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Modeling the combined influence of maturation and organic matter content on terahertz dielectric properties of oil shales 模拟成熟度和有机质含量对油页岩太赫兹介电性质的综合影响。
IF 2 4区 化学 Q3 CHEMISTRY, ANALYTICAL Pub Date : 2025-08-19 DOI: 10.1007/s44211-025-00834-5
Federico Sanjuan, Charles Aubourg, Bertrand Fasentieux, Maria Angels Subirana, François Baudin, Maxime Bernier

Maturation and organic matter content are critical factors influencing the hydrocarbon generation potential and economic viability of oil shales. Accurate assessment of these parameters is essential for optimizing extraction techniques and evaluating resource quality. While previous studies have individually linked maturation and organic content to dielectric permittivity in the terahertz (THz) range, their combined influence has not yet been thoroughly investigated. In this study, we explore the interdependence between maturation, organic matter content, and THz dielectric properties. Fifteen oil shale samples from two distinct basins were analyzed using Rock-Eval thermal analysis to quantify organic content, vitrinite reflectance to determine thermal maturity, and THz time-domain spectroscopy to estimate dielectric permittivity. Based on these analyses, we propose an empirical model that links these three parameters through a fitted surface, achieving a 75% accuracy in data representation. These findings provide a more robust framework than previous approaches for characterizing oil shales and enhancing resource evaluation.

Graphical abstract

成熟度和有机质含量是影响油页岩生烃潜力和经济可行性的关键因素。准确评估这些参数对于优化提取技术和评价资源质量至关重要。虽然以前的研究分别将成熟度和有机含量与太赫兹(THz)范围内的介电常数联系起来,但它们的综合影响尚未得到彻底的研究。在这项研究中,我们探讨了成熟度,有机质含量和太赫兹介电性能之间的相互关系。来自两个不同盆地的15个油页岩样品使用Rock-Eval热分析来量化有机含量,镜质组反射率来确定热成熟度,太赫兹时域光谱来估计介电常数。基于这些分析,我们提出了一个经验模型,通过拟合曲面将这三个参数联系起来,在数据表示上达到75%的精度。这些发现为油页岩特征和加强资源评价提供了比以前的方法更强大的框架。
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引用次数: 0
Simple and rapid TLC blotting-based methodology for screening membrane protein-specific lipids 基于薄层色谱印迹的膜蛋白特异性脂质的简单快速筛选方法。
IF 2 4区 化学 Q3 CHEMISTRY, ANALYTICAL Pub Date : 2025-08-19 DOI: 10.1007/s44211-025-00841-6
Supakorn Wangamnuayporn, Nobuaki Matsumori

We present a novel methodology for the rapid and simplified screening of membrane protein (MP)-specific lipids, utilizing thin-layer chromatography (TLC) to separate lipid mixtures, followed by colorimetric detection using our recently developed MP-immobilized gold nanoparticles (AuNPs). After separation, the lipids on the TLC plate were transferred to a polyvinylidene difluoride (PVDF) membrane and visualized colorimetrically with MP-functionalized AuNPs. Lipid species on the TLC or PVDF membrane were further annotated via mass spectrometry. To enhance the visualization of specifically interacting lipids and minimize non-specific binding on the PVDF membrane, several factors, including AuNP size, blocking with bovine serum albumin, and detergent washing, were optimized using bacteriorhodopsin (bR)-immobilized AuNPs. Consequently, S-TGD-1, a known bR-specific lipid, was strongly detected, confirming the effectiveness of this method. We then applied this approach to the potassium channel KcsA and demonstrated that cardiolipin band on the PVDF was most strongly stained by KcsA-immobilized AuNPs. This is consistent with previous reports identifying cardiolipin as a KcsA-specific lipid. To more quantitatively identify MP-specific lipids, we also introduced the Binding Index (BI), which reproduced that S-TGD-1 and cardiolipin are specific to bR and KcsA, respectively. Thus, the utility of this methodology was demonstrated through studies with bR and KcsA. This technique offers a broadly applicable approach for identifying MP-binding lipids without requiring extensive lipid purification or sophisticated instrumentation, providing a versatile tool for studying MP–lipid interactions.

