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Automatic and precise segmentation of gas chromatographic peaks by temporal semantic segmentation for prolonged monitoring of volatile organic compounds 基于时间语义分割的气相色谱峰自动精确分割,用于挥发性有机物的长时间监测。
IF 4 2区 化学 Q1 BIOCHEMICAL RESEARCH METHODS Pub Date : 2025-12-23 DOI: 10.1016/j.chroma.2025.466650
Wei Luo , Jingping Hu , Huijie Hou , Jiakuan Yang
Long-term continuous monitoring of volatile organic compounds (VOCs) is essential for atmospheric pollution control, environmental health assessment, and climate change mitigation. Gas chromatography (GC) serves as the primary analytical technique for precise VOCs quantification in prolonged atmospheric monitoring programs. However, accurate chromatographic peak segmentation critically depends on labor-intensive manual analysis by experienced specialists, particularly when dealing with overlapping peaks caused by instrument degradation or prolonged monitoring. This study presents an innovative artificial intelligence framework combining a peak identification model (ResGRU) and time-series semantic segmentation model (UGRU) for automated gas chromatographic peak segmentation. The UGRU model innovatively improves traditional semantic segmentation frameworks by replacing convolutional feature extractors with sequential algorithms based on the temporal dynamics characteristics of chromatographic signals, achieving superior performance across four monitoring sites in Shanghai, Hubei, and Jiangsu, China, with over 85% of samples achieving absolute percentage errors below 10% and over 90% achieving errors below 20%. Cross-site transfer experiments demonstrated robust generalizability, requiring only 512 target-site samples to achieve effective adaptation through fine-tuning strategies. This work provides a transformative solution for large-scale automated VOC monitoring networks, significantly reducing manual analysis costs while enhancing data standardization, thereby enabling more effective atmospheric pollution management.
挥发性有机化合物(VOCs)的长期连续监测对于大气污染控制、环境健康评估和减缓气候变化至关重要。气相色谱(GC)是长期大气监测项目中VOCs精确定量的主要分析技术。然而,准确的色谱峰分割严重依赖于由经验丰富的专家进行的劳动密集型人工分析,特别是在处理由仪器退化或长时间监测引起的重叠峰时。本文提出了一种结合峰识别模型(ResGRU)和时间序列语义分割模型(UGRU)的人工智能框架,用于气相色谱自动峰分割。UGRU模型创新地改进了传统的语义分割框架,基于色谱信号的时间动态特征,用序列算法取代卷积特征提取器,在中国上海、湖北和江苏的4个监测点上取得了优异的性能,超过85%的样本绝对百分比误差在10%以下,超过90%的样本误差在20%以下。跨位点迁移实验表明,只需512个靶点样本就可以通过微调策略实现有效的自适应。这项工作为大规模自动化VOC监测网络提供了一种变革性的解决方案,大大降低了人工分析成本,同时增强了数据标准化,从而实现了更有效的大气污染管理。
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引用次数: 0
Investigating the influence of solvent molecular structure on the separation of α-olefins in Fischer-Tropsch naphtha 研究了溶剂分子结构对费托石脑油中α-烯烃分离的影响
IF 4 2区 化学 Q1 BIOCHEMICAL RESEARCH METHODS Pub Date : 2025-12-23 DOI: 10.1016/j.chroma.2025.466652
Tong Tong , Li Li , Yuhao Zhang , Liang Zhao , Jinsen Gao , Chunming Xu
The rapid expansion of high-end polyolefin and photovoltaic industries has pushed the annual demand for C6C8 α-olefins to million tons. Fischer-Tropsch naphtha contains over 50 % α-olefins, yet their boiling points differ very little from those of the corresponding alkanes, rendering conventional distillation unfeasible. Extractive distillation is regarded as a viable industrial separation approach. Using the n-hexane/1-hexene, we combine quantum-chemical calculations with vapor-liquid equilibrium experiments to systematically evaluate four solvents-2-pyrrolidone (2-P), dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF) and γ-butyrolactone (GBL)-and establish a quantitative “solvent structure-interaction energy-separation efficiency” relationship. Molecular polarity index and electrostatic surface potential are introduced for rapid solvent pre-screening; weak interaction analysis and interaction-energy computations clarify the selective recognition of 1-hexene. Experimental data are in agreement with theoretical predictions: solvents containing S/N heteroatoms-DMSO, 2-P and DMF-augment the negative charge on oxygen via inductive effects. Among them, the oxygen atom of DMSO exhibits the highest electron density and thus delivers the most efficient separation, whereas GBL, bearing only oxygen atoms with lower electron density, shows the poorest performance. The greater the number of electronegative functional groups and the tighter their spatial arrangement, the stronger the solvent-1-hexene interaction and the higher the separation efficiency. The proposed model provides a robust theoretical and experimental basis for the rational design of high-performance extractants and it can also be extended to the separation of other systems with polarity differences.
