Journal of Chromatography A最新文献_第6页

Comprehensive chromatographic profiling and structural analysis of key anticoagulant components in enoxaparin 对依诺肝素中的主要抗凝成分进行全面色谱分析和结构分析。

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2024-10-18 DOI: 10.1016/j.chroma.2024.465457

Wen Zhu , Lei Chen , Wenjing Zhang , Luyun Qiu , Jingtao Fu , Lin Yi , Jianzhou Cui , Yilan Ouyang , Zhenqing Zhang

Heparin is the most widely used anticoagulant in clinical practice, with enoxaparin being one of the most important low molecular weight heparins (LMWHs). In this study, an antithrombin III (ATIII) affinity column was used. Enoxaparin and its oligosaccharides of varying sizes, prepared using preparative size exclusion chromatography (SEC), were fractionated through the ATIII affinity column. The different affinity fractions from each oligosaccharide size were profiled using strong anion exchange (SAX) chromatography. Each peak was automatically transferred to an SEC column for desalting prior to mass spectrometry (MS) analysis, which enabled structural identification using a multiple heart-cut (MHC) 2D LC-MS system (SAX-SEC-MS). The high-affinity fraction from enoxaparin was further analyzed using the MHC 2D LC system (SEC-SAX). SAX profiles of the high-affinity oligosaccharides, prepared by both size and affinity fractionation, were consistent with those obtained by direct SEC-SAX analysis. The possible sequences of several high-affinity hexasaccharides and the domain compositions of high-affinity octa- and decasaccharides in enoxaparin were further elucidated by disaccharide analysis after manual collection of the oligosaccharides. This work advances the understanding of enoxaparin's structural features and offers a potential approach to improve the quality of enoxaparin, as well as to identify key structural motifs in heparin/LMWHs that contribute to protein binding.

肝素是临床上使用最广泛的抗凝剂，其中依诺肝素是最重要的低分子量肝素（LMWHs）之一。本研究使用了抗凝血酶 III（ATIII）亲和柱。用制备型尺寸排阻色谱法（SEC）制备的不同尺寸的依诺肝素及其寡糖通过 ATIII 亲和柱进行分馏。使用强阴离子交换（SAX）色谱法对每种寡糖的不同亲和性馏分进行了分析。在进行质谱（MS）分析之前，每个峰都会自动转移到一个 SEC 柱上进行脱盐，从而利用多心切片（MHC）二维 LC-MS 系统（SAX-SEC-MS）进行结构鉴定。利用 MHC 二维液相色谱系统（SEC-SAX）进一步分析了依诺肝素的高亲和力馏分。通过大小分馏和亲和性分馏制备的高亲和性寡糖的 SAX 图谱与直接 SEC-SAX 分析获得的结果一致。通过人工收集寡糖后进行双糖分析，进一步阐明了烯诺肝素中几种高亲和性六糖的可能序列以及高亲和性八糖和十糖的结构域组成。这项工作加深了人们对依诺肝素结构特征的了解，为提高依诺肝素的质量以及确定肝素/LMWHs 中有助于蛋白质结合的关键结构基团提供了一种潜在的方法。

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引用次数: 0

Implementation of multiobjective decision-making algorithms and image analysis in HPTLC-guided extraction optimization of natural products 多目标决策算法和图像分析在 HPTLC 引导的天然产品提取优化中的应用

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2024-10-17 DOI: 10.1016/j.chroma.2024.465443