Graphical Abstract

我们提出了一种快速和简化筛选膜蛋白(MP)特异性脂质的新方法,利用薄层色谱(TLC)分离脂质混合物,然后使用我们最近开发的MP固定化金纳米颗粒(AuNPs)进行比色检测。分离后,将TLC板上的脂质转移到聚偏二氟乙烯(PVDF)膜上,用mp功能化的aunp比色法进行可视化。TLC或PVDF膜上的脂质种类通过质谱进一步注释。为了增强特异性相互作用脂质的可视化,并减少PVDF膜上的非特异性结合,使用细菌视紫红质(bR)固定化AuNP,优化了AuNP大小、牛血清白蛋白阻断和洗涤剂洗涤等几个因素。因此,已知的br特异性脂质S-TGD-1被强烈检测到,证实了该方法的有效性。然后,我们将这种方法应用于钾通道KcsA,并证明PVDF上的心磷脂带被KcsA固定的aunp染色最强烈。这与先前的报道一致,认为心磷脂是ksa特异性脂质。为了更定量地鉴定mp特异性脂质,我们还引入了结合指数(BI),该指数再现了S-TGD-1和心磷脂分别对bR和KcsA特异性。因此,通过bR和KcsA的研究证明了这种方法的实用性。该技术提供了一种广泛适用的方法来鉴定mp结合脂质,而不需要广泛的脂质纯化或复杂的仪器,为研究mp -脂质相互作用提供了一个通用的工具。
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引用次数: 0
Effect of ammonium fluoride as a mobile phase additive on quantitativity of fatty acids in electrospray ionization–liquid chromatography–tandem mass spectrometry 流动相添加剂氟化铵对电喷雾电离-液相色谱-串联质谱法中脂肪酸定量的影响。
IF 2 4区 化学 Q3 CHEMISTRY, ANALYTICAL Pub Date : 2025-08-18 DOI: 10.1007/s44211-025-00832-7
Kohei Kawabata, Haruka Muraoka, Yuya Ohtsuki, Soo Takasu, Yukihiro Esaka, Akira Tokumura, Hiroyuki Nishi

Fatty acids (FAs) are essential molecules in biological systems and have crucial roles for fundamental components of cellular membranes, energy stores and mediators for cellular functions. The growing importance of FAs has also paid attention to analytical methods for the determination of FA contents in various samples accurately. Liquid chromatography tandem mass spectrometry (LC–MS/MS) analysis is a powerful tool due to less time for sample preparation and analysis. This analytical approach enables to quantify levels of FA and other lipid classes in various samples simultaneously without derivatization. In the present study, the effects of ammonium salts on the sensitivity of FAs in LC–MS/MS analysis were evaluated. First, authors performed the comparison of FA analysis with different mobile phases, which contain ammonium formate, ammonium fluoride, ammonium acetate or ammonium carbonate. Interestingly, the mobile phase containing ammonium fluoride enhanced the sensitivity of targeted FA species more than other ammonium salts. Second, the difference of quantativity of FA species was examined. It was indicated that both carbon chain length and the number of double bonds affect ionization of FA species. Finally, the method of FA analysis based on ammonium fluoride was applied to FA profiling of lotus root. It is indicated that mobile phase containing ammonium fluoride enabled to evaluate FA contents with highly sensitivity in LC–MS/MS analysis.

Graphical Abstract

脂肪酸(FAs)是生物系统中必不可少的分子,是细胞膜的基本成分、能量储存和细胞功能介质的重要组成部分。脂肪酸含量的日益重要也引起了人们对准确测定各种样品中脂肪酸含量的分析方法的关注。液相色谱串联质谱(LC-MS/MS)分析是一个强大的工具,由于较少的时间样品制备和分析。这种分析方法能够同时量化各种样品中的FA和其他脂类水平,而无需衍生化。本研究评价了铵盐对LC-MS/MS分析中FAs敏感性的影响。首先,对不同流动相甲酸铵、氟化铵、乙酸铵和碳酸铵的FA分析结果进行了比较。有趣的是,含氟化铵的流动相比其他铵盐更能增强目标FA物种的敏感性。其次,考察了FA种数的差异。结果表明,碳链长度和双键数都影响FA的电离。最后,将基于氟化铵的FA分析方法应用于莲藕的FA谱分析。结果表明,在LC-MS/MS分析中,含氟化铵的流动相具有较高的灵敏度。
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引用次数: 0
Sterically hindered phenolic azomethine dyes derived from aliphatic amines: solvatochromism, DFT studies and antioxidant activity 由脂肪胺衍生的位阻酚类亚甲基染料:溶剂变色、DFT研究和抗氧化活性。
IF 2 4区 化学 Q3 CHEMISTRY, ANALYTICAL Pub Date : 2025-08-14 DOI: 10.1007/s44211-025-00837-2
Iveta S. Turomsha, Maxim Y. Gvozdev, Natalia V. Loginova