高端聚烯烃和光伏产业的快速扩张,推动C6C8 α-烯烃年需求量达到百万吨。费托石脑油含有超过50%的α-烯烃,但它们的沸点与相应的烷烃相差很小,使得传统的蒸馏不可行。萃取精馏被认为是一种可行的工业分离方法。利用正己烷/己烯,结合量子化学计算和汽液平衡实验,系统评价了2-吡咯烷酮(2-P)、二甲基亚砜(DMSO)、N,N-二甲基甲酰胺(DMF)和γ-丁内酯(GBL)四种溶剂,并建立了定量的“溶剂结构-相互作用能分离效率”关系。引入分子极性指数和静电表面电位进行溶剂快速预筛选;弱相互作用分析和相互作用能计算阐明了1-己烯的选择性识别。实验数据与理论预测一致:含有S/N杂原子的溶剂- dmso, 2-P和dmf -通过感应效应增加氧的负电荷。其中,DMSO的氧原子电子密度最高,分离效率最高,而GBL只携带电子密度较低的氧原子,分离效果最差。电负性官能团数量越多,空间排列越紧密,溶剂-己烯相互作用越强,分离效率越高。该模型为高效萃取剂的合理设计提供了坚实的理论和实验依据,也可推广应用于其他极性差异体系的分离。
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引用次数: 0
An octadecyl (C18) sorbent via cyanuric chloride condensation for the QuEChERS-HPLC-FLD analysis of four fluoroquinolones in cosmetic samples 十八烷基(C18) -三聚氰胺缩合吸附剂用于化妆品样品中四种氟喹诺酮类药物的QuEChERS-HPLC-FLD分析。
IF 4 2区 化学 Q1 BIOCHEMICAL RESEARCH METHODS Pub Date : 2025-12-23 DOI: 10.1016/j.chroma.2025.466649
Liang Qi, Xinting Zhang, Longjiang Li, Xilan Li, Xiangna Chang
Prolonged use of cosmetics containing banned fluoroquinolones can cause skin disorders and increase drug resistance. The QuEChERS method holds considerable application prospect in the pretreatment of cosmetic samples. Although octadecyl (C18)-bonded silica sorbent is commonly used as a QuEChERS clean-up material, the conventionally commercially available bulk C18 sorbent is relatively costly and has a limited purification mechanism. In this study, using dendritic silica sphere (dSiO2) as the substrate, and through the condensation reaction between cyanuric chloride (CNCl) and the amino group, a dNSiO2-CNCl-C18 sorbent was synthesized. The sorbent was characterized using infrared spectroscopy, transmission electron microscopy, surface area and pore size analysis, and water contact angle measurements. The experimental results regarding the matrix removal from the model cosmetic lotion showed that dNSiO2-CNCl-C18 exhibited a higher matrix removal efficiency compared to a commercial C18 sorbent. Furthermore, a QuEChERS-HPLC-FLD method was developed using dNSiO2-CNCl-C18 for the simultaneous detection of four fluoroquinolones, norfloxacin (NOR), pefloxacin (PEF), enrofloxacin (ENR), and difloxacin (DIF). The linear ranges were 0.10 to 100.0 μg L−1 for NOR and PEF, and 0.05 to 100.0 μg L−1 for ENR and DIF, with coefficient of determination exceeding 0.999. Satisfactory spiked recoveries for the lotion sample ranged from 91.5% to 107.0%, with intra-day and inter-day precision values not exceeding 7.6%. The established method was subsequently validated through its successful application in additional cream and emulsion samples. dNSiO2-CNCl-C18 exhibits low synthesis costs and demonstrates promising potential for matrix purification in various complex samples, facilitating the rapid determination of target compounds.
