Advances in Sample Preparation最新文献

Innovative ultrasound-assisted and vacuum manifold-assisted pipette tip solid-phase extraction using MSU-2-C18 sorbent for the extraction and purification of glycoalkaloids in potato-based snacks prior to UHPLC-MS/MS analysis 在UHPLC-MS/MS分析之前，使用MSU-2-C18吸附剂，采用创新的超声辅助和真空歧管辅助移液尖端固相萃取法提取和纯化马铃薯零食中的糖生物碱

IF 6.5 Q1 CHEMISTRY, ANALYTICAL

Advances in Sample Preparation

Pub Date : 2025-11-25 DOI: 10.1016/j.sampre.2025.100228

Isabel Martínez-García , Damián Pérez-Quintanilla , Sonia Morante-Zarcero , Isabel Sierra

A miniaturized and environmentally conscious analytical workflow was developed and validated for the extraction, purification, and quantification of major glycoalkaloids (α-solanine, α-chaconine), the degradation product γ-chaconine, and the aglycone solanidine in potato-based snack products. The method combines ultrasound-assisted extraction (UAE) with pipette-tip solid-phase extraction (PT-SPE), followed by UHPLC-MS/MS analysis. UAE conditions were optimized using a Box-Behnken statistical design, which evaluated the extraction time, ultrasound amplitude, and solid:liquid (SL) ratio. Optimal conditions were determined to be 5 min, 100 % amplitude, and a 1:9 w/v of SL ratio, with methanol as the most effective extraction solvent. MSU-2-C18 mesostructured silica sorbent, packed into pipette tips (5 mg) connected to a SPE vacuum manifold (VMA-PT-SPE), was employed under the optimized conditions to simultaneously purify up to 12 extracts. The method's greenness was evaluated using the AGREEprep metric, yielding a score of 0.65, indicating good environmental performance. Limits of detection (LOD) and quantification (LOQ), ranging from 0.55–4.40 µg/kg and 1.82–14.67 µg/kg, respectively, were achieved for the target analytes. Application to four commercial potato-based snacks revealed major (α-solanine and α-chaconine) and minor glycoalkaloids (γ-chaconine and solanidine) levels, ranging from 2.0 to 16.0 mg/kg fresh weight, highlighting substantial variability among products and providing a more comprehensive characterization of the glycoalkaloid profile. Compared to conventional SPE formats, this UAE-VMA-PT-SPE strategy offers superior reproducibility while reducing sample and solvent consumption. The method represents a powerful tool for routine monitoring of glycoalkaloids in potato snacks, supporting food safety assessments and addressing analytical priorities established by the European Food Safety Authority.

开发并验证了一种小型化、环保的分析流程，用于提取、纯化和定量马铃薯零食产品中主要的糖生物碱（α-龙葵碱、α-恰康碱）、降解产物γ-恰康碱和茄碱苷元。该方法将超声辅助提取（UAE）与移液头固相萃取（PT-SPE）相结合，然后进行UHPLC-MS/MS分析。采用Box-Behnken统计设计优化UAE条件，评估提取时间、超声振幅和固液比。以甲醇为最佳提取溶剂，提取时间为5 min，提取幅度为100%，SL比为1:9 w/v。MSU-2-C18介结构二氧化硅吸附剂装在连接到SPE真空歧管（VMA-PT-SPE）的移液头（5mg）中，在优化的条件下同时纯化多达12个提取物。该方法的绿色度使用AGREEprep指标进行评估，得分为0.65，表明环境性能良好。目标分析物的检出限（LOD）和定量限（LOQ）分别为0.55 ~ 4.40µg/kg和1.82 ~ 14.67µg/kg。对四种商业马铃薯零食的研究显示，主要的（α-龙葵碱和α-恰康碱）和次要的糖生物碱（γ-恰康碱和茄碱）含量在2.0到16.0 mg/kg新鲜重量之间，突出了产品之间的巨大差异，并提供了更全面的糖生物碱谱表征。与传统的SPE格式相比，这种UAE-VMA-PT-SPE策略在减少样品和溶剂消耗的同时提供了卓越的重现性。该方法是马铃薯零食中糖生物碱常规监测的有力工具，支持食品安全评估和解决欧洲食品安全局确定的分析重点。

