>Quercetin (QR) is a bioactive flavonoid naturally present in various fruits and vegetables, known for its potent antioxidant, antidiabetic, and anti-inflammatory activities. Efficient and sustainable extraction of QR is essential for its wide-ranging applications as a nutraceutical; however, conventional extraction techniques are often time-consuming, solvent-intensive, and environmentally unfriendly. In this study, a quercetin-imprinted polymer (QR-MIP) was synthesized via bulk polymerization using 2-hydroxyethyl methacrylate (HEMA) as the functional monomer and ethylene glycol dimethacrylate (EGDMA) as the crosslinker. The resulting polymer was characterized by SEM, FT-IR, BET, and TGA to confirm its morphological, structural, and thermal properties. Batch rebinding experiments revealed that the QR-MIP exhibited a high binding capacity of 26.7 mg/g, markedly exceeding that of the non-imprinted polymer (6.9 mg/g), with an imprinting factor of 3.8. The adsorption behavior was well-described by the Langmuir isotherm and pseudo-second-order kinetic model, indicating homogeneous and specific binding interactions. Selectivity assessments demonstrated the superior molecular recognition of QR-MIP toward quercetin compared to structurally similar analogs, confirming the presence of specific imprinting sites. The developed MIP was successfully integrated into an HPLC column and a smart syringe system for selective extraction and preconcentration of quercetin from complex matrices utilizing a low volume of less toxic tetrahydrofuran The proposed approach enables sustainable multi-cycle purification while consuming only a few milliliters of organic solvent, in contrast to the liters typically required in conventional protocols. This work presents a novel, green, and cost-effective approach for targeted enrichment of quercetin, offering promising potential for the selective isolation of other nutraceuticals and natural bioactive compounds.</div></div>","PeriodicalId":347,"journal":{"name":"Journal of Chromatography A","volume":"1767 ","pages":"Article 466651"},"PeriodicalIF":4.0,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145837206","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

Cyclodextrin-assisted vortex dispersive solid-phase extraction coupled with sweeping-field amplified sample stacking for CE analysis of weakly ionized components in complex matrices 环糊精辅助涡旋色散固相萃取与扫场放大样品堆积相结合用于复杂基质中弱电离组分的CE分析

IF 4 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2025-12-23 DOI: 10.1016/j.chroma.2025.466647

Yaxin Cheng , Yaxin Qin , Wenli Sun , Jian Xu , Guanghui Zhong , Xin Peng , Chu Chu

Simultaneous multi-component analysis of trace-level weakly ionized analytes in complex matrices remains a critical challenge for capillary electrophoresis (CE). To address this, this study developed a novel green analytical strategy by integrating cyclodextrin vortex-assisted dispersive solid-phase extraction (CD-VA-DSPE) with CD-assisted sweeping-field amplified sample stacking (CD-sweeping-FASS) in micellar electrokinetic chromatography (MEKC). The core innovation lies in the dual role of hydroxypropyl-β-cyclodextrin (HP-β-CD) as both an extraction solvent and a pseudostationary phase, enabling a seamless integration of sample preparation and online enrichment. Using the traditional Chinese medicine "Wenyangxiaozheng formula" as a model, the optimized method achieved baseline separation of four target components (lobetyolin, echinacoside, acteoside, calycosin), marking the first demonstration of CD-sweeping-FASS in MEKC for phytochemical analysis. Method validation demonstrated excellent linearity (r ≥ 0.9992) over a concentration range of 1–100 µg mL⁻¹, with limits of detection (LODs) of 0.02–0.05 µg mL⁻¹. The precision was satisfactory (intra- and inter-day RSDs < 2.98 %). Remarkably, compared with conventional CE injection, the method achieved sensitivity enhancements of 106- to 208-fold. With the successful application in quantitative analysis of target components (0.46–9.93 µg mg⁻¹) in both herbal formulations and spiked rat serum, the proposed approach establishes itself as a high-throughput and sustainable solution for the simultaneous determination of trace weakly ionized compounds in complex matrices.

复杂基质中痕量弱电离分析物的同时多组分分析一直是毛细管电泳（CE）的一个关键挑战。为了解决这一问题，本研究将环糊精涡旋辅助分散固相萃取（CD-VA-DSPE）与cd辅助扫场放大样品堆积（cd -sweep - fass）结合在胶束电动色谱（MEKC）中，开发了一种新的绿色分析策略。核心创新在于羟丙基-β-环糊精（HP-β-CD）作为萃取溶剂和假固定相的双重作用，实现了样品制备和在线富集的无缝集成。优化后的方法以中药“温阳消正方”为模型，实现了四种目标成分（莲子苷、紫锥花苷、毛蕊花苷、毛蕊花苷）的基线分离，首次在MEKC中应用cd -扫描法进行植物化学分析。方法验证表明，在1-100µg mL⁻¹的浓度范围内，线性良好（r≥0.9992），检测限（lod）为0.02-0.05µg mL⁻¹。精密度满意（日内、日间rsd = 2.98%）。值得注意的是，与传统的CE注射相比，该方法的灵敏度提高了106- 208倍。与目标组件的成功应用在定量分析(0.46 - -9.93µg mg⁻¹)草药配方和尖刺鼠血清,建议的方法建立本身作为一种高通量和可持续的解决方案的同时测定微量弱电离的化合物在复杂的矩阵。

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引用次数: 0