Advances in Sample Preparation最新文献_第2页

Ionic liquid-grafted aminosilica-graphene oxide sorbent for efficient microextraction by packed sorbent of multiclass pesticides in wine 离子液体接枝氨基硅-氧化石墨烯吸附剂对葡萄酒中多类农药的高效微萃取

IF 6.5 Q1 CHEMISTRY, ANALYTICAL

Advances in Sample Preparation

Pub Date : 2025-10-01 Epub Date: 2025-10-13 DOI: 10.1016/j.sampre.2025.100217

Alessandra Timóteo Cardoso , Gloria Domínguez-Rodríguez , Alejandro Cifuentes , Fernando Mauro Lanças

Monitoring pesticide residues in wine is essential for ensuring food safety, as these compounds and their metabolites can persist in the final product and pose potential health risks. This study reports the development of a hybrid sorbent based on graphene oxide anchored to aminosilica particles (GO@Si), functionalized with ionic liquids (ILs) via direct anion-exchange. Among the tested combinations, GO@Si-[VHIm]⁺PF₆⁻ exhibited the best extraction performance due to its multiple interaction mechanisms with analytes. This sorbent was integrated into a microextraction by packed sorbent (MEPS) system for the extraction of six multiclass pesticides from wine, followed by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) analysis. After optimizing extraction conditions using univariate and multivariate approaches, the method demonstrated excellent linearity (r² ≥ 0.9958), satisfactory precision (RSDs < 15 %), and recoveries ranging from 49 % to 112 %. Limits of quantification were from 0.030 to 0.130 ng mL⁻¹, with negligible matrix effects in white, red, and rosé wines. The method also presented notable green advantages, including device reusability (up to six cycles) and low solvent consumption (0.7 mL per extraction). Sustainability assessments using AGREEprep and BAGI yielded favourable scores (0.52 and 57.5, respectively). This pilot study provides a promising and environmentally conscious analytical approach for multiclass pesticide monitoring in wines, with potential for further development into routine analysis.

监测葡萄酒中的农药残留对确保食品安全至关重要，因为这些化合物及其代谢物可能持续存在于最终产品中，并构成潜在的健康风险。本研究报告了一种基于氧化石墨烯锚定到氨基二氧化硅颗粒（GO@Si）的混合吸附剂的开发，通过直接阴离子交换与离子液体（ILs）功能化。在测试的组合中，GO@Si-[VHIm]⁺PF₆⁻由于与被测物的多重作用机制，表现出最好的萃取性能。将该吸附剂集成到包装吸附剂（MEPS）微萃取系统中，用于从葡萄酒中提取6种多类农药，并进行高效液相色谱-串联质谱（HPLC-MS/MS）分析。采用单因素和多因素优化提取条件，结果表明，该方法线性度高（r²≥0.9958），精密度高（rsd = 15%），加样回收率为49% ~ 112%。定量限为0.030 ~ 0.130 ng mL（毒血症），在白、红、红葡萄酒中基质效应可以忽略不计。该方法还具有显著的绿色优势，包括设备可重复使用（多达6次循环）和低溶剂消耗（每次提取0.7 mL）。使用AGREEprep和BAGI的可持续性评估获得了有利的分数（分别为0.52和57.5）。本初步研究为葡萄酒中多种农药的监测提供了一种有前景的、环保的分析方法，并有进一步发展为常规分析的潜力。

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引用次数: 0

Introducing a modified sample preparation and straightforward elemental ratio determination strategy with LA-ICP-MS to expand the nanoparticle probing toolkit 引入改进的样品制备和直接元素比测定策略与LA-ICP-MS扩展纳米颗粒探测工具箱

IF 6.5 Q1 CHEMISTRY, ANALYTICAL

Advances in Sample Preparation

Pub Date : 2025-10-01 Epub Date: 2025-11-02 DOI: 10.1016/j.sampre.2025.100223

Olga Lanaridi , Yan Chen , Jakob Nils Blaschke , Pablo Ayala , Bernhard C. Bayer , Dominik Eder , Andreas Limbeck

Nanoparticles (NPs) are employed in a wide range of applications due to some of their unique characteristics. Since their properties are partly determined by their composition, accurate determination of their stoichiometry is of paramount importance for optimization and fine tuning of their properties.