Displaying versatile biological activity, Schiff bases are known to possess prominent optical, thermal, and metal coordination properties, rendering them prospective for the design of dyes, photonic devices, ion sensors, molecular probes, etc. Furthermore, azomethine compounds bearing a phenolic moiety may exert antioxidant action. In this work, the antioxidant activity of the bis-substituted and mono-substituted phenolic azomethine dyes derived from 4,6-di-tert-butyl-2,3-dihydroxybenzaldehyde was determined in DPPH radical and ABTS cation radical scavenging assays, FRAP and CUPRAC metal reducing assays, and ferrous iron chelating activity assay. The effects of aliphatic amine substituents, steric factors, and the coordination behavior of the compounds on their antioxidant activity were studied. Experimental results of the antioxidant activity assays and plausible mechanisms of antioxidant action were elucidated with reference to the reaction parameters and global reactivity descriptors calculated for the DFT-optimized compound structures. The studied phenolic Schiff bases were characterized by spectroscopic and quantum chemical methods. Solvatochromic properties of the compounds were investigated in terms of the influence of solvent nature and the acidity and basicity of the medium on their catechol imine/quinone methide tautomerism.

Graphical abstract

希夫碱具有广泛的生物活性,具有突出的光学、热学和金属配位特性,在染料、光子器件、离子传感器、分子探针等方面具有广阔的应用前景。此外,含有酚基部分的亚甲基化合物可能具有抗氧化作用。以4,6-二叔丁基-2,3-二羟基苯甲醛为原料制备的双取代和单取代酚类亚甲基染料,在DPPH自由基和ABTS阳离子自由基清除实验、FRAP和CUPRAC金属还原实验以及亚铁螯合活性实验中测定了其抗氧化活性。研究了脂肪胺取代基、位阻因子和化合物的配位行为对其抗氧化活性的影响。根据dft优化后化合物结构的反应参数和整体反应活性描述符,对实验结果和抗氧化作用的可能机制进行了阐述。用光谱和量子化学方法对所研究的酚类席夫碱进行了表征。从溶剂性质和介质的酸碱度对化合物的邻苯二酚亚胺/甲基醌互变异构的影响等方面考察了化合物的溶剂致变色性质。
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引用次数: 0
Evaporation of volatile guest compounds incorporated into solid-state cyclodextrins 挥发性客体化合物并入固态环糊精的蒸发。
IF 2 4区 化学 Q3 CHEMISTRY, ANALYTICAL Pub Date : 2025-08-08 DOI: 10.1007/s44211-025-00833-6
Ikuo Ueta, Nan Jin, Tetsuo Kuwabara, Yoshihiro Saito

The evaporation of volatile naphthalene compounds incorporated into solid-state cyclodextrins (CDs) was quantitatively evaluated using a solid-phase extraction (SPE) device and high-performance liquid chromatography (HPLC). Initially, an aqueous CD solution was spiked on a quartz filter and dried. Then, solution of naphthalene compounds in acetone was spiked on the filter, resulting in the formation of guest–CD complexes on the filter. The filter was fixed in a filter holder, and the SPE device was connected to the filter holder. Subsequently, clean air was collected via the filter holder and the SPE device using a gas sampling pump. During air sampling, naphthalene compounds evaporated from the filter and were collected on the SPE device. Subsequently, naphthalene compounds in the SPE device and the filter were eluted with acetone, followed by quantification with HPLC. The results indicated that the inclusion in solid-state β-CD suppressed the evaporation of naphthalene compounds. In addition, the inclusion effect was stronger for the dry than for the wet CDs. The inclusion effect was also found to increase with temperature.