长期使用含有禁用氟喹诺酮类药物的化妆品会引起皮肤疾病并增加耐药性。QuEChERS方法在化妆品样品的前处理中具有相当大的应用前景。虽然十八烷基(C18)键合二氧化硅吸附剂通常被用作QuEChERS清理材料,但传统的商用散装C18吸附剂相对昂贵,并且净化机制有限。本研究以树枝状二氧化硅球(dSiO2)为底物,通过三聚氰胺(CNCl)与氨基的缩合反应,合成了一种dNSiO2-CNCl-C18吸附剂。采用红外光谱、透射电镜、表面积、孔径、水接触角等方法对吸附剂进行了表征。实验结果表明,与商用C18吸附剂相比,dNSiO2-CNCl-C18具有更高的基质去除效率。建立了采用dNSiO2-CNCl-C18同时检测诺氟沙星(NOR)、培氟沙星(PEF)、恩诺沙星(ENR)、双氟沙星(DIF) 4种氟喹诺酮类药物的QuEChERS-HPLC-FLD方法。NOR和PEF的线性范围为0.10 ~ 100.0 μ L-1, ENR和DIF的线性范围为0.05 ~ 100.0 μ L-1,决定系数均大于0.999。洗剂样品的加标回收率为91.5% ~ 107.0%,日内和日内精密度值不超过7.6%。建立的方法随后通过其在其他乳膏和乳液样品中的成功应用进行了验证。dNSiO2-CNCl-C18具有较低的合成成本,在各种复杂样品的基质纯化中具有良好的潜力,有助于快速测定目标化合物。
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引用次数: 0
Thermosensitive magnetic molecularly imprinted polymers for selective recognition and detection of sinomenine in traditional Chinese medicines and biological sample 热敏磁分子印迹聚合物在中药和生物样品中青藤碱的选择性识别和检测
IF 4 2区 化学 Q1 BIOCHEMICAL RESEARCH METHODS Pub Date : 2025-12-22 DOI: 10.1016/j.chroma.2025.466645
Jinlai Cheng , Xiaoyu Zhang , Yuyan Xu , Yu Zhao , Guozhuang Zhang , Gejing De , Yuqing Tan , Huajing Wang , Miyi Yang
A thermo-responsive magnetic molecularly imprinted polymer (TMMIP) based on magnetic graphene oxide (MGO) was prepared via surface molecular imprinting technique for selective recognition of sinomenine (SIN) in various complex matrices. The obtained nanoparticles were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), vibrating sample magnetometry (VSM), and thermogravimetric analysis (TGA). The results indicated that the TMMIP exhibited a typical core-shell structure, comprising a molecularly imprinted shell, and demonstrated both magnetic susceptibility and excellent stability. The adsorption performance of TMMIP was also studied via adsorption kinetics, adsorption isotherms and selectivity experiments. The TMMIP exhibited high adsorption capacity, high selectivity for SIN, and mild acidic elution conditions. Under the optimal conditions, an analytical methodology combining TMMIP based dispersive solid-phase microextraction with high-performance liquid chromatography (HPLC) was subsequently established. TMMIP can rapidly adsorb SIN in solution and easily collected with assistance of outer magnetic field. The analysis method exhibited linearity across 0.05–150 μg/mL with a correlation coefficient of 0.9993, while demonstrating detection sensitivity at 0.1 ng/mL (DL) and quantification capability at 0.3 ng/mL (QL). Validation using Caulis sinomenii, oral liquid and blood samples acquired recoveries of 88.8–110.4 %. This integrated approach demonstrates high efficiency for SIN extraction and detection in complex matrices and provided an efficient, eco-friendly strategy for SIN analysis.