Filip Andrić , Minami Imamoto , Milica Jankov

A new, efficient, and low-cost approach for monitoring extraction optimization was proposed based on high-performance thin-layer chromatography (HPTLC) coupled with digital image analysis. Since HPTLC produces rich chromatographic signals corresponding to various analytes which may be differently affected by extraction conditions, four multicriteria decision-making (MCDM) techniques were compared for their ability to aggregate multiple chromatographic responses: Derringer's desirability approach, Technique for Order of Preference by Similarity to Ideal Solution (TOPSIS), Preference Ranking Organization Method for Enrichment Evaluations (PROMETHEE-2), and the Sum of ranking differences (SRD). Ultrasound-assisted extraction (UAE) of green tea leaves with ethanol-water mixtures was used as a model system. The amount of ethanol and extraction time were varied according to the central composite design. Ranking eleven extracts by Derringer's desirability approach, TOPSIS, and PROMETHEE-2 showed the same results. SRD analysis yielded slightly different results from previous methods. Response surface models (RSM) based on the previous three MCDM approaches demonstrated that extraction conditions with moderate amounts of ethanol (73%) and extraction times (46 min) lead to optimal chromatographic profiles. RSM optimization performed on individual peaks, tentatively corresponding to rutin, chlorophyll, and gallic acid, led to different results, which justified the use of MCDM algorithms for aggregation of multiple responses. Aside from natural products, the proposed approach has the potential to be implemented in various extraction optimizations.

基于高效薄层色谱法（HPTLC）和数字图像分析，提出了一种新型、高效、低成本的萃取优化监测方法。由于 HPTLC 会产生丰富的色谱信号，这些信号对应的各种分析物可能会受到萃取条件的不同影响，因此对四种多标准决策 (MCDM) 技术进行了比较，以确定它们汇总多种色谱响应的能力：这四种多标准决策（MCDM）技术分别是：德林格尔可取性方法（Derringer's desirability approach）、与理想解决方案相似度排序技术（TOPSIS）、用于富集评价的偏好排序组织方法（PROMETHEE-2）以及排序差异总和（SRD）。以乙醇-水混合物超声辅助萃取（UAE）绿茶叶为模型系统。乙醇量和萃取时间根据中心复合设计进行改变。通过德林格尔可取性方法、TOPSIS 和 PROMETHEE-2 对 11 种提取物进行排序，结果相同。SRD 分析得出的结果与之前的方法略有不同。基于前三种多因素强迫管理（MCDM）方法的响应面模型（RSM）表明，适量乙醇（73%）和萃取时间（46 分钟）的萃取条件可获得最佳色谱图。对暂定对应芦丁、叶绿素和没食子酸的单个峰进行的 RSM 优化得出了不同的结果，这证明了使用 MCDM 算法来汇总多个响应是正确的。除天然产品外，所提出的方法还可用于各种萃取优化。

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引用次数: 0

Exploring electromembrane extraction coupled to fast LC-MS/MS as a high-throughput platform for determination of 12 polar endogenous metabolites in human plasma 探索将电解质膜萃取与快速 LC-MS/MS 联用，作为测定人体血浆中 12 种极性内源性代谢物的高通量平台

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2024-10-16 DOI: 10.1016/j.chroma.2024.465451

Anne Oldeide Hay, Frederik André Hansen

High efficiency in the analytical workflow, including fast sample preparation and LC-MS/MS analysis, is an advantage when analyzing a high number of samples. It can however be a challenge when determining polar analytes in complex, biological samples, and one must expect to make a compromise between a simple sample preparation followed by a long chromatographic separation, or vice versa, to limit matrix effects. In this proof-of-concept work, a one-step 96-well (parallel extraction) electromembrane extraction (EME) method was coupled to flow injection-MS/MS of 0.7 min per sample, allowing a very high-throughput analysis of 12 polar, endogenous metabolites from unprecipitated plasma of limited dilution. The throughput of the EME method matched the subsequent analysis. Recoveries ranged from 6 to 93 %, and repeatability and linearity were 2–15 % and R² ≥ 0.9949, respectively, for all but two compounds. Matrix effects were approximately 50 % after EME and varied <11 % between 6 plasma donors, which represented a major improvement relative to a simple protein precipitation where signals were entirely suppressed. The work demonstrates a potential for EME coupled to flow injection-MS/MS to serve as a high-throughput platform for bioanalysis, not just of polar analytes, but also hydrophobic drugs both basic and acidic.