We propose a laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) procedure which enables determination of NP composition. Small NP quantities (approx. 1 mg) are dispersed in a polymeric solution which is then spin coated onto a Si wafer, thereby ensuring uniform distribution of the NPs within the thin polymer film deposited on the Si substrate. Matrix-matched standards are similarly prepared by mixing elemental aqueous stock solutions with the same polymer solution, followed by spin coating.

After thorough optimization of the sample preparation, and the parameters used for laser-ablation and subsequent ICP-MS analysis, the content of the analytes could be determined with a relative standard deviation (RSD) of < 2 % for standards and < 3–8 % for the NP samples, depending on the NP type, with detection limits lower than 0.2000 µg/g for all elements. Based on the results determined for the individual NP constituents, prevailing elemental ratios have been assessed.

Yttria-doped zirconia of known stoichiometry, i.e., (ZrO₂)_0.98(Y₂O₃)_0.08, was used as a reference material to validate the fit of the developed approach for the stoichiometric determination of NPs. The experimentally determined stoichiometry is in agreement with the one provided by the manufacturer. The applicability of the method is further demonstrated by assessment of the loading of CdS rods with medium-entropy (CoNiMoW)S NPs, which are interesting as novel catalysts and stoichiometric determination of Zr-based metal organic frameworks (MOFs), which function as catalysts in CO₂ reduction.

纳米粒子（NPs）由于其一些独特的特性而被广泛应用。由于它们的性质部分是由它们的组成决定的，因此准确测定它们的化学计量对于优化和微调它们的性质至关重要。我们提出了一种激光烧蚀-电感耦合等离子体质谱（LA-ICP-MS）程序，可以确定NP组成。小的NP数量(大约。1毫克)分散在聚合物溶液中，然后自旋涂覆在硅晶片上，从而确保NPs在沉积在硅衬底上的薄聚合物薄膜内均匀分布。基质匹配的标准品同样是通过将元素水原液与相同的聚合物溶液混合，然后进行旋转涂层来制备的。经过对样品制备、激光烧蚀及后续ICP-MS分析参数的全面优化，根据NP类型，标准样品的相对标准偏差（RSD）为2%，NP样品的相对标准偏差（RSD）为3 - 8%，所有元素的检出限均低于0.2000µg/g。根据对单个NP成分确定的结果，评估了普遍的元素比率。以已知化学计量的氧化锆（ZrO2）0.98(Y2O3)0.08作为对照物质，验证了该方法测定NPs化学计量的拟合性。实验测定的化学计量与厂家提供的一致。该方法的适用性通过评估具有中熵（CoNiMoW）S NPs的CdS棒的负载以及化学计量学测定作为CO2还原催化剂的zr基金属有机框架（mof）进一步得到验证。

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引用次数: 0

Versatile sorbent materials in sample preparation: Where do we go next? 样品制备中的多功能吸附材料：我们下一步要做什么？

IF 6.5 Q1 CHEMISTRY, ANALYTICAL

Advances in Sample Preparation

Pub Date : 2025-10-01 Epub Date: 2025-09-04 DOI: 10.1016/j.sampre.2025.100211

Rafael Oliveira Martins, Maria Flávia Assunção Magalhães, Winnie Evelyn Valeria Perez Vite, Jussara da Silva Alves, Camila Will, Fernando Mauro Lanças

Continuous advances in sample preparation methods have led to the development of enhanced strategies to address the complexity of diverse matrices in both qualitative and quantitative analyses. These methods are designed to facilitate sample clean-up and preconcentration of target analytes before analysis by different analytical instruments. In both conventional and miniaturized solid-based approaches, the analytical performance of the extraction is primarily influenced by the sorbent phase. As the sorbent is responsible for mediating the interaction between the target analytes and the extraction material, careful selection is essential. In this context, a wide range of sorbent materials has been introduced to ensure efficient and selective interactions, supporting their application in sample preparation protocols. Nevertheless, the literature still lacks comprehensive and up-to-date reviews that highlight recent advances in sorbent development, including both conventional and bio-based alternatives. Therefore, this review aims to provide a current overview of sorbent innovations, discuss emerging trends, and outline potential future directions in the field.