采用表面分子印迹技术制备了一种基于磁性氧化石墨烯(MGO)的热响应磁性分子印迹聚合物(TMMIP),用于选择性识别各种复杂基质中的青藤碱(SIN)。采用扫描电镜(SEM)、透射电镜(TEM)、x射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、振动样品磁强计(VSM)和热重分析(TGA)对所得纳米颗粒进行了表征。结果表明,TMMIP具有典型的核壳结构,包括分子印迹壳,具有良好的磁化率和稳定性。通过吸附动力学、吸附等温线和选择性实验研究了TMMIP的吸附性能。TMMIP具有高吸附量、高选择性和温和的酸性洗脱条件。在最佳条件下,建立了基于TMMIP的分散固相微萃取与高效液相色谱相结合的分析方法。TMMIP可以快速吸附溶液中的SIN,并且在外部磁场的帮助下易于收集。该方法在0.05 ~ 150 μg/mL范围内呈线性关系,相关系数为0.9993,检测灵敏度为0.1 ng/mL (DL),定量能力为0.3 ng/mL (QL)。用青藤、口服液和血液样品验证,回收率为88.8 ~ 110.4%。该综合方法证明了复杂矩阵中SIN的高效提取和检测,并为SIN分析提供了高效,环保的策略。
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引用次数: 0
Update and expansion of a system constant database for biphasic liquid-liquid partition systems 双相液-液分区系统常数数据库的更新与扩展
IF 4 2区 化学 Q1 BIOCHEMICAL RESEARCH METHODS Pub Date : 2025-12-22 DOI: 10.1016/j.chroma.2025.466646
Colin F. Poole
The solvation parameter model is used to characterize the distribution of neutral organic compounds in 8 gas-liquid, 8 water-organic solvent and 22 organic solvent-organic solvent biphasic systems. The Wayne State University (WSU-2025) compound descriptor database is used exclusively as the sole source for compound descriptors to unify the model system constants with a verified descriptor database. The gas-liquid partition models provide insight into solvent properties used to explain the driving force for the distribution of varied compounds in liquid-liquid partition systems. For aqueous biphasic systems formed with cyclohexane, n-hexadecane, toluene, chlorobenzene, 1,2-dichloroethane, chloroform, or n-octanol as a counter solvent water plays a dominant role in the distribution mechanism and the selectivity space is comparatively narrow. For totally organic biphasic systems employing acetonitrile, dimethyl formamide, dimethyl sulfoxide, ethanolamine, ethylene glycol, formamide, 1,1,1,3,3,3-hexafluoroisopropanol, methanol, propylene carbonate, or 2,2,2-trifluoroethanol as the polar solvent with n-heptane (or n-hexane), isopentyl ether, 1,2-dichloroethane, n-octanol, or triethylamine as counter solvents forming biphasic systems the selectivity space is densely occupied without redundancy among the systems reflecting the wide range of properties possible for polar organic solvents and the absence of a dominant solvent in the database. The selectivity space for the aqueous and totally organic biphasic systems do not overlap on account of the significant difference for the range of the v and b system constants. Hierarchical cluster analysis with the system constants as variables is used to visualize the selectivity space to facilitate system selection.