分析工作流程的高效率，包括快速样品制备和 LC-MS/MS 分析，是分析大量样品时的一大优势。然而，在测定复杂生物样品中的极性分析物时，这可能是一个挑战，人们必须在简单的样品制备和长时间的色谱分离之间做出折衷，或者反之亦然，以限制基质效应。在这项概念验证工作中，将一步法 96 孔（平行萃取）电膜萃取（EME）方法与每个样品 0.7 分钟的流动进样-MS/MS 相结合，可以非常高通量地分析来自稀释度有限的未沉淀血浆中的 12 种极性内源性代谢物。EME 方法的通量与后续分析相匹配。除两种化合物外，所有化合物的回收率为 6% 至 93%，重复性和线性度分别为 2% 至 15%，R2 ≥ 0.9949。EME 后基质效应约为 50%，6 位血浆供体之间的基质效应差异为 11%，与信号完全被抑制的简单蛋白质沉淀相比，这是一项重大改进。这项工作证明了 EME 与流动注射-MS/MS 相结合作为生物分析高通量平台的潜力，不仅适用于极性分析物，也适用于碱性和酸性疏水性药物。

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引用次数: 0

Integrated multidimensional chromatography on preparative scale for oligonucleotides purification 制备规模的集成多维色谱法用于寡核苷酸纯化

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2024-10-15 DOI: 10.1016/j.chroma.2024.465440

Chiara Nosengo , Desiree Bozza , Giulio Lievore , Sebastian Vogg , Martina Catani , Alberto Cavazzini , Thomas Müller-Späth , Chiara De Luca , Simona Felletti

Therapeutic oligonucleotides represent a recent breakthrough in the pharmaceutical industry due to their ability to regulate gene expression with great specificity. This aspect allows treatment of a wide range of diseases. However, since oligonucleotides are used for therapeutic purposes, the Active Pharmaceutical Ingredient (API) must fulfill strict purity levels which require intensive purification steps. For oligonucleotides, and biomolecules in general, preparative liquid chromatography is the technique of choice to perform large scale purifications, typically in batch mode, i.e. using a single column. Specifically, since ONs are mainly large, hydrophilic and charged molecules, Anion Exchange chromatography (AEX) and Ion Pair Reversed Phase chromatography (IP-RP) are the preferred chromatographic modes for their downstream processing. Nevertheless, these approaches suffer from a purity-yield trade-off, and for this reason, more than one purification step is usually required. The two chromatographic modes can therefore be used consequently to remove different groups of impurities, thanks to their orthogonality.

In this work, a multidimensional and orthogonal approach on a (semi)preparative scale, namely “Integrated Batch process”, was applied for the purification of a single-stranded DNA oligonucleotide. This process combines two chromatographic steps without any hold step, operator intervention or sampling of the first step. The performance parameters of the Integrated Batch were compared to those obtained in the single batch runs under different experimental conditions (chromatographic mode, eluent systems), showing the potential of this integrated approach. This proof-of-concept study illustrates how this technique can considerably reduce overall production time and how it allows to increase the robustness and reproducibility of the method, since the process is highly automated.

治疗性寡核苷酸具有高度特异性的基因表达调控能力，是制药业的最新突破。在这方面，寡核苷酸可以治疗多种疾病。然而，由于寡核苷酸用于治疗目的，活性药物成分（API）必须满足严格的纯度要求，这就需要密集的纯化步骤。对于寡核苷酸和一般生物大分子而言，制备型液相色谱法是进行大规模纯化的首选技术，通常采用批处理模式，即使用单一色谱柱。具体来说，由于 ONs 主要是大分子、亲水性分子和带电分子，因此阴离子交换色谱（AEX）和离子对反相色谱（IP-RP）是其下游处理的首选色谱模式。然而，这些方法在纯度-产量之间存在权衡，因此通常需要一个以上的纯化步骤。在这项工作中，我们采用了一种（半）制备规模的多维正交方法，即 "集成批次工艺"，用于纯化单链 DNA 寡核苷酸。该工艺将两个色谱步骤结合在一起，第一步没有任何保持步骤、操作员干预或取样。在不同的实验条件（色谱模式、洗脱液系统）下，集成批次的性能参数与单批次运行的性能参数进行了比较，显示了这种集成方法的潜力。这项概念验证研究说明了该技术如何大大缩短整体生产时间，以及如何通过高度自动化的流程提高方法的稳健性和可重复性。