样品制备方法的不断进步导致了增强策略的发展，以解决定性和定量分析中不同矩阵的复杂性。这些方法的目的是在不同的分析仪器分析之前，方便样品的清理和目标分析物的预浓缩。在传统和小型固体基方法中，萃取的分析性能主要受吸附相的影响。由于吸附剂负责调节目标分析物和萃取物质之间的相互作用，因此仔细选择是必不可少的。在这种情况下，广泛的吸附剂材料已经被引入，以确保有效和选择性的相互作用，支持它们在样品制备方案中的应用。然而，文献仍然缺乏全面和最新的评论，强调吸附剂发展的最新进展，包括传统和生物基替代品。因此，本综述旨在提供吸附剂创新的当前概述，讨论新兴趋势，并概述该领域潜在的未来方向。

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引用次数: 0

In-situ simultaneous extraction of non-steroidal anti-inflammatory drugs from wastewater using 3D-printed device and UHPLC-DAD/FLD analysis 利用3d打印装置和UHPLC-DAD/FLD分析同时提取废水中非甾体类抗炎药

IF 6.5 Q1 CHEMISTRY, ANALYTICAL

Advances in Sample Preparation

Pub Date : 2025-10-01 Epub Date: 2025-09-01 DOI: 10.1016/j.sampre.2025.100210

César Castro-García , Arianna Palermo , Edwin Palacio , Luz O. Leal , Laura Ferrer

Non-steroidal anti-inflammatory drugs (NSAIDs) are widely employed in medicine for their anti-inflammatory and antipyretic properties. Their occurrence has been documented in effluents from wastewater treatment plants (WWTPs), as well as in aquatic ecosystems. NSAIDs are classified as emerging contaminants, thereby underscoring the importance of their environmental monitoring. This study presents a novel approach for the simultaneous on-site extraction of six NSAIDs –acetylsalicylic acid (ASP), celecoxib (CEL), diclofenac (DIC), ibuprofen (IBU), ketoprofen (KET), and naproxen (NAP)– from wastewater, followed by ultra-high performance liquid chromatography coupled with photodiode array and fluorescence detection (UHPLC-DAD/FLD). A 3D-printed device, coated with a highly selective solid-phase extraction (SPE) resin (Oasis HLB®), enabled on-site extraction and preconcentration of the analytes, avoiding to handle large sample volumes. A peristaltic pump helps both retention and elution steps. Method detection limits were 0.12 µg L^-1 for ASP, 0.16 µg L^-1 for CEL and IBU, 1.5 µg L^-1 for DIC, 0.09 µg L^-1 for KET and 0.19 µg L^-1 for NAP. The analytical performance of the 3D-printed device was demonstrated by precision below 5 % and the possibility of reusing up to 24 times without significant loss of extraction efficiency. An AGREEprep score of 0.53 classifies this methodology as moderately green. On-site analysis was conducted at the Calvià WWTP (Mallorca, Spain), where five NSAIDs were detected at various stages, demonstrating the feasibility of the on-site extraction across a broad concentration range. Except for ASP, which exhibited a recovery rate below 47 %, the remaining analytes showed satisfactory recoveries, ranging from 90 to 98 %.

非甾体抗炎药（NSAIDs）因其抗炎和解热的特性而被广泛应用于医学领域。它们在废水处理厂（WWTPs）的流出物以及水生生态系统中都有记录。非甾体抗炎药被归类为新兴污染物，因此强调了其环境监测的重要性。本研究建立了一种从废水中同时现场提取乙酰水杨酸（ASP）、塞来昔布（CEL）、双氯芬酸（DIC）、布洛芬（IBU）、酮洛芬（KET）和萘普生（NAP） 6种非甾体抗炎药的新方法，并采用超高效液相色谱-光电二极管阵列和荧光检测（UHPLC-DAD/FLD）。3d打印设备，涂有高选择性固相萃取（SPE）树脂（Oasis HLB®），可以现场提取和预浓缩分析物，避免处理大样本量。蠕动泵有助于保留和洗脱步骤。方法检出限分别为ASP 0.12µg L-1、CEL和IBU 0.16µg L-1、DIC 1.5µg L-1、KET 0.09µg L-1、NAP 0.19µg L-1。3d打印设备的分析性能被证明精度低于5%，并且可以重复使用多达24次，而不会显著降低提取效率。AGREEprep得分为0.53，将这种方法归类为中度绿色。在calvio污水处理厂（西班牙Mallorca）进行了现场分析，在不同阶段检测到五种非甾体抗炎药，证明了在广泛浓度范围内现场提取的可行性。除ASP回收率低于47%外，其余分析物的回收率均在90% ~ 98%之间，令人满意。