采用溶剂化参数模型对8种气液、8种水-有机溶剂和22种有机溶剂-有机溶剂双相体系中中性有机化合物的分布进行了表征。韦恩州立大学(WSU-2025)复合描述符数据库专门用作复合描述符的唯一来源,将模型系统常数与经过验证的描述符数据库统一起来。气液分配模型提供了对溶剂性质的深入了解,用于解释液液分配系统中各种化合物分布的驱动力。对于以环己烷、正十六烷、甲苯、氯苯、1,2-二氯乙烷、氯仿或正辛醇为反溶剂形成的双水相体系,水在分配机制中起主导作用,选择性空间相对较窄。以乙腈、二甲基甲酰胺、二甲基亚砜、乙醇胺、乙二醇、甲酰胺、1,1,1,3,3,3-六氟异丙醇、甲醇、碳酸丙烯酯或2,2,2-三氟乙醇为极性溶剂的全有机双相体系,其极性溶剂为正庚烷(或正己烷)、异戊基醚、1,2-二氯乙烷、正辛醇、或者三乙胺作为反溶剂形成双相体系,选择性空间被密集占据,系统之间没有冗余,反映了极性有机溶剂可能的广泛性质和数据库中没有主导溶剂。由于系统常数v和b范围的显著差异,水相和全有机双相体系的选择性空间不重叠。采用以系统常数为变量的层次聚类分析将选择空间可视化,以方便系统选择。
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引用次数: 0
Selectivity for full AAV capsids in affinity capture with camelid ligands 骆驼配体亲和捕获全AAV衣壳的选择性
IF 4 2区 化学 Q1 BIOCHEMICAL RESEARCH METHODS Pub Date : 2025-12-20 DOI: 10.1016/j.chroma.2025.466644
Lukas Bongers , Linda E. Franken , Dominik Hoch , Veronika E. Huber , Veronika Öttl , Elena B. Raaf , Jürgen Hubbuch , Roberto Falkenstein , Andres D. Martinez
The industry standard for downstream processing of adeno-associated viral vectors (AAV) is purification by affinity capture and anion exchange polishing (AEX). Affinity capture is an attractive method for capturing AAVs as it can remove process-related impurities and selectively enrich AAVs. Full capsids are then separated on AEX-resin from product related impurities based on net surface charge. Enrichment of full capsids remains a big challenge, as biophysical properties of full and empty capsids are very similar. We present a novel approach to enrich full capsids during capture chromatography using affinity resins. We examined the impact of additives (NaCl, MgCl2, Na2SO4), NaCl concentrations (0 – 1000 mM), temperature and different affinity ligands (POROS™ CaptureSelect™ AAVX, AAV8, AAV9; CaptoAVB and AVIPure AAV8). We tested our approach for the serotypes AAV8 wild type (WT), AAV9 WT and an rAAV2 derivative and demonstrated 2.5-fold full capsid enrichment in a robotic screening. Analyzing an elution peak in fine increments yielded in multiple fractions approaching 100% full capsids. While several affinity resins demonstrated full capsid selectivity, we report that AAVX achieved the highest resolution. The selectivity was then linked to the affinity ligands specific binding mechanism towards an AAV capsid.
This novel capture method offers a trade-off between full capsid yield and purity without the need for additional unit operations while using an already established process. With enriched loading material for the subsequent anion exchange step, the polished elution pool has a higher full-to-total ratio (FTR) compared to a process based on standard affinity capture conditions.
腺相关病毒载体(AAV)下游处理的行业标准是通过亲和捕获和阴离子交换抛光(AEX)纯化。亲和捕获是一种有吸引力的捕获aav的方法,因为它可以去除过程相关的杂质并选择性地富集aav。然后,根据净表面电荷,在aex树脂上从产品相关杂质中分离出完整的衣壳。完整衣壳的富集仍然是一个很大的挑战,因为完整衣壳和空衣壳的生物物理性质非常相似。我们提出了一种利用亲和树脂在捕获色谱中富集全衣壳的新方法。我们研究了添加剂(NaCl, MgCl2, Na2SO4), NaCl浓度(0 - 1000 mM),温度和不同亲和配体(POROS™CaptureSelect™AAVX, AAV8, AAV9; CaptoAVB和AVIPure AAV8)的影响。我们对血清型AAV8野生型(WT)、AAV9 WT和rAAV2衍生物进行了测试,并在机器人筛选中证明了2.5倍的全衣壳富集。分析细增量的洗脱峰,得到接近100%完整衣壳的多个馏分。虽然几种亲和树脂表现出完全的衣壳选择性,但我们报告AAVX达到了最高的分辨率。然后将选择性与亲和配体对AAV衣壳的特异性结合机制联系起来。这种新颖的捕获方法提供了全衣壳收率和纯度之间的权衡,而不需要额外的单元操作,同时使用已经建立的工艺。与基于标准亲和捕获条件的过程相比,经过抛光的洗脱池具有更高的全-总比(FTR),为后续阴离子交换步骤提供了富集的负载材料。
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引用次数: 0
Engineered hydrophobic porous Fe3O4 microparticles for solvent-confined dispersive liquid-phase microextraction 用于溶剂约束分散液相微萃取的工程疏水多孔Fe3O4微粒。
IF 4 2区 化学 Q1 BIOCHEMICAL RESEARCH METHODS Pub Date : 2025-12-20 DOI: 10.1016/j.chroma.2025.466641
Meiijian Wang , Hao Wang , Shiyun Lou , Dexi Tao , Yaolin Tang , Bingfang Zou , Yongqiang Wang