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引用次数: 0

Cyano-modified molecular cage silica gel stationary phase: Multi-functional chromatographic performance by high-performance liquid chromatography 氰基改性分子笼硅胶固定相：高效液相色谱的多功能色谱性能

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2024-10-15 DOI: 10.1016/j.chroma.2024.465441

Zhen Li , Zixia Tang , Junxiang Cao , Xingyu Yao , Jia Chen , Kang Xu , Ruixue Sun , Xiaoyi Shao , Mei Lv , Litao Wang

This study successfully prepared different loading levels of cyano-functionalized RCC3 molecular cage silica gel stationary phase (RCC3-CN@SiO₂) through aldehyde-amine condensation reaction and subsequent modification strategies. Fourier transform infrared spectroscopy, thermogravimetric analysis, nitrogen adsorption-desorption, and scanning electron microscopy confirmed the successful synthesis of RCC3-CN@SiO₂ chromatographic stationary phase. The research demonstrates that due to hydrophobic/hydrophilic interactions, π-π interactions, hydrogen bonding, and size-selective porous structure, the stationary phase effectively separates moderately polar and weakly polar compounds in reversed-phase liquid chromatography (RPLC) mode, exhibiting hydrophobic selectivity comparable to the commercial DaisoC18-RP columns. Additionally, the tertiary amine and cyanogen groups on the molecular cage surface enhance the interaction with polar compounds, successfully separating nucleosides, sulfonamides, amino acids, and sugars in hydrophilic interaction chromatography (HILIC) mode. Further applications in the separation analysis of acidic drugs, alkaline drugs, cinnamic acid natural products, and chiral compounds demonstrate the multifunctional chromatographic capabilities for diverse compound types. Compared to Unitary Diol commercial columns, the prepared stationary phase showed significant advantages in wide polarity range separation performance. Moreover, through nucleoside compound separation mode switching analysis, RCC3-CN@SiO₂ stationary phase further validates its favorable performance in both RPLC and HILIC modes, demonstrating extensive potential applications in the field of analytical chemistry. Importantly, the stationary phase exhibits efficient separation of nucleoside compounds in pure water systems, aligning with the principles of green analysis.

本研究通过醛胺缩合反应及后续改性策略，成功制备了不同负载水平的氰基功能化 RCC3 分子笼硅胶固定相（RCC3-CN@SiO2）。傅立叶变换红外光谱、热重分析、氮吸附-解吸和扫描电子显微镜证实了 RCC3-CN@SiO2 色谱固定相的成功合成。研究表明，由于疏水/亲水相互作用、π-π相互作用、氢键和尺寸选择性多孔结构，该固定相在反相液相色谱（RPLC）模式下可有效分离中等极性和弱极性化合物，其疏水选择性与商用 DaisoC18-RP 色谱柱相当。此外，分子笼表面的叔胺和氰基还能增强与极性化合物的相互作用，从而在亲水相互作用色谱（HILIC）模式下成功分离核苷、磺胺、氨基酸和糖类。在酸性药物、碱性药物、肉桂酸天然产品和手性化合物的分离分析中的进一步应用，证明了该色谱柱具有针对不同化合物类型的多功能色谱能力。与 Unitary Diol 商用色谱柱相比，制备的固定相在宽极性范围分离性能方面具有显著优势。此外，通过核苷化合物分离模式切换分析，RCC3-CN@SiO2 固定相进一步验证了其在 RPLC 和 HILIC 两种模式下的良好性能，展示了其在分析化学领域的广泛应用潜力。重要的是，该固定相能在纯水体系中高效分离核苷化合物，符合绿色分析的原则。

