Advances in Sample Preparation最新文献_第2页

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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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 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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引用次数: 0

Chicken egg white coated paper, a sustainable mixed-mode cationic exchange biocomposite to extract antidepressants from saliva samples prior to their determination by direct infusion mass spectrometry 鸡蛋清涂布纸是一种可持续的混合模式阳离子交换生物复合材料，用于直接输注质谱法测定唾液样品中的抗抑郁药物

IF 6.5 Q1 CHEMISTRY, ANALYTICAL

Advances in Sample Preparation

Pub Date : 2025-10-01 DOI: 10.1016/j.sampre.2025.100226

Ana M. Pedraza-Soto, Rafael Lucena, Soledad Cárdenas

Proteinaceous materials are useful precursors for preparing sustainable and cost-effective sorptive phases. Among them, chicken egg white is an excellent alternative, serving as a source of ovalbumin that can be used as a biosorbent. In this article, the combination of egg white with cellulose paper is evaluated to synthesize a planar protein-based sorptive phase with high porosity and surface area. For this purpose, the paper was dip-coated in egg-white, followed by thermal curing that induced protein denaturation and self-crosslinking. The preparation was quite simple and affordable, since it did not require subsequent functionalization procedures, allowing the preparation of 25 sorptive phases with only 1 mL of pasteurized egg white. The resulting egg-white paper (EW-paper) enabled the isolation of the analytes through a mixed-mode interaction mechanism, comprising both hydrophobic and cation-exchange interactions. This potential was corroborated by evaluating the extraction capacity of the EW-paper towards some selective serotonin reuptake inhibitors (SSRI) (fluoxetine, paroxetine, sertraline, and venlafaxine) from saliva samples. The analytes were finally determined by direct infusion mass spectrometry analysis. Once optimized, the method allows the determination of the target compounds in the low µgL^-1 range, also fulfilling the validation criteria in terms of precision (better than 9.1 % and 11.8 % in intra- and inter-day precision, respectively) and accuracy (in the range 84 -118 %). Finally, the applicability of the method was demonstrated by analyzing real saliva samples from a patient under paroxetine treatment.

蛋白质材料是制备可持续和具有成本效益的吸附相的有用前体。其中，蛋清是一个很好的替代品，作为卵白蛋白的来源，可以用作生物吸附剂。本文研究了蛋清与纤维素纸的结合，合成了一种具有高孔隙率和高表面积的平面蛋白基吸附相。为此，将纸浸在蛋白中，然后进行热固化，诱导蛋白质变性和自交联。该制备非常简单且价格合理，因为它不需要后续的功能化程序，仅用1ml巴氏灭菌的蛋清即可制备25个吸附相。由此产生的蛋清纸（EW-paper）通过混合模式相互作用机制（包括疏水和阳离子交换相互作用）分离分析物。通过评估ew论文对唾液样本中一些选择性血清素再摄取抑制剂（氟西汀、帕罗西汀、舍曲林和文拉法辛）的提取能力，证实了这一潜力。最后用直接输注质谱法测定分析物。优化后，该方法可在低µgL-1范围内测定目标化合物，精密度（日内精密度分别优于9.1%和11.8%）和准确度（范围为84 - 118%）均满足验证标准。最后，通过分析帕罗西汀治疗患者的真实唾液样本，证明了该方法的适用性。

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引用次数: 0

Green metric for microwave-assisted sample preparation for elemental analysis: GreenPrep MW Score 用于元素分析的微波辅助样品制备的绿色度量：GreenPrep MW评分

IF 6.5 Q1 CHEMISTRY, ANALYTICAL

Advances in Sample Preparation

Pub Date : 2025-10-01 DOI: 10.1016/j.sampre.2025.100216

Joaquim A. Nóbrega , Lorenzo Rossi , Gianpaolo Rota , Mirco Rossetti , Valentina Carrara , Camillo Pirola , Giulio Colnaghi , Diego Carnaroglio

Rapidly moving to the 3^rd decade of the 21^st century, it is clear that our technologies must evolve to sustainable processes, not aggressive to the environment nor to all forms of life. Chemical sciences are going green and surely analytical chemistry is moving towards this same direction. But we need to speed up the pace. To evaluate an analytical procedure, we should be able to validate it. Nowadays, method validation is not only the demonstration that analytical results are accurate, in fact method validation is also related to green chemistry aspects. If we think about elemental analysis, we can state that the sample preparation step has been improved, nonetheless it certainly requires further improvements through the development of greener procedures. In this contribution, we propose a set of green metrics named GreenPrep MW Score for the evaluation of microwave-assisted sample preparation procedures using different technologies, either based on cavity microwave oven, or on a single reaction chamber system. The GreenPrep MW Score was proposed considering the whole analytical procedure and how chemical parameters, technology variables and workflow can be optimized, and how these factors impact green metrics score. The authors do not intend to substitute sound metrics already proposed for evaluating the sample preparation step. Our goal is to propose a complementary strategy which helps us identify specific points to be improved in microwave-assisted procedures. The application of the developed metric was demonstrated for several samples containing different matrices, such as foods, multivitamin tablets, spodumene; in addition, strategies for improving green chemistry aspects were discussed.