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引用次数: 0

Investigating the impact of novel brominated flame retardants (NBFRs) on metabolite and nutritional profiles in aquatic organisms by in vivo solid-phase microextraction (SPME) 利用体内固相微萃取（SPME）技术研究新型溴化阻燃剂对水生生物代谢物和营养成分的影响

IF 6.5 Q1 CHEMISTRY, ANALYTICAL

Advances in Sample Preparation

Pub Date : 2025-10-01 Epub Date: 2025-09-04 DOI: 10.1016/j.sampre.2025.100212

Tianning Chen , Pengfei Ye , Chen Yuan , Ling Fang , Nan Li , Guosheng Chen , Junlang Qiu , Fang Zhu , Gangfeng Ouyang

Novel brominated flame retardants (NBFRs), due to their ubiquitous environmental distribution in aquatic ecosystems and potential adverse effects to aquatic biota, have initiated global concerns. NBFRs were absorbed and bioaccumulated into aquatic organisms, impairing their growth while significantly disrupting metabolic and nutritional profiles deserves further elucidation, especially for in vivo and in situ characterization. In this study, we selected tilapia (Oreochromis mossambicus) as a model and developed an innovative in vivo sampling method using solid-phase microextraction (SPME) with a cationic covalent organic framework (COF) coating fiber, coupled with high performance liquid chromatography-electrospray ionization-Orbitrap mass spectrometry (HPLC-ESI-Orbitrap-MS) analysis. Our results demonstrated that self-made SPME fibers possessed excellent broad-spectrum extraction ability (totally 5250 molecular features were detected), and the developed analysis method has the advantages of greenness. SPME technology based on our self-made fiber was successfully applied in research of the impacts of NBFRs on tilapia. After statistical analysis, a total of 811 metabolites exhibited significant differential expression, including the nutritional components such as amino acids, glycosides, and lipids, which resulted in a decline in nutritional quality. These findings provided a new perspective for evaluating the ecological risk assessment of NBFRs, nutritional quality assessment of aquatic organisms and securing fishery products.

新型溴化阻燃剂（NBFRs）由于其在水生生态系统中普遍存在的环境分布和对水生生物群的潜在不利影响，引起了全球的关注。nfrs被吸收并积累到水生生物中，损害了它们的生长，同时显著破坏了它们的代谢和营养特征，值得进一步阐明，特别是在体内和原位表征方面。本研究以罗非鱼（Oreochromis mossambicus）为研究对象，采用阳离子共价有机骨架（COF）涂层纤维固相微萃取（SPME），结合高效液相色谱-电喷雾电离-轨道阱质谱（HPLC-ESI-Orbitrap-MS）分析，建立了一种创新的体内取样方法。结果表明，自制SPME纤维具有优异的广谱提取能力（共检测到5250个分子特征），所建立的分析方法具有绿色环保的优点。基于自制纤维的SPME技术成功应用于nfrs对罗非鱼的影响研究。经统计分析，共有811种代谢物表现出显著的差异表达，包括氨基酸、糖苷、脂类等营养成分，导致营养品质下降。这些发现为nfrs生态风险评价、水生生物营养质量评价和水产品安全提供了新的视角。

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引用次数: 0

Recent progress in solid- and liquid-phase microextraction methods for the extraction and quantification of current-use pesticides 固体微萃取法和液相微萃取法用于农药提取和定量的研究进展