Liquid-phase microextraction (LPME) relies critically on precise solvent control to achieve efficient extractant recovery. To address this, we developed a magnetic microparticle-based dispersive liquid-phase microextraction (MP-DLPME) strategy, employing hydrophobic porous Fe3O4 microparticles (∼1 μm) as solvent-stabilizing microcarriers. These microparticles were functionalized via covalent grafting of 3-chloropropyltriethoxysilane (CPS) and optimized porosity, enabling rigid confinement of organic solvents (e.g., 1-octanol) through dual mechanisms: (I) hydrophobic solvent anchoring to modified surfaces and (II) capillary trapping within mesopores. When applied to hydrophobic polycyclic aromatic hydrocarbons (PAHs) and organophosphorus pesticides (OPPs), the system generates solvent-encapsulated magnetic aggregates that dynamically fragment into microdroplets under vortex-induced shear forces, facilitating efficient analyte extraction via magnetic collection. By integrating the high efficiency of dispersive extraction with the rapid recovery of magnetic separation, the MP-DLPME method provides a robust sample pretreatment solution for environmental water analysis.
液相微萃取(LPME)关键依赖于精确的溶剂控制,以实现有效的萃取剂回收。为了解决这个问题,我们开发了一种基于磁性微粒子的分散液相微萃取(MP-DLPME)策略,采用疏水多孔Fe3O4微粒子(~ 1 μm)作为溶剂稳定微载体。这些微粒通过3-氯丙基三乙氧基硅烷(CPS)的共价接枝和优化的孔隙度实现功能化,通过双重机制实现有机溶剂(如1-辛醇)的刚性约束:(I)疏水溶剂锚定在修饰的表面上;(II)中孔内的毛细管捕获。当应用于疏水多环芳烃(PAHs)和有机磷农药(OPPs)时,该系统产生溶剂封装的磁性聚集体,在涡旋诱导的剪切力下动态破碎成微滴,促进通过磁性收集高效提取分析物。MP-DLPME方法将高效的分散萃取与快速回收的磁分离相结合,为环境水分析提供了一种可靠的样品前处理方案。
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引用次数: 0
Confined silica particles in dually directional 1,2,3-triazolyl phthalonitrile based network: A robust nitrogen-rich Sorbent for the enrichment of nitroaromatics from water using HPLC-UV 双向1,2,3-三唑基邻苯二腈网络中的受限二氧化硅颗粒:一种高效液相色谱-紫外富集水中硝基芳烃的富氮吸附剂
IF 4 2区 化学 Q1 BIOCHEMICAL RESEARCH METHODS Pub Date : 2025-12-20 DOI: 10.1016/j.chroma.2025.466640
Mohamed Rashad , AbdullahAlhendal , Laila Alshatti , Ali Husain
Owing to their extreme energetic properties, nitroaromatics (NACs) are well-recognized as explosive materials as well as toxic contaminations and source of environmental pollution. Thus, the development of accurate and extremely sensitive technologies for detecting NACs is critically necessary. In this study, the synthesis of a nitrogen-rich cross-linked polymer confining silica particles within its network structure (TPN-SiO2) is being described. The TPN-SiO2 material was successfully prepared, in situ, via the Cu(I)-mediated azide-alkyne cycloaddition (CuAAC) polymerization of dually directional alkyne-terminated phthalonitrile monomers with 1,4-bis(azidomethyl)benzenes in the presence of silica particles. The resulting encapsulated silica network was fully characterized using its respective XPS, SEM, TEM, and FT-IR spectroscopic data, along with TGA analysis. TPN-SiO2 was applied as an effective sorbent in solid phase extraction (SPE) for the enrichment of nitrobenzene compounds (NBs) before quantification by HPLC-UV. Three NBs (nitrobenzene, 4-nitrotoluene, and 2-nitrobenzaldehyde) were used to evaluate the effectiveness of the prepared SPE sorbent. Accordingly, and under optimal analytical extraction conditions, the results revealed a good linearity from 0.1-50 μgmL-1 with correlation coefficients (R2) higher than 0.990. As well to this, the limits of detection and quantification were determined to be 2.4-33.9 μgL-1 and 7.17–102.88 μgL-1, respectively, making this hybrid silica triazolyl-rich cross-linked sorbent appropriate for NBs enrichment and detection.