Graphical abstract

采用固相萃取法(SPE)和高效液相色谱法(HPLC)定量评价了挥发性萘化合物掺入固态环糊精(CDs)的挥发性。首先,将CD水溶液加在石英过滤器上并干燥。然后,将萘化合物的丙酮溶液加在过滤器上,在过滤器上形成客体cd配合物。将过滤器固定在过滤器支架上,固相萃取装置连接在过滤器支架上。随后,使用气体取样泵通过过滤器支架和SPE装置收集清洁空气。在空气取样过程中,萘化合物从过滤器中蒸发出来,并在SPE装置上收集。随后,用丙酮洗脱固相萃取装置和过滤器中的萘化合物,然后用高效液相色谱进行定量。结果表明,固相β-CD包合物抑制萘类化合物的蒸发。此外,干燥cd的包合效应强于湿cd。夹杂物效应也随着温度的升高而增大。
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引用次数: 0
Light-up RNA aptamer-based T-NASBA: a one-pot, label-free strategy for miRNA detection 基于点亮RNA适配体的T-NASBA:一种单罐、无标记的miRNA检测策略。
IF 2 4区 化学 Q3 CHEMISTRY, ANALYTICAL Pub Date : 2025-08-04 DOI: 10.1007/s44211-025-00811-y
Yao Fu, Xuejuan Pei, Junhua Cao, Qiang Chen, Shixiong Deng

MicroRNAs (miRNAs) are pivotal regulators of cellular processes, with dysregulation linked to diverse diseases, particularly cancer. Current methods, while effective, are often expensive, complex, and require sophisticated equipment. To address these limitations, we developed a label-free, one-pot miRNA detection platform integrating toehold-mediated strand displacement (TMSD) with nucleic acid sequence-based amplification (NASBA). This method utilizes a TMSD-regulated hairpin Primer1 that selectively responds to target miRNA, triggering NASBA to generate a light-Up RNA aptamer for real-time, target-dependent fluorescence signaling-eliminating the need for fluorophore-labeled probes or additional modifications. By systematic optimization of the reaction conditions, the platform achieved a detection limit of 4.31 pM, with a strong linear correlation between fluorescence intensity and miRNA concentration over a range from 10 pM to 1 nM. The platform also demonstrated excellent reproducibility and precision in spike-and-recovery tests with human serum, with recovery rates between 99.85(%) and 108.28(%). T-NASBA provides a novel, cost-effective, and label-free platform for miRNA detection, offering a simple alternative that requires no complex instrumentation. This makes T-NASBA ideal for a wide range of applications, including point-of-care diagnostics and research, further advancing the field of miRNA-based diagnostics and monitoring.

Graphical abstract

MicroRNAs (miRNAs)是细胞过程的关键调节因子,其失调与多种疾病,特别是癌症有关。目前的方法虽然有效,但往往昂贵、复杂,需要精密的设备。为了解决这些局限性,我们开发了一种无标记的单罐miRNA检测平台,将脚位介导的链位移(TMSD)与核酸序列扩增(NASBA)相结合。该方法利用tmsd调控的发夹引物1选择性地响应目标miRNA,触发NASBA产生点亮RNA适体,用于实时,目标依赖的荧光信号,从而消除了对荧光团标记探针或其他修饰的需要。通过对反应条件的系统优化,该平台的检出限为4.31 pM,在10 pM ~ 1 nM范围内,荧光强度与miRNA浓度呈较强的线性相关关系。该平台对人血清的加标回收率为99.85% ~ 108.28%,具有良好的重现性和精密度。T-NASBA提供了一种新颖、经济、无标签的miRNA检测平台,提供了一种简单的替代方案,不需要复杂的仪器。这使得T-NASBA成为广泛应用的理想选择,包括即时诊断和研究,进一步推进基于mirna的诊断和监测领域。
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引用次数: 0
A conjugated pyridine diimine fluorene-based polymer for the detection of furaltadone 一种检测呋喃他酮的共轭吡啶二亚胺芴基聚合物。
IF 2 4区 化学 Q3 CHEMISTRY, ANALYTICAL Pub Date : 2025-08-01 DOI: 10.1007/s44211-025-00829-2
Lindan Gong, Yan Sun, Hongju Zhang, Junqing Li, Aohui Qin, Lu-an Fan