IF 6.5 Q1 CHEMISTRY, ANALYTICAL

Advances in Sample Preparation

Pub Date : 2025-10-01 Epub Date: 2025-09-28 DOI: 10.1016/j.sampre.2025.100215

Seyedeh Bentolhoda Hosseinian , Milad Ghani , Jahan Bakhsh Raoof

The widespread use of pesticides has led to their pervasive presence in diverse environmental matrices such as water, air, and soil. Therefore, accurate and reliable determination of pesticides in various sample types is essential. In recent years, a range of miniaturized extraction techniques, particularly solid-phase microextraction (SPME) and liquid-phase microextraction (LPME), have been developed. This review provides a comprehensive overview of recent advancements in liquid- and solid-phase microextraction techniques for separation and quantification of pesticides, while also critically evaluating their respective advantages and limitations. In addition, different configurations of solid- and liquid phase microextraction used for the extraction of pesticides are discussed. Moreover, various advanced materials such as molecularly imprinted polymers (MIPs), metal–organic frameworks (MOFs), 3D printed devices, Mxenes, and biopolymers used for the microextraction of pesticides were also discussed.

农药的广泛使用导致它们普遍存在于各种环境基质中，如水、空气和土壤。因此，准确、可靠地测定各种样品类型中的农药至关重要。近年来，以固相微萃取（SPME）和液相微萃取（LPME）为代表的一系列小型化萃取技术得到了发展。本文综述了用于农药分离和定量的液相微萃取和固相微萃取技术的最新进展，并对其各自的优点和局限性进行了批判性评价。此外，还讨论了用于农药提取的固、液相微萃取的不同配置。此外，还讨论了用于农药微提取的各种先进材料，如分子印迹聚合物（MIPs），金属有机框架（MOFs）， 3D打印设备，Mxenes和生物聚合物。

引用次数: 0

From lemon peels to bioactive peptides: protein recovery by pressurized liquid extraction and hydrolysates characterization by UHPLC-ESI-QTOF-MS/MS 从柠檬皮到生物活性肽：加压液体萃取法提取蛋白质和UHPLC-ESI-QTOF-MS/MS表征水解产物

IF 6.5 Q1 CHEMISTRY, ANALYTICAL

Advances in Sample Preparation

Pub Date : 2025-10-01 Epub Date: 2025-10-16 DOI: 10.1016/j.sampre.2025.100218

Esther Gómez-Mejía , María Concepción García , María Castro-Puyana , María Luisa Marina

This study aimed to develop a sustainable and efficient method for protein recovery from lemon peels using Pressurized Liquid Extraction (PLE), optimized through experimental design and response surface methodology. The final protocol, employing 18 % (v/v) ethanol, 110 °C, and a 7-min extraction time, demonstrated high extraction efficiency (66 %) and environmental compatibility, achieving a greenness score of 0.59 (AGREEprep). The optimized protein extract was subsequently hydrolyzed using alcalase and thermolysin, and the resulting peptide fractions were characterized by spectrophotometric methods and by Ultra High-Performance Liquid Chromatography coupled to Electrospray Ionization Quadrupole Time-of-Flight Mass Spectrometry (UHPLC-ESI-QTOF-MS/MS). A total of 58 peptides were identified, 39 of which originated from lemon proteins, along with 19 polyphenols, such as vicenin-2, narirutin or subaphylin, and other compounds (e.g., organic acids, amino acids, and purine nucleosides), revealing a diverse and multifunctional bioactive profile. Bioactivity assays demonstrated that the thermolysin hydrolysate exhibited the highest antioxidant (97 ± 1 % inhibition of hydroxyl radicals), antimicrobial (MIC = 0.75 mg/mL against Staphylococcus aureus), and antihypertensive activities (49 ± 3 % angiotensin-converting enzyme inhibition), likely due to the presence of peptides enriched in aromatic amino acids such as phenylalanine and tyrosine.