迅速进入21世纪的第三个十年，很明显，我们的技术必须发展到可持续的进程，而不是对环境和所有形式的生命造成破坏。化学科学正在走向绿色，毫无疑问，分析化学也在朝着同样的方向发展。但我们需要加快步伐。为了评估一个分析程序，我们应该能够验证它。如今，方法验证不仅仅是证明分析结果的准确性，事实上，方法验证还涉及到绿色化学的各个方面。如果我们考虑元素分析，我们可以说样品制备步骤已经改进，尽管如此，它肯定需要通过开发更环保的程序进一步改进。在这篇文章中，我们提出了一套绿色指标，称为GreenPrep MW Score，用于评估使用不同技术的微波辅助样品制备程序，无论是基于空腔微波炉还是单一反应室系统。GreenPrep MW评分的提出考虑了整个分析过程，以及如何优化化学参数、技术变量和工作流程，以及这些因素如何影响绿色指标评分。作者不打算取代已经提出的评估样品制备步骤的健全指标。我们的目标是提出一种补充策略，帮助我们确定微波辅助手术中需要改进的具体点。该方法应用于几种含有不同基质的样品，如食品、复合维生素片、锂辉石；此外，还讨论了绿色化学方面的改进策略。

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引用次数: 0

Polyhedral oligomeric silsesquioxane hybrid monolithic microcartridges for the determination of β-lactoglobulin in food by on-line solid-phase extraction capillary electrophoresis-mass spectrometry 在线固相萃取-毛细管电泳-质谱联用测定食品中β-乳球蛋白的多面体低聚硅氧烷杂化整体微盒

IF 6.5 Q1 CHEMISTRY, ANALYTICAL

Advances in Sample Preparation

Pub Date : 2025-10-01 DOI: 10.1016/j.sampre.2025.100220

Renan Vitek , Tahereh Tehrani , Laura Pont , María Vergara-Barberán , José Manuel Herrero-Martínez , Fernando Benavente , Jorge C. Masini

A novel polyhedral oligomeric silsesquioxane methacryl substituted (POSS-MA) monolithic microcartridge was prepared for the determination of low levels of the allergenic protein β-lactoglobulin (β-LG) in food by on-line solid-phase extraction capillary electrophoresis-mass spectrometry (SPE-CE-MS). The material was synthesized inside a 250 μm inner diameter (i.d.) capillary column by free radical polymerization using a simple "one-pot" method. This capillary column was subsequently cut and straightforwardly assembled as microcartridges connected in-line with 75 μm i.d. separation capillaries for SPE-CE-MS. Several SPE-CE-MS parameters (such as loading time, type of eluent, or time and pressure of elution) were optimized using an acidic background electrolyte (BGE) composed of 2 M acetic acid (HAc, pH 2.2). Under optimized conditions, the protein sample was loaded at 930 mbar for 20 min (ca. 110 μL), followed by a washing step with BGE at 930 mbar for 1 min, and finally eluted with 2 M HAc in methanol at 100 mbar for 60 s (ca. 600 nL). The method exhibited linearity from 0.25 to 10 μg·mL⁻¹ of β-LG, with a limit of detection of 0.1 μg·mL⁻¹, and a 100-fold increase in sensitivity compared to CE-MS. It was successfully applied to the determination of β-LG in dairy free white breads, yielding satisfactory results. These outcomes highlight the strong potential of the developed SPE-CE-MS method, using plug-and-play POSS-MA monolithic microcartridges, for precise food safety and quality control.

采用在线固相萃取-毛细管电泳-质谱联用技术（SPE-CE-MS）制备了一种新型多面体低聚硅氧烷甲基丙烯酸取代（POSS-MA）单片微瓶，用于食品中低含量致敏蛋白β-乳球蛋白（β-LG）的检测。在内径为250 μm （i.d）的毛细管柱内，采用简单的“一锅法”，采用自由基聚合法制备了该材料。该毛细管柱随后被切割并直接组装成与75 μm id分离毛细管直线连接的微盒，用于SPE-CE-MS。采用由2 M乙酸（HAc, pH 2.2）组成的酸性背景电解质（BGE），优化了SPE-CE-MS的几个参数（如上样时间、洗脱液类型或洗脱时间和压力）。在优化后的条件下，蛋白样品在930 mbar下负载20 min（约110 μL），然后用BGE在930 mbar下洗涤1 min，最后用2 M HAc在100 mbar的甲醇中洗脱60 s（约600 nL）。该方法在β-LG浓度0.25 ~ 10 μg·mL−1范围内呈线性关系，检出限为0.1 μg·mL−1，灵敏度比CE-MS提高100倍。该法成功地应用于无乳白面包中β-LG的测定，结果令人满意。这些结果突出了开发的SPE-CE-MS方法的强大潜力，该方法使用即插即用的POSS-MA单片微盒，用于精确的食品安全和质量控制。