The potential risks posed by antibiotics to human health and the ecological environment have long been a major public concern. Consequently, developing probe technologies capable of efficiently detecting trace levels of antibiotics in environments has emerged as a critical research priority. In this study, a conjugated fluorene-based pyridine diimine polymeric probe (FPD) was employed as a fluorescent probe for the specific recognition and detection of furaltadone. Experimental results showed that FPD rapidly interacts with furaltadone, resulting in a significant fluorescence quenching of FPD, and its fluorescence intensity could quickly reach a stable state. In the ethanol-PBS mixed solution system, the fluorescence quenching efficiency of FPD exhibits an excellent linear relationship with furaltadone concentrations ranging from 0 to 12 µM, achieving a detection limit as low as 0.0490 µM. In the presence of interfering substances, FPD maintains superior selectivity and anti-interference capability. Furthermore, a recovery experiment was conducted by spiking furaltadone into egg white, yielding recovery rates ranging from 97.29% to 104.22%, with a relative standard deviation (RSD) of less than 3.73%. This study develops a novel and reliable method for the efficient and precise detection of furaltadone, demonstrating broad application potential.

Graphical abstract

抗生素对人类健康和生态环境的潜在风险一直是公众关注的焦点。因此,开发能够有效检测环境中微量抗生素水平的探针技术已成为关键的研究重点。本研究采用共轭芴基吡啶二亚胺聚合物探针(FPD)作为荧光探针,对呋喃他酮进行特异性识别和检测。实验结果表明,FPD与呋喃他酮快速相互作用,导致FPD的荧光明显猝灭,其荧光强度可以快速达到稳定状态。在乙醇- pbs混合溶液体系中,FPD的荧光猝灭效率与氟拉他酮浓度在0 ~ 12µM范围内呈良好的线性关系,检出限低至0.0490µM。在干扰物质存在的情况下,FPD保持了优越的选择性和抗干扰能力。在蛋白中加入呋喃他酮,回收率为97.29% ~ 104.22%,相对标准偏差(RSD)小于3.73%。本研究为高效、精确检测呋喃他酮提供了一种新颖可靠的方法,具有广阔的应用前景。
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引用次数: 0
Surfactant aggregates for preconcentration of trace analytes 痕量分析物预富集用表面活性剂聚集体。
IF 2 4区 化学 Q3 CHEMISTRY, ANALYTICAL Pub Date : 2025-07-29 DOI: 10.1007/s44211-025-00810-z
Hiroaki Matsumiya
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引用次数: 0
Simultaneous determination of mumefural and citric acid in Japanese apricot fruit juice concentrate using LC with intramolecular excimer-forming derivatization 分子内模拟衍生液相色谱法同时测定日本杏浓缩汁中的乳酸菌和柠檬酸。
IF 2 4区 化学 Q3 CHEMISTRY, ANALYTICAL Pub Date : 2025-07-29 DOI: 10.1007/s44211-025-00822-9
Hideyuki Yoshida, Yuka Imura, Sayaka Minematsu, Misaki Ono, Reiko Koga, Hitoshi Nohta

Mumefural (MF) which is one of the citrate esters with 5-hydoxymethyl-2-furfural is a component of Japanese apricot fruit juice concentrate (plum extract). A selective LC-fluorescence detection method was developed for the simultaneous quantification of MF and citric acid in plum extracts using intramolecular excimer-forming derivatization. Analytes were derivatized to their corresponding polypyrene derivatives using 4-(1-pyrene)butyric hydrazide (PBH) in the presence of condensation reagent, separated by reversed-phase LC, and detected in the pyrene-excimer fluorescence region (Ex/Em, 345/475 nm). The detection limits (S/N = 3) for the analytes were sub-picomole levels per 10-μL injection volume. The method was applied for the determination of MF and citric acid in plum extracts and a typical plum wine with a simple pretreatment. Large amounts of citric acid were detected in the plum extracts and the plum wine, whereas MF was detected only in the commercial plum extracts.