本研究旨在建立一种可持续、高效的从柠檬皮中提取蛋白质的加压液体萃取方法，并通过实验设计和响应面法对其进行优化。最终方案采用18% （v/v）乙醇，110°C，提取时间为7 min，具有较高的提取效率（66%）和环境相容性，绿色评分为0.59 （AGREEprep）。利用alcalase和thermolysin对优化后的蛋白提取物进行水解，并通过分光光度法和超高效液相色谱-电喷雾电离四极杆飞行时间质谱联用（UHPLC-ESI-QTOF-MS/MS）对所得到的肽段进行表征。共鉴定出58个多肽，其中39个来自柠檬蛋白，以及19种多酚，如vicenin-2、narirutin或subaphylin，以及其他化合物（如有机酸、氨基酸和嘌呤核苷），揭示了多样化和多功能的生物活性谱。生物活性分析表明，热溶菌素水解产物具有最高的抗氧化活性（97±1%的羟基自由基抑制），抗菌活性（对金黄色葡萄球菌的MIC = 0.75 mg/mL）和降压活性（49±3%的血管紧张素转换酶抑制），这可能是由于富含苯基丙氨酸和酪氨酸等芳香族氨基酸的肽的存在。

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引用次数: 0

Comparison of biodegradable polycaprolactone nanofibers and synthetic polyamide nanofibers as a novel, sustainable sorbent for a spin filter microextraction of xenobiotics from river water 生物可降解聚己内酯纳米纤维与合成聚酰胺纳米纤维在自旋过滤器微萃取河水中异种生物中的吸附效果比较

IF 6.5 Q1 CHEMISTRY, ANALYTICAL

Advances in Sample Preparation

Pub Date : 2025-10-01 Epub Date: 2025-09-16 DOI: 10.1016/j.sampre.2025.100214

Ewelina Czyz , Karolína Macháčková , Jakub Erben , Pavel Holec , František Švec , Dalibor Šatínský

We evaluated the application of nanofibers made from different biodegradable and synthetic polymers as sorbents in a new technique of spin filter fiber-microextraction. Biodegradable polycaprolactone fibers, produced via the meltblowing process exhibited robust hydrophobic interactions with lipophilic analytes and were the most effective. The highly porous and permeable structure of the fibrous material ensured exhaustive extraction of xenobiotics from river water. Recovery rates ranged from 81.8 to 105.2 %, except for 4-nitrophenol, a more polar analyte, for which the recovery was 60 %. Only 10 s were needed for activation, extraction, and elution, significantly reducing the time required to complete the procedure in only 30 s per sample. Our method exhibited excellent analytical performance, achieving linearity in the range of 50–2000 µg L⁻¹ for most analytes (100–2000 µg L⁻¹ for PNP and 2-CP; and 100–1000 µg L⁻¹ for PER) with a coefficient of determination (R²) greater than 0.9952. The limits of detection were recalculated based on the slope of the calibration curves and the standard deviation of six replicate measurements at the lowest calibration point for each analyte, yielding values in the range of 7.0–36.6 µgL^-1. Repeatability between extractions (i.e. inter-extraction precision) was evaluated by performing six parallel runs using different cartridges (n = 6). The obtained RSD precision values ranged from 2.2 to 3.3 % demonstrating the excellent uniformity of the nanofibrous materials filled in the devices . We also assessed the reusability of the individual cartridges by performing six consecutive extractions on the same spin filter (i.e. intra-cartridge precision, n = 6), yielding RSD values between 1.1 and 3.6 %. These results confirm that the spin filters cartridges filled with polycaprolactone nanofibers can be effectively reused for multiple extractions in absence of sample carry-over effect.