硝基芳烃由于其具有极强的能量特性,是公认的爆炸性物质,也是有毒污染物和环境污染源。因此,开发准确和极其敏感的检测NACs的技术是非常必要的。在本研究中,描述了一种将二氧化硅颗粒限制在其网络结构内的富氮交联聚合物(TPN-SiO2)的合成。在二氧化硅颗粒存在下,通过Cu(I)介导的叠氮-炔环加成(CuAAC)聚合,在原位成功制备了TPN-SiO2材料。通过XPS、SEM、TEM和FT-IR光谱数据以及TGA分析,对所得到的封装二氧化硅网络进行了全面表征。采用固相萃取法(SPE)富集硝基苯类化合物(NBs),并用高效液相色谱-紫外法(HPLC-UV)定量。用硝基苯、4-硝基甲苯和2-硝基苯甲醛三种NBs对制备的固相萃取吸附剂的效果进行了评价。在最佳分析提取条件下,样品在0.1 ~ 50 μgmL-1范围内线性良好,相关系数(R2)均大于0.990。检测限和定量限分别为2.4 ~ 33.9 μgL-1和7.17 ~ 102.88 μgL-1,表明该富三氮杂化二氧化硅交联吸附剂适用于NBs的富集和检测。
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引用次数: 0
pH-dependent separation and identification of saponins from Beta vulgaris L. using high-speed countercurrent chromatography and high-resolution mass spectrometry 高速逆流色谱和高分辨率质谱法分离鉴定甜菜皂苷的ph依赖性。
IF 4 2区 化学 Q1 BIOCHEMICAL RESEARCH METHODS Pub Date : 2025-12-20 DOI: 10.1016/j.chroma.2025.466643
Anna Tekieli , Mariusz Kowalczyk , Sławomir Wybraniec , Aneta Spórna-Kucab
This study investigated the saponins from Beta vulgaris L. cv. Cylindra roots using a combination of semi-preparative high-speed countercurrent chromatography (HSCCC) and ultra high-performance liquid chromatography coupled with high-resolution mass spectrometry (UHPLC-HRMS/MS). A new solvent system was developed for the HSCCC purification of saponins under varying pH conditions (3, 5, and 7), which significantly affected their separation. The solvent system consisted of 1-butanol, acetone, acetonitrile, and citrate-phosphate buffer (1.0:0.1:0.05:0.8; v/v/v/v).
The pH adjustment in HSCCC noticeably affected separation efficiency, with higher pH values generally leading to faster elution. The separation behavior of saponins depended primarily on the type, number, and arrangement of sugar substituents. In the HSCCC system, compounds bearing more sugar residues tend to be eluted earlier because their greater hydrophilicity enhances interactions with the mobile phase. Despite this overall trend, saponins containing terminal hexose or pentose units were eluted later, indicating that such sugars can significantly extend elution time. Additionally, saponins featuring dioxolane moieties showed a particularly strong pH dependence, with pH adjustments causing reversible shifts in the elution order of isomeric pairs.
Ten predominant saponins, including the highly concentrated betavulgaroside IV and betavulgaroside III, were quantified with high accuracy using UHPLC-HRMS/MS. The total saponin content in Cylindra was found to be 7.2 g/kg dry extract (DE), significantly higher than previously reported for other B. vulgaris cultivars. Additionally, the study identified 47 saponins, including the novel aglycone norhederagenin (m/z 455.31), thus expanding the phytochemical profile of beetroot.