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引用次数: 0

Electromembrane extraction of tetracyclines in foods and human plasma prior to LC-MS/MS analysis: Impact of sample matrix on extraction performance LC-MS/MS分析前食品和人血浆中四环素的电膜提取：样品基质对提取性能的影响

IF 6.5 Q1 CHEMISTRY, ANALYTICAL

Advances in Sample Preparation

Pub Date : 2025-11-21 DOI: 10.1016/j.sampre.2025.100227

Anne Oldeide Hay, Frederik André Hansen

Tetracyclines are widely used antibiotics in animal farming, raising concerns over their residues in food and associated health risks. Current methods for residue determination are complex, time-consuming, and produce substantial solvent waste. Electromembrane extraction (EME) offers high clean-up efficiency, minimal solvent use, and direct LC-MS/MS compatibility. This study evaluates EME for extraction of four tetracyclines (oxytetracycline, tetracycline, chlorotetracycline, doxycycline) from complex matrices including milk, egg white, honey, and human plasma. Optimal parameters varied across matrices, underscoring the need for matrix-specific optimization. Optimized methods achieved recoveries of 66–101 %, excellent linearity (R² = 0.9929–0.9998), and minimal matrix effects (-14 % to 1 %). LLOQs ranged from 0.5 to 2.1 ng/g, with calibration curves extending to 1000 ng/g, covering concentrations relevant for residue monitoring. These results demonstrate EME’s potential for reliable analysis of challenging polar and zwitterionic compounds in food and biological samples. Finally, the greenness was evaluated by the AGREEprep metric tool, gaining a total score of 0.64.

四环素是动物养殖中广泛使用的抗生素，引起了人们对其在食品中的残留和相关健康风险的担忧。目前的残留测定方法复杂，耗时，并且产生大量的溶剂浪费。电膜萃取（EME）具有清洁效率高、溶剂用量少、LC-MS/MS直接兼容等优点。本研究评估了EME从复杂基质（包括牛奶、蛋清、蜂蜜和人血浆）中提取四种四环素（土霉素、四环素、氯四环素、强力霉素）的效果。最优参数因矩阵而异，强调了对矩阵特定优化的需求。优化后的方法回收率为66% ~ 101%，线性良好（R²= 0.9929 ~ 0.9998），基质效应最小（- 14% ~ 1%）。LLOQs范围为0.5 ~ 2.1 ng/g，校准曲线延伸至1000 ng/g，涵盖了与残留监测相关的浓度。这些结果证明了EME在食品和生物样品中具有挑战性的极性和两性离子化合物的可靠分析方面的潜力。最后，采用AGREEprep指标工具对绿度进行评价，得到总分0.64分。

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引用次数: 0

Green hydrophobic deep eutectic solvent-based rapid synergistic cloud point extraction and quantification of ultra-trace lead 绿色疏水深共晶溶剂基快速协同云点萃取及超痕量铅定量

IF 6.5 Q1 CHEMISTRY, ANALYTICAL

Advances in Sample Preparation

Pub Date : 2025-10-01 DOI: 10.1016/j.sampre.2025.100225

Ingrid Hagarová , Vasil Andruch , Alina Kalyniukova

In this study, a novel and environmentally friendly analytical procedure was developed for the fast separation and preconcentration of ultra-trace levels of lead from water samples at room temperature. The method is based on a hydrophobic deep eutectic solvent–assisted rapid synergistic cloud point extraction (HDES-RS-CPE), followed by electrothermal atomic absorption spectrometry (ETAAS) for quantification. The selected HDES was composed of l-menthol and 1-octanol in a 1:1 molar ratio, while ammonium pyrrolidine dithiocarbamate (APDC) and Triton X-114 were employed as the chelating agent and nonionic surfactant, respectively. Key experimental parameters influencing extraction efficiency were systematically investigated and optimized. Under optimal conditions, the method achieved a limit of detection (LOD) of 0.04 µg/L, a limit of quantification (LOQ) of 0.12 µg/L, and an enrichment factor (EF) of 38, with spike recoveries ranging from 94 % to 104 %. The method’s greenness, practicality and robustness were confirmed using various metrics demonstrated compliance with the principles of Green Analytical Chemistry, highlighting the method’s potential as a sustainable and efficient approach for ultra-trace lead quantification in environmental samples.