研究了由不同生物可降解聚合物和合成聚合物制成的纳米纤维作为吸附剂在自旋过滤纤维微萃取新技术中的应用。通过熔吹工艺生产的可生物降解聚己内酯纤维与亲脂分析物表现出强大的疏水相互作用，并且是最有效的。纤维材料的高度多孔性和渗透性结构确保了从河水中彻底提取异种生物。除极性较强的4-硝基苯酚的回收率为60%外，回收率为81.8% ~ 105.2%。活化、提取和洗脱只需要10秒，大大减少了完成每个样品仅需30秒的时间。我们的方法具有良好的分析性能，大多数分析物在50-2000µg L -⁻¹范围内呈线性（PNP和2-CP为100-2000µg L -⁻¹；PER为100-1000µg L -⁻），决定系数（R2）大于0.9952。根据校准曲线的斜率和每种分析物在最低校准点的6次重复测量的标准差重新计算检出限，得到的值范围为7.0-36.6µgL-1。通过使用不同的萃取盒（n = 6）进行6次平行运行来评估萃取之间的重复性（即萃取间的精密度）。得到的RSD精度值在2.2 ~ 3.3%之间，表明填充在器件中的纳米纤维材料具有良好的均匀性。我们还通过在相同的旋转过滤器上进行六次连续提取（即盒内精度，n = 6）来评估单个墨盒的可重复使用性，产生的RSD值在1.1到3.6%之间。这些结果证实了填充聚己内酯纳米纤维的自旋过滤器可以有效地重复使用多次提取，没有样品携带效应。

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引用次数: 0

Optimization and enzymatic intensification of bioactive compound extraction from carob pulps with potential weight management applications 具有体重管理应用潜力的角豆粕生物活性化合物提取优化及酶促强化

IF 6.5 Q1 CHEMISTRY, ANALYTICAL

Advances in Sample Preparation

Pub Date : 2025-10-01 Epub Date: 2025-10-20 DOI: 10.1016/j.sampre.2025.100219

Iván Benito-Vázquez , Manuel Garrido-Romero , Gema Hontoria-Caballo , Marina Díez-Municio , Francisco Javier Moreno , Ignacio Jiménez-Amezcua

Carob pulps (Ceratonia siliqua L.) are a rich source of bioactive compounds with potential benefits for weight management, particularly inositols, flavonoids and phenolic acids (e.g. gallic acid). This study aimed to develop and optimize a sustainable extraction method to maximize the recovery of these target compounds. A solid–liquid extraction (SLE) was first optimized using a Box–Behnken experimental design, evaluating different variables (temperature, time, sample concentration and ethanol content). A two-variable (2 V) model focused on the extraction of inositols and gallic acid was identified as the most efficient allowing high extraction yields (45 °C, 28 min, 100 mg/mL, pure water) compared to the three-variable (3 V) model (90 ºC, 42 min, 100 mg/mL, ethanol 50 %), which additionally prioritized the extraction of flavonoids. To further intensify the extraction, enzyme-assisted extraction (EAE) using two commercial cellulases were studied and significantly enhanced gallic acid release (up to 2.39 mg/g), confirming its selective extraction from the plant matrix. A two-step strategy combining EAE under 2 V conditions (inositols and gallic acid) with a second cycle of 3 V SLE (flavonoids) was selected as an ecofriendly alternative to maximize the content of bioactives and applied on different carob samples. Pinitol was the most abundant compound across all samples (16.7–73.0 mg/g) and gallic acid also achieved high values (1.9–8.4 mg/g). Regarding flavonoids, kaempferol and luteolin glucosides were the most abundant. This study provides a comprehensive framework for efficient and sustainable sample preparation of carob-derived bioactives intended for functional food or nutraceutical applications targeting weight management.

角豆浆（Ceratonia silqua L.）富含生物活性化合物，对体重管理有潜在的好处，特别是肌醇、类黄酮和酚酸（如没食子酸）。本研究旨在开发和优化一种可持续的提取方法，以最大限度地提高这些目标化合物的回收率。首先采用Box-Behnken实验设计，对不同的变量（温度、时间、样品浓度和乙醇含量）进行优化。与三变量（3 V）模型（90℃，42 min, 100 mg/mL，乙醇50%）相比，专注于提取肌醇和没食子酸的双变量（2 V）模型效率最高，提取率高（45°C, 28 min, 100 mg/mL，纯水），其中黄酮类化合物的提取更为优先。为了进一步加强提取，研究了两种商用纤维素酶的酶辅助提取（EAE），显著提高了没食子酸的释放（高达2.39 mg/g），证实了没食子酸从植物基质中的选择性提取。选择2 V条件下（肌醇和没食子酸）EAE与2 V条件下（黄酮类化合物）SLE相结合的两步策略作为最大限度地提高生物活性含量的生态替代方案，并应用于不同的角豆样品。蒎醇是所有样品中含量最高的化合物（16.7 ~ 73.0 mg/g），没食子酸也达到了很高的含量（1.9 ~ 8.4 mg/g）。黄酮类化合物以山奈酚和木犀草素苷含量最多。本研究为有效和可持续的碳水化合物衍生生物活性物质的样品制备提供了一个全面的框架，用于功能食品或营养保健应用，以控制体重。