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引用次数: 0

Application of magnetic AlFu MOF nanocomposite for the extraction and preconcentration of some pesticides from different distillates 应用磁性 AlFu MOF 纳米复合材料萃取和预富集不同蒸馏物中的某些农药

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2024-10-12 DOI: 10.1016/j.chroma.2024.465436

Mir Ali Farajzadeh , Zahra Hallaji , Sakha Pezhhanfar , Mohammad Reza Afshar Mogaddam

This research used a magnetic AlFu nano-metal-organic framework as an adsorbent for the first time. This approach extracts and preconcentrates eight pesticides from various distillates through a two-step process: magnetic dispersive micro solid phase extraction and dispersive liquid-liquid microextraction. Initially, the nanocomposite is dispersed into a sample solution containing the pesticides and Na₂SO₄. The target pesticides are then adsorbed onto the nanocomposite, which is subsequently isolated from the aqueous phase using an external magnetic field. Acetonitrile is used to elute the adsorbed analytes pesticides from the nanocomposite surface. The resulting acetonitrile extract, containing the concentrated pesticides, is then mixed with a tiny amount of another solvent and injected into a NaCl solution. Centrifugation allows the organic phase, enriched with the pesticides, to settle down. An aliquot of this organic layer is then analyzed using a gas chromatography-flame ionization detector. Optimization of the procedure led to favorable performance, including good extraction recovery of the pesticides (68–98 %), significant enrichment (enrichment factors of 340–489), a wide range of detectable concentrations (2.90–1400 µg L⁻¹), and low detection (0.15–0.88 µg L⁻¹) and quantification limits. (0.49–2.90 µg L⁻¹)

该研究首次使用磁性 AlFu 纳米金属有机框架作为吸附剂。该方法通过磁性分散微固相萃取和分散液-液微萃取两个步骤，从各种蒸馏物中提取并预浓缩八种农药。首先，将纳米复合材料分散到含有农药和 Na2SO4 的样品溶液中。然后将目标农药吸附到纳米复合材料上，再利用外加磁场将其从水相中分离出来。使用乙腈洗脱纳米复合材料表面吸附的农药分析物。含有浓缩农药的乙腈提取物与少量其他溶剂混合后注入 NaCl 溶液中。离心使富含农药的有机相沉淀下来。然后使用气相色谱-火焰离子化检测器对有机层的等分样品进行分析。通过优化程序，该方法取得了良好的性能，包括良好的农药萃取回收率（68-98%）、显著的富集效果（富集因子为 340-489）、较宽的可检测浓度范围（2.90-1400 µg L-1）、较低的检测限（0.15-0.88 µg L-1）和定量限（0.49-2.90 µg L-1）。(0.49-2.90 微克/升）。

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引用次数: 0

Evaluating the reliability of solid phase extraction techniques for hydrocarbon analysis by GC–MS 评估固相萃取技术在气相色谱-质谱法碳氢化合物分析中的可靠性。

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2024-10-12 DOI: 10.1016/j.chroma.2024.465435

Poorna Srinivasan , Estefania Michelle Endara Arguello , Ibrahim Atwah

Saturate and aromatic compounds are essential in the petroleum industry for assessing the thermal maturity of source rocks and oils, which is critical for basin modeling and sweet-spot mapping. These compounds also play a role in environmental applications, such as oil spill fingerprinting and biogeochemistry. However, the analysis of these compounds by gas chromatography-mass spectrometry (GC–MS) requires meticulous and time-consuming separation processes. Traditional methods like normal-phase liquid column chromatography (LCC) involve large volumes of harmful solvents. This study evaluates the effectiveness of five different sorbents using solid-phase extraction (SPE) techniques—neutral Si, SiOH, Ag-ion, neutral Al, and Ag-ion mixed with activated silica—compared to LCC. The goal was to discern differences in peak resolution, concentration, and isomer ratios of saturate and aromatic compounds for thermal maturity and source rock assessments. The results show that SiOH, neutral Si, and neutral Al do not fully separate aromatic compounds from the saturate fraction, sometimes leaving 40–100% of aromatics within the saturate fraction. Ag-ion mixed with activated silica provided the best separation, resulting in up to 23 times higher aromatic concentration than SiOH. This method is more reliable for quantifying both saturate and aromatic compounds, increases the efficiency of hydrocarbon evaluations, and reduces solvent consumption by 63%, offering a more sustainable approach to hydrocarbon analysis.