在本研究中，开发了一种新的环境友好的分析方法，用于在室温下快速分离和富集水样中的超痕量铅。该方法基于疏水深共晶溶剂辅助快速协同云点萃取（HDES-RS-CPE），然后采用电热原子吸收光谱法（ETAAS）进行定量。选用l-薄荷醇和1-辛醇以1:1的摩尔比组成HDES，吡咯烷二硫代氨基甲酸铵（APDC）和Triton X-114分别作为螯合剂和非离子表面活性剂。对影响萃取效率的关键实验参数进行了系统研究和优化。在最佳条件下，该方法的检出限为0.04µg/L，定量限为0.12µg/L，富集因子为38，峰回收率为94% ~ 104%。该方法的绿色、实用性和稳健性得到了各种指标的证实，这些指标符合绿色分析化学的原则，突出了该方法作为环境样品中超痕量铅定量的可持续和有效方法的潜力。

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引用次数: 0

Compatibility of NADES and ABS with CE-SDS analysis of bovine milk proteins NADES和ABS与牛乳蛋白CE-SDS分析的相容性

IF 6.5 Q1 CHEMISTRY, ANALYTICAL

Advances in Sample Preparation

Pub Date : 2025-10-01 DOI: 10.1016/j.sampre.2025.100222

Cristian Gonzalez-Jimenez, Paula Tejedor-Matellanes, Mercedes de Frutos, Angel Puerta

The rising interest in studying milk proteins is due to several factors such as the food supplement consumption based on them and the circular economy of the whey obtained as a byproduct in the dairy industry. Modifications of the milk proteins, such as fragmentation, aggregation and denaturation happening during manufacturing need to be tightly controlled. In this work the use of an aqueous biphasic system (ABS) consisting of a natural deep eutectic solvent (NADES) and a salt to recover proteins from milk that could be applied to the extraction of milk proteins from byproducts in the dairy industry, was evaluated. As NADES betaine:urea:water (1:2:1 molar ratio) was employed. Back-extraction of milk proteins into water was evaluated by UV spectroscopy and by capillary electrophoresis with sodium dodecyl sulfate (CE-SDS). This study included the prior assessment of the usefulness of non-reducing CE-SDS method with laboratory-made gel-buffers for analyzing bovine caseins and whey proteins. Afterwards the compatibility of this CE method with the use of this NADES as protein solvent was established. The study allowed demonstrating that caseins as well as whey proteins mainly partition in the NADES-rich phase of the ABS, with recovery yield values higher than 77 %, extraction efficiencies higher than 97 % and back-extraction into water using centrifugal filter devices higher than 28 %. This work supports a procedure for recovering milk proteins from dairy industry byproducts using chemicals considered environmentally friendly. Sustainability of the ABS and back-extraction method was assessed using the AGREEprep tool. Besides the green characteristics of the sample preparation, the CE-SDS method established consumes a very low volume of sample and reagents and allows analyzing the individual caseins and whey proteins in less than 6 min as well as measuring the back-extraction recovery in water.

人们对研究牛奶蛋白的兴趣日益浓厚，这是由于几个因素，比如以牛奶蛋白为基础的食品补充剂消费，以及乳清作为乳制品工业副产品的循环经济。牛奶蛋白的修饰，如在生产过程中发生的破碎、聚集和变性，需要严格控制。在这项工作中，评估了由天然深共熔溶剂（NADES）和盐组成的双水相体系（ABS）从牛奶中回收蛋白质的应用，该体系可用于从乳制品工业的副产品中提取牛奶蛋白质。NADES采用甜菜碱：尿素：水（1:2:1）的摩尔比。采用紫外光谱法和毛细管电泳法对乳蛋白反提进行了评价。这项研究包括预先评估非还原CE-SDS方法与实验室自制的凝胶缓冲液分析牛酪蛋白和乳清蛋白的有效性。然后建立了该方法与NADES作为蛋白质溶剂的相容性。该研究表明，酪蛋白和乳清蛋白主要在ABS的富nades相分离，回收率高于77%，提取效率高于97%，使用离心过滤装置反提取到水中的效率高于28%。这项工作支持了一种使用环保化学品从乳制品工业副产品中回收牛奶蛋白的方法。使用AGREEprep工具评估ABS和反拔方法的可持续性。除了样品制备的绿色特性外，建立的CE-SDS方法消耗的样品和试剂体积非常小，可以在不到6分钟的时间内分析单个酪蛋白和乳清蛋白，并测量水中反萃取回收率。