Graphical abstract

枸橼酸酯(MF)是一种含有5-羟基甲基-2-糠醛的柠檬酸酯,是日本杏浓缩果汁(李子提取物)的主要成分。建立了分子内模拟衍生法同时定量测定李子提取物中MF和柠檬酸的选择性lc -荧光检测方法。在缩合剂存在下,用4-(1-芘)丁基肼(PBH)将分析物衍生为相应的芘衍生物,用反相LC分离,在芘准分子荧光区(Ex/Em, 345/475 nm)检测。检出限(S/N = 3)为亚皮摩尔/ 10 μ l。采用简单的前处理方法测定了李子提取物和典型李子酒中MF和柠檬酸的含量。枸杞提取物和枸杞酒中检测到大量的柠檬酸,而枸杞提取物中仅检测到枸杞酸。
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引用次数: 0
Direct visualization of phase-separation multiphase flow in a silica bead-packed microchannel using fluorescence microscopy 用荧光显微镜直接观察硅珠填充微通道中相分离多相流。
IF 2 4区 化学 Q3 CHEMISTRY, ANALYTICAL Pub Date : 2025-07-26 DOI: 10.1007/s44211-025-00830-9
Yuya Yamashiro, Takeshi Iharada, Kazuhiko Tsukagoshi

We previously developed a high-performance liquid chromatography (HPLC) system employing phase-separation multiphase flow (PSMF) as the eluent, referred to as the phase-separation mode in HPLC. However, direct visualization of the flow behavior within the HPLC column had not yet been achieved. In this study, we directly visualized the PSMF behavior in a silica bead-packed microchannel using fluorescence microscopy. A two-phase separation mixed solution composed of 1-butyl-3-methylimidazolium chloride [(C4mim)Cl, an ionic liquid], K₂HPO₄, and water, with Eosin Y as a fluorescent dye, was introduced into a microchannel (200 μm wide, 40 μm deep) packed with 10 μm silica beads. Phase separation was induced by cooling from 40 to 25 °C, resulting in an ionic liquid-rich phase containing Eosin Y and a K2HPO4-rich phase. Fluorescence microscopy equipped with a CMOS color camera enabled visualization of the flow distribution. When the ionic liquid-rich solution was used, non-fluorescent (black) circular regions approximately 10 μm in diameter—corresponding to the silica beads—were observed, surrounded by green fluorescent areas resulting from the distribution of Eosin Y in the ionic liquid phase. These observations indicate that the ionic liquid-rich phase predominantly flows away from the surfaces of the beads. Conversely, when the K2HPO4-rich solution was used, green fluorescent regions appeared at the bead locations, surrounded by non-fluorescent areas. This indicates that the ionic liquid-rich phase, which contains Eosin Y, preferentially flows near the surfaces of the silica beads. These results provide the first direct visual evidence of PSMF behavior within a particle-packed microchannel. The findings support the proposed flow dynamics of PSMF in HPLC columns and validate the separation mechanism of the phase-separation mode.

Graphical abstract

我们之前开发了一种采用相分离多相流(PSMF)作为洗脱液的高效液相色谱(HPLC)系统,在HPLC中称为相分离模式。然而,在高效液相色谱柱内的流动行为的直接可视化尚未实现。在这项研究中,我们使用荧光显微镜直接观察了PSMF在硅珠填充微通道中的行为。将离子液体1-丁基-3-甲基咪唑氯[(C4mim)Cl]、K₂HPO₄和水组成的两相分离混合溶液,以伊红Y为荧光染料,引入宽200 μm、深40 μm、填充10 μm硅珠的微通道中。在40 ~ 25℃的冷却条件下进行相分离,得到一个富含伊红Y的富离子液体相和一个富含k2hpo4的相。配备CMOS彩色相机的荧光显微镜使流动分布可视化。当使用富离子液体溶液时,观察到直径约为10 μm的非荧光(黑色)圆形区域-与二氧化硅珠相对应-被离子液相中曙红Y分布的绿色荧光区域所包围。这些观察结果表明,富含离子液体的相主要从珠子表面流出。相反,当使用富k2hpo4溶液时,在珠状位置出现绿色荧光区域,被非荧光区域包围。这表明含有伊红Y的离子富液相优先流动在硅珠表面附近。这些结果提供了粒子填充微通道内PSMF行为的第一个直接视觉证据。研究结果支持了PSMF在HPLC柱中的流动动力学,验证了相分离模式的分离机理。
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引用次数: 0
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Analytical Sciences
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