饱和化合物和芳香化合物在石油工业中至关重要，可用于评估源岩和石油的热成熟度，这对于盆地建模和甜点绘图至关重要。这些化合物在石油泄漏指纹识别和生物地球化学等环境应用中也发挥着重要作用。然而，使用气相色谱-质谱法（GC-MS）分析这些化合物需要细致而耗时的分离过程。传统方法（如正相液相色谱法（LCC））需要使用大量有害溶剂。本研究利用固相萃取 (SPE) 技术评估了五种不同吸附剂（中性硅、SiOH、Ag-离子、中性铝和与活性二氧化硅混合的 Ag-离子）与 LCC 相比的效果。目的是找出饱和化合物和芳香化合物在峰值分辨率、浓度和异构体比率方面的差异，以便进行热成熟度和源岩评估。结果表明，SiOH、中性硅和中性铝不能完全将芳香族化合物从饱和组分中分离出来，有时会在饱和组分中残留 40-100% 的芳香族化合物。与活性二氧化硅混合的 Ag-ion 分离效果最好，其芳烃浓度比 SiOH 高出 23 倍。这种方法对饱和化合物和芳香族化合物的定量更为可靠，提高了碳氢化合物评估的效率，并将溶剂消耗量减少了 63%，为碳氢化合物分析提供了一种更具可持续性的方法。

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引用次数: 0

Ultrasound-assisted rapid growth of chemically bonded bifunctional mesoporous covalent organic framework submicrospheres on a nickel-chromium alloy support for efficient solid-phase microextraction of bisphenols from water and milk samples 超声波辅助双功能化学键介孔共价有机框架亚微球在镍铬合金载体上的快速生长，用于从水和牛奶样品中高效固相微萃取双酚

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2024-10-12 DOI: 10.1016/j.chroma.2024.465438

Haixia Liu , Honghong Rao , Jinxin Guo , Baolan Lu , Yuyun Wang , Rongxi Zhu , Xinzhen Du

A layer-by-layer chemical bonding strategy was developed for fast in situ growth of bifunctional mesoporous covalent organic framework submicrospheres (COF SMSs) on the nickel-chromium alloy (Ni-Cr) fiber substrate via the ultrasound-assisted Schiff-base reaction for the first time. COF SMSs showed well-defined morphology, extraordinary high surface area (1211 m²·g⁻¹) and narrow mesopore (2.50 nm) as well as excellent stability. Furthermore, the resulting Ni-Cr fiber presented outstanding adsorption capability and improved selectivity for bisphenols (BPs). Consequently, an attractive SPME-HPLC-UV approach with the Ni-Cr@Ni-Cr LDHs NSs@COF SMSs fiber was proposed for rapid preconcentration and sensitive determination of BPs. By optimizing adsorption parameters, the SPME-HPLC-UV method presented good linearity for five BPs in the ranges of 0.02–200 ng·mL⁻¹ with coefficients of determination (R²) higher than 0.999. Limits of detection and limits of quantitation were obtained from 0.003 ng·mL⁻¹ to 0.006 ng·mL⁻¹ and from 0.010 to 0.019 ng·mL⁻¹, respectively. Moreover, the intra-day and inter-day precision expressed as relative standard deviations (RSDs) was 1.57–3.52 % and 2.65–4.38 % for the proposed method with a single fiber, respectively. RSDs of the proposed method with different duplicate fibers were 3.25–6.72 %. The proposed SPME-HPLC-UV method was available for efficient preconcentration and sensitive detection of five BPs from real water and milk samples. The relative recoveries at three spiking levels of BPs were achieved in the range of 80.00–118.8 % with RSDs below 7.81 %. In addition, the prepared fiber still exhibited satisfactory adsorption performance after 120 adsorption-desorption cycles.