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引用次数: 0

Sorbent-less dried blood spot microsampling 无吸附剂干血斑显微取样

IF 6.5 Q1 CHEMISTRY, ANALYTICAL

Advances in Sample Preparation

Pub Date : 2025-10-01 DOI: 10.1016/j.sampre.2025.100221

Miloš Dvořák , Sylvie Profousová , Pavel Kubáň

Dried blood spots (DBSs) are typically sampled on porous sorbents, which may retain analytes in their structure during DBS rehydration but also release various species into the eluates and contaminate them. To eliminate the eluate contamination, a novel concept for sorbent-less DBS microsampling was suggested, and a comprehensive study was carried out investigating the effect of the novel and the standard DBS sampling procedures on the contamination. In the novel concept, a small drop of capillary blood with a known volume was quantitatively pipetted into a non-porous polypropylene vial (compatible with capillary electrophoresis (CE) instruments for subsequent analysis) without being absorbed by any sorbent. All procedures, including DBS sampling, drying, rehydration, and homogenization, were done directly in-vial, and the blood drying time was < 3 h. By neglecting the porous sorbent, contamination of the resulting DBS eluates by sorbent-borne species was eliminated, which was demonstrated by the CE determination of inorganic cations/anions and organic anions. The ionic composition of the rehydrated sorbent-less DBSs showed no statistical difference from the original liquid capillary blood. On the contrary, all commercial sorbents released considerable levels of ions into the eluates (Ca²⁺, Mg²⁺, Na⁺ and Cl^-, NO₃^-, SO₄^2-, HCOO^- being the major cationic and anionic contaminants, respectively), resulting in up to 3.5-fold higher concentrations in standard vs. sorbent-less DBS samples and having a detrimental effect on quantitative DBS analyses. Moreover, additional ionic contamination was observed for DBSs sampled on pre-impregnated sorbents and/or by volumetric devices treated with anticoagulants. Consequently, a simple, precise, and accurate procedure was presented for sorbent-less DBS microsampling in medical as well as patient-centric conditions. The most convenient and economical DBS sampling was achieved by a low-cost micropipette with adjustable volume, resulting in precision and accuracy of ≤ 1.7 and 1.4%, respectively, for quantitative blood transfers, and CE analyses repeatability of ≤ 7.2%, after the whole DBS processing.

干血斑（DBS）通常在多孔吸附剂上取样，在DBS再水化过程中，这种吸附剂可能保留分析物的结构，但也会释放各种物质到洗脱液中并污染它们。为了消除洗脱液污染，提出了一种无吸附剂DBS微采样的新概念，并对新型DBS采样程序和标准DBS采样程序对污染的影响进行了全面研究。在这个新概念中，一小滴已知体积的毛细管血被定量地移液到一个无孔聚丙烯小瓶中（与毛细管电泳（CE）仪器兼容，用于后续分析），而不被任何吸附剂吸收。所有步骤，包括DBS取样、干燥、复水化和均质，都是直接在瓶中完成的，血液干燥时间为3小时。通过忽略多孔吸附剂，消除了吸收剂携带的物质对所得DBS洗脱物的污染，无机阳离子/阴离子和有机阴离子的CE测定证明了这一点。再水合无吸附剂DBSs的离子组成与原始液体毛细血管血无统计学差异。相反，所有商业吸附剂释放相当水平的离子到洗脱物中（Ca2+, Mg2+， Na+和Cl-， NO3-, SO42-， HCOO-分别是主要的阳离子和阴离子污染物），导致标准DBS样品中的浓度比无吸附剂的高3.5倍，并对DBS定量分析产生不利影响。此外，在预浸渍吸附剂和/或经抗凝剂处理的体积装置上取样的DBSs观察到额外的离子污染。因此，提出了一种简单、精确和准确的程序，用于医疗和以患者为中心的条件下的无吸附剂DBS微采样。DBS取样最方便、最经济的方法是使用低成本、可调节体积的微移管，定量输血的精密度和准确度分别≤1.7和1.4%，整个DBS处理后CE分析的重复性≤7.2%。

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引用次数: 0

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 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 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

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 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

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 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

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 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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