本文对甜菜皂甙进行了研究。采用半制备高速逆流色谱(HSCCC)和超高效液相色谱-高分辨率质谱(UHPLC-HRMS/MS)相结合的方法对圆柱根进行分析。在不同的pH条件(3、5和7)下,开发了一种新的HSCCC纯化皂苷的溶剂体系,该溶剂体系对皂苷的分离有显著影响。溶剂体系由1-丁醇、丙酮、乙腈和柠檬酸盐-磷酸盐缓冲液(1.0:0.1:0.05:0.8;v/v/v/v)组成。HSCCC中pH值的调整对分离效率影响显著,pH值越高,洗脱速度越快。皂苷的分离行为主要取决于糖取代基的类型、数量和排列。在HSCCC体系中,含有更多糖残基的化合物倾向于更早地被洗脱,因为它们更大的亲水性增强了与流动相的相互作用。尽管有这样的总体趋势,但含有末端己糖或戊糖单位的皂苷被洗脱得较晚,这表明这些糖可以显著延长洗脱时间。此外,具有二恶烷基团的皂苷表现出特别强的pH依赖性,pH值的调整会导致同分异构体对的洗脱顺序发生可逆的变化。采用UHPLC-HRMS/MS对10种主要的皂苷进行了定量分析,包括高浓度的倍柳皂苷IV和倍柳皂苷III。总皂苷含量为7.2 g/kg,显著高于其他品种。此外,该研究还鉴定出了47种皂苷,其中包括一种新的苷元北hederagenin (m/z 455.31),从而扩大了甜菜根的植物化学图谱。
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引用次数: 0
Integrated dual adaptive control of continuous chromatographic separation processes via reinforcement learning 基于强化学习的连续色谱分离过程集成双自适应控制。
IF 4 2区 化学 Q1 BIOCHEMICAL RESEARCH METHODS Pub Date : 2025-12-19 DOI: 10.1016/j.chroma.2025.466638
Foteini Michalopoulou , Maria M. Papathanasiou
Continuous chromatographic processes involve nonlinear dynamics, cyclic operation, and strong interactions between operating variables, which make real-time control inherently complex. As process variability and integration increase, there is a growing need for adaptive control frameworks that can maintain performance under changing conditions. In this work, a reinforcement learning (RL) control framework is developed for adaptive operation of continuous chromatographic systems. The controller is trained based on a mechanistic simulation environment and learns to coordinate multiple process inputs based on observed system states. A phase-dependent reward formulation captures the trade-offs between product purity, yield, and operational efficiency, guiding the agent toward stable, high-performance operation from process start-up. The RL controller maintains the target purity under feed variations, flowrate disturbances, and measurement noise, achieves cyclic steady state (CSS) within 10 process cycles, improves process yield from 86 % to 91 %, and increases product recovery by 79 % compared to nominal operation. These results demonstrate that RL can deliver robust and adaptive control for complex multivariable chromatographic systems, providing a framework for intelligent and adaptive process operation.
连续色谱过程涉及非线性动力学、循环操作和操作变量之间的强相互作用,这使得实时控制具有内在的复杂性。随着过程可变性和集成的增加,对能够在不断变化的条件下保持性能的自适应控制框架的需求日益增长。在这项工作中,开发了一个用于连续色谱系统自适应操作的强化学习(RL)控制框架。控制器基于机械仿真环境进行训练,并根据观察到的系统状态学习协调多个过程输入。阶段相关的奖励公式捕获了产品纯度、产量和操作效率之间的权衡,引导代理从工艺启动开始走向稳定、高性能的操作。RL控制器在进料变化、流量干扰和测量噪声下保持目标纯度,在10个工艺周期内实现循环稳态(CSS),将工艺收率从86%提高到91%,与标称操作相比,产品回收率提高了79%。这些结果表明,RL可以为复杂的多变量色谱系统提供鲁棒和自适应控制,为智能和自适应过程操作提供了框架。
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引用次数: 0
期刊
Journal of Chromatography A
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