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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 : 2025-09-16 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

Recovery of proteins and bioactive compounds from turmeric (Curcuma longa) and ginger (Zingibber officinale) wastes using sustainable extraction techniques. Tentative identification of main extracted compounds by UHPLC-Q-TOF-MS/MS 利用可持续提取技术从姜黄（Curcuma longa）和姜（Zingibber officinale）废料中回收蛋白质和生物活性化合物。UHPLC-Q-TOF-MS/MS对主要提取物进行初步鉴定

IF 6.5 Q1 CHEMISTRY, ANALYTICAL

Advances in Sample Preparation

Pub Date : 2025-09-13 DOI: 10.1016/j.sampre.2025.100213

Rubio-Marín Carlos , María Luisa Marina , María Concepción García

Ginger and turmeric are spices increasingly employed in juice production due to their outstanding composition and health benefits. This practice results in wastes that, like whole spices, likely constitute a cheap and sustainable source of proteins, as well as antioxidant and antimicrobial compounds, whose recovery has not yet been proposed. This work aims to evaluate low environmental impact techniques to make the most of these wastes: high-intensity focused ultrasounds (HIFU), subcritical water extraction (SWE), and enzyme-assisted extraction (EAE). In all cases, water was used as extracting solvent and experimental design chemometric tools (Box-Behnken and factorial 3² design) were employed to maximize the recovery of proteins, antioxidants, and antimicrobial compounds, while minimizing the formation of potentially harmful Maillard products during extraction. HIFU demonstrated a greater capability for extracting proteins, which increased significantly when combined with EAE using a polysaccharidase enzyme. The largest protein extraction was achieved from the ginger extract using HIFU for 18 min, at 60 ºC and 80 % amplitude, combined with EAE using Celluclast enzyme. The extracts obtained using SWE showed significant antioxidant activity, with a slight improvement observed when using 2 cycles instead of one. The highest antioxidant activity was observed in the extract obtained from the turmeric waste using SWE at 175 ºC for 15 min. The extracts also exhibited antimicrobial activity, especially against Staphylococcus aureus, highlighting the minimum inhibitory concentration obtained from the turmeric waste extract using SWE at 155 ºC for 9 min (0.15 mg/mL). The extracts showing the highest antioxidant or antimicrobial activity were analyzed by ultrahigh-performance liquid chromatography coupled to high-resolution tandem mass spectrometry for the tentative identification of main compounds responsible for the observed activities. Phenolic compounds, such as 6-gingerol and its derivatives in ginger waste extracts, and curcuminoids in turmeric waste extracts, were tentatively identified as the predominant constituents.

生姜和姜黄由于其出色的成分和健康益处而越来越多地用于果汁生产。这种做法产生的废物，就像整个香料一样，可能构成廉价和可持续的蛋白质来源，以及抗氧化和抗菌化合物，其回收尚未提出。这项工作旨在评估低环境影响技术，以充分利用这些废物：高强度聚焦超声（HIFU）、亚临界水提取（SWE）和酶辅助提取（EAE）。在所有情况下，均使用水作为提取溶剂，并采用实验设计化学测量工具（Box-Behnken和析因32设计）来最大限度地回收蛋白质、抗氧化剂和抗菌化合物，同时最大限度地减少提取过程中潜在有害美拉德产物的形成。HIFU显示出更大的蛋白质提取能力，当使用多糖酶与EAE联合使用时，蛋白质提取能力显著提高。在60ºC和80%振幅下，HIFU作用18 min，结合使用Celluclast酶的EAE，从姜提取物中提取的蛋白质最多。SWE提取的提取物具有显著的抗氧化活性，当使用2个周期而不是1个周期时，其抗氧化活性略有提高。从姜黄废料中提取的抗氧化活性最高，SWE在175℃下加热15 min。该提取物还显示出抗菌活性，特别是对金黄色葡萄球菌，突出显示姜黄废物提取物在155ºC下使用SWE处理9分钟（0.15 mg/mL）获得的最低抑制浓度。采用高效液相色谱联用高分辨率串联质谱法对抗氧化或抗菌活性最高的提取物进行了分析，初步确定了主要活性成分。初步确定了生姜提取物中的6-姜辣素及其衍生物和姜黄素等酚类化合物为主要成分。

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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 : 2025-09-04 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

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 : 2025-09-04 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

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 : 2025-09-01 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