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引用次数: 0

In-house metal-organic framework material for stir-bar sorptive extraction of acidic pharmaceutical compounds from environmental water samples 用于搅拌棒吸附萃取环境水样中酸性药物化合物的内部金属有机框架材料

IF 6.5 Q1 CHEMISTRY, ANALYTICAL

Advances in Sample Preparation

Pub Date : 2025-10-01 Epub Date: 2025-11-10 DOI: 10.1016/j.sampre.2025.100224

Abril Trullàs , Héctor Martínez-Pérez-Cejuela , Francesc Borrull , Mónica Catalá-Icardo , José Manuel Herrero-Martínez , Rosa Maria Marcé , Núria Fontanals

Pharmaceutical residues are increasingly recognized as emerging contaminants in aquatic environments due to their widespread consumption, improper disposal, and insufficient removal in wastewater treatment plants. These compounds, often found at trace levels, pose ecological risks owing to their bioaccumulation potential and biological activity. Micro-extraction techniques, especially stir-bar sorptive extraction (SBSE), have gained widespread use for their effectiveness in preconcentration and analytical applications. However, commercial SBSE coatings show limited retention of polar analytes and suffer from poor mechanical stability as well as high purchase cost. To address these limitations, this study presents the development and evaluation of an in-house hybrid coating material for SBSE with a total cost <5€/unit, based on metal-organic frameworks (MOFs) functionalized with amine groups that provide weak anion exchange (WAX) interactions. The performance of the amino-functionalized MOF attached to a glycidyl methacrylate-based monolith (GMA@NH₂-UiO-66(Zr)) was assessed for the extraction of acidic pharmaceutical compounds from environmental water samples, followed by determination using liquid chromatography-tandem mass spectrometry (LC-MS/MS). After the proper optimization, good analytical figures were obtained for river water samples, including the method’s limits of detection as low as 2 ng/L, adequate recoveries (22–41 %), matrix effect between +9 and -2 % and acceptable precision expressed as relative standard deviation below 25 %. Once validated, the method was applied for the determination of acidic pharmaceuticals from environmental water samples, which were found at ng/L level. The new material exhibited improved retention of polar pharmaceuticals, high stability, and reproducibility, demonstrating its potential as an effective tool for environmental monitoring of pharmaceutical contaminants.

由于药物残留的广泛使用、处置不当和废水处理厂去除不足，它们越来越被认为是水生环境中的新兴污染物。这些化合物通常以微量水平发现，由于其生物蓄积潜力和生物活性而构成生态风险。微萃取技术，特别是搅拌棒吸附萃取（SBSE），因其在富集和分析方面的有效性而得到了广泛的应用。然而，商用SBSE涂料显示极性分析物的保留有限，机械稳定性差，购买成本高。为了解决这些限制，本研究提出了一种用于SBSE的内部混合涂层材料的开发和评估，总成本为5欧元/单位，该材料基于具有弱阴离子交换（WAX）相互作用的胺基功能化的金属有机框架（MOFs）。采用液相色谱-串联质谱（LC-MS/MS）分析了氨基功能化MOF对环境水样中酸性药物的萃取性能，并对其与甲基丙烯酸缩水甘油酯基单体（GMA@NH₂- uui -66(Zr)）的吸附性能进行了评价。经过适当的优化，获得了良好的分析数据，包括方法的检出限低至2 ng/L，适当的回收率（22 - 41%），矩阵效应在+9 ~ - 2%之间，可接受的精密度表示为相对标准偏差低于25%。验证后，该方法可用于环境水样中酸性药物的测定，其含量为ng/L。新材料表现出极性药物保留率的提高，稳定性和可重复性高，表明其作为药物污染物环境监测的有效工具的潜力。

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