通过超声辅助席夫碱反应，首次在镍铬合金（Ni-Cr）纤维基底上开发了一种逐层化学键策略，用于快速原位生长双功能介孔共价有机框架亚微球（COF SMSs）。COF SMSs 形状清晰，具有超常的高比表面积（1211 m2-g-1）和窄中孔（2.50 nm），且稳定性极佳。此外，所制备的镍铬纤维具有出色的吸附能力，并提高了对双酚（BPs）的选择性。因此，利用 Ni-Cr@Ni-Cr LDHs NSs@COF SMSs 纤维进行快速预富集和灵敏测定双酚的 SPME-HPLC-UV 方法极具吸引力。通过优化吸附参数，SPME-HPLC-UV方法在0.02-200 ng-mL-1范围内对5种BPs具有良好的线性关系，测定系数（R2）大于0.999。检出限和定量限分别为 0.003 ng-mL-1 至 0.006 ng-mL-1 和 0.010 至 0.019 ng-mL-1。此外，使用单根纤维的拟议方法的日内和日间精密度（以相对标准偏差（RSD）表示）分别为 1.57%-3.52% 和 2.65%-4.38%。使用不同重复纤维的拟议方法的 RSD 为 3.25-6.72%。所提出的SPME-HPLC-UV方法可用于实际水和牛奶样品中5种溴化萘的高效预浓缩和灵敏检测。在三个添加水平下，BPs的相对回收率为80.00-118.8%，RSD低于7.81%。此外，所制备的纤维在经过 120 次吸附-解吸循环后仍具有令人满意的吸附性能。

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引用次数: 0

Production and radiochemical separation of Tb-161 as a feasible beta therapeutic radioisotope from reactor irradiated Gd target 从反应堆辐照过的钆靶中生产出 Tb-161 并进行放射化学分离，将其作为一种可行的β治疗放射性同位素。

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2024-10-12 DOI: 10.1016/j.chroma.2024.465439

Mohamed A. Gizawy , A.M. Shahr El-Din , E.H. Borai , Nader M.A. Mohamed

Terbium-161 (¹⁶¹Tb) is a promising therapeutic radionuclide that has gained significant attention in the field of nuclear medicine in recent years. ¹⁶¹Tb has several favorable characteristics that make it a valuable candidate for targeted radionuclide therapy. The production of No-carrier-added ¹⁶¹Tb was carried out by the neutron activation of natural gadolinium target in the Egyptian Second Research Reactor (ETRR-2) at a thermal neutron flux position of 1.8 × 10¹⁴ ncm^-2s^-1. The radioactivities of ¹⁶¹Tb as well as coproduced Gd radioimpurities were computed theoretically by the MCNPX2.7.0 code and verified by actual measurements, where accepted discrepancies were obtained. The purification of ¹⁶¹Tb from irradiated Gd target was developed by Chelex-100 resin. The elution performance was studied using different eluents, and 0.1 M HNO₃ was found to be the best medium to obtain a high separation efficiency of more than 92% in a short time. The eluted ¹⁶¹Tb was of high chemical, radiochemical, and radionuclidic purities, indicating its potential for effective application in radiopharmaceutical preparation.

铽-161（161Tb）是一种很有前途的治疗用放射性核素，近年来在核医学领域备受关注。161Tb 具有多种有利特性，是放射性核素靶向治疗的重要候选材料。埃及第二研究堆（ETRR-2）在 1.8 × 1014 ncm-2s-1 的热中子通量条件下，通过对天然钆靶进行中子活化，生产出了无载流子添加的 161Tb。通过 MCNPX2.7.0 代码对 161Tb 以及共生钆放射性杂质的放射性活度进行了理论计算，并通过实际测量进行了验证，得到了可接受的差异。利用 Chelex-100 树脂开发了从辐照钆靶中提纯 161Tb 的方法。使用不同的洗脱剂对洗脱性能进行了研究，发现 0.1 M HNO3 是最佳介质，可在短时间内获得 92% 以上的高分离效率。洗脱出的 161Tb 化学纯度、放射化学纯度和放射性核素纯度都很高，表明其有望在放射性药物制备中得到有效应用。

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引用次数: 0

Simultaneous determination of pesticides, mycotoxins and ferulic acid in Angelica sinensis by GC/LC-Q-TOF/MS 利用 GC/LC-Q-TOF/MS 同时测定当归中的农药、霉菌毒素和阿魏酸

IF 3.8 2区化学 Q1 BIOCHEMICAL RESEARCH METHODS

Journal of Chromatography A

Pub Date : 2024-10-12 DOI: 10.1016/j.chroma.2024.465437

Ruobin Bai , Qiaoying Chang , Hongyan Zhang , Xiaofang Wang , Hui Chen , Yuting Bai , Guoyu Qiu , Guofang Pang , Kuikui Wang , Mengmeng Zhao , Xiaojing Zhang

In this study, a strong applicable method that could determine a total of 33 pesticides (54 compounds), 11 mycotoxins and functional components (ferulic acid) simultaneously in Angelica sinensis was developed. The compatibility of the sample pretreatment method for pesticides, mycotoxins, and functional components was improved by optimizing the acidity of extraction solvents, the sequence of ice bath and oscillation, the volumetric solution, and so on. The PRiME HLB SPE pretreatment method was chosen as the optimal one when comparing four pretreatment methods. Among the 65 contaminants, 38 of those determined by liquid chromatography and 41 of those by gas chromatography, which showed good linearity (R² > 0.9801), 97 % of them had a limit of quantitation (LOQ) of lower than 0.02 mg kg^-1. The recovery of all compounds were suited between 70 % to 120 % and the RSD were all lower than 20 % at the spiked levels of LOQ, 2 × LOQ, and 10 × LOQ. For ferulic acid, the LOQ was 50 ng/mL, and it showed good linearity (R²=0.9988) within the range of 0.5 to 10 μg/mL. The recovery and RSD were 98.1 %, and 3.2 % (n = 6), respectively. The simultaneous determination of cross-category compounds in a single sample preparation was obtained by the combination of SPE and GC/LC-Q-TOF/MS. Therefore, this study could not only shorten the time for data acquisition and data analysis, but also improve the experimental efficiency.

本研究建立了一种可同时测定当归中33种农药（54个化合物）、11种真菌毒素和功能成分（阿魏酸）的适用性强的方法。通过优化萃取溶剂的酸度、冰浴和振荡的顺序、体积溶液等条件，提高了样品前处理方法对农药、真菌毒素和功能成分的兼容性。在对四种前处理方法进行比较后，PRiME HLB SPE 前处理方法被选为最佳方法。在 65 种污染物中，有 38 种采用液相色谱法测定，41 种采用气相色谱法测定，其线性关系良好（R2 > 0.9801），97%的污染物的定量限（LOQ）低于 0.02 mg kg-1。在 LOQ、2 倍 LOQ 和 10 倍 LOQ 加标水平下，所有化合物的回收率均在 70% 至 120% 之间，RSD 均低于 20%。阿魏酸的最低检出限为 50 ng/mL，在 0.5 至 10 μg/mL 范围内线性关系良好（R2=0.9988）。回收率和 RSD 分别为 98.1 % 和 3.2 %（n = 6）。通过将 SPE 和 GC/LC-Q-TOF/MS 结合使用，可在单一样品制备过程中同时测定跨类别化合物。因此，该研究不仅缩短了数据采集和数据分析的时间，还提高了实验效率。

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引用次数: 0