Journal of Molecular Liquids最新文献_第6页

Supramolecular deep eutectic solvents as extraction media: A green approach for recovering carob pulp antioxidants 以超分子深共晶溶剂为萃取介质：回收角豆果肉抗氧化剂的绿色方法

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-11-30 DOI: 10.1016/j.molliq.2025.129043

Atalanti Christou , Katerina A. Ioannou , Georgia D. Ioannou , Ioanna Mavrou , Ioannis J. Stavrou , Constantina P. Kapnissi-Christodoulou

The carob industry generates significant amounts of by-products, particularly carob kibbles, which are rich in phenolic antioxidants that can be recovered and reused in the food, cosmetic, and pharmaceutical industries. This study investigates the potential of carob pulp waste as a source of polyphenol-rich extracts through a novel and sustainable extraction medium. β-Cyclodextrin (CD)-acid-based supramolecular deep eutectic solvents (SUPRADESs), which combine the host-guest inclusion features of CDs and the exceptional solvation capacity of DESs, were prepared and used for polyphenol isolation. Among the solvents examined, the β-CD:malonic acid SUPRADES achieved the highest extraction efficiency for polyphenols, significantly higher than that obtained using common organic solvents. Ultrasound-assisted extraction (UAE) was optimized using response surface methodology to identify the optimal solvent-to-solid ratio (30 mL/g), extraction time (59 min), and SUPRADES water content (32.4 % w/w). The integration of SUPRADES and UAE significantly enhanced the recovery of total polyphenols, flavonoids, proanthocyanidins, and hydrolysable tannins, as well as antioxidant activity measured by DPPH, FRAP, and ABTS assays. The polyphenolic composition of the carob pulp extract was further characterized by chromatographic analysis, and solvent performance as a storage medium was evaluated by monitoring polyphenol stability under various storage conditions. The results demonstrate that the proposed methodology is an effective approach for recovering bioactive compounds from carob pulp residue and position this by-product as a promising source of antioxidants.

角豆工业产生了大量的副产品，特别是角豆杂碎，它富含酚类抗氧化剂，可以在食品、化妆品和制药工业中回收和再利用。本研究通过一种新型的可持续提取介质，探讨了角豆果肉废料作为富含多酚的提取物来源的潜力。制备了β-环糊精(CD)-酸基超分子深度共晶溶剂（SUPRADESs），该溶剂结合了CD的主-客体包合特性和DESs优异的溶剂化能力，并用于多酚的分离。在检测的溶剂中，β-CD：丙二酸SUPRADES对多酚的提取效率最高，显著高于普通有机溶剂。采用响应面法对超声辅助提取（UAE）工艺进行优化，确定最佳溶剂固比（30 mL/g）、提取时间（59 min）和SUPRADES水含量（32.4% w/w）。SUPRADES和UAE的整合显著提高了总多酚、类黄酮、原花青素和水解单宁的回收率，以及DPPH、FRAP和ABTS测定的抗氧化活性。通过色谱分析进一步表征了角豆果肉提取物的多酚成分，并通过监测多酚在不同储存条件下的稳定性来评价溶剂作为储存介质的性能。结果表明，该方法是一种有效的从角豆果肉残渣中回收生物活性化合物的方法，并将角豆果肉残渣作为一种有前途的抗氧化剂来源。

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引用次数: 0

Mutual separation of Ru, Rh, and Pd via reflux-assisted extraction and reverse-extraction using ion-pair and solvation with S- and amino-N-donor reagents 通过回流辅助萃取和离子对反萃取以及S-和氨基- n供体试剂溶剂化相互分离Ru、Rh和Pd

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-11-29 DOI: 10.1016/j.molliq.2025.129013

Yuji Sasaki , Masashi Kaneko , Masahiko Matsumiya , Yuta Kumagai

This study determined extraction and back-extraction conditions for the mutual separation of three light PGMs—Ru, Rh, and Pd. Results revealed that reagents containing soft N and S donor atoms efficiently extract and strip Pd through solvation. In comparison, Ru and Rh undergo ion-pair extraction, requiring both anionic metal species and cationic extractants to achieve high distribution ratios (D). These essential chlorinated PGM anions and protonated extractants having amino N atoms are present in HCl media. D(Ru) and D(Rh) values of approximately 100 and 10, respectively, were obtained using nitrilo-triacet-amide (NTAamide), which exhibits tetradentate coordination. Refluxing in 3–6 M HCl at 250 °C, a condition that promotes the formation of highly chlorinated PGM anionic species, increased D(Ru) and D(Rh). Additionally, Ru and Rh exhibited low reactivity with S-donor extractants, allowing Pd to be selectively extracted from a mixture of the three PGMs in HCl media using thio-reagents. Ru was extracted with separating Rh by methyl-imino-di-octyl-acetamide, a tridentate ligand, and was subsequently stripped using ethylenediamine and ethylenediaminetetraacetic acid (EDTA). Finally, Rh, the least reactive of the three metals, was extracted using NTAamide after refluxing in 6 M HCl for 60 min and was stripped using ethylenediamine. Based on these findings, a flow diagram for the mutual separation of the aforementioned three PGMs was developed. Thus, novel amino-amide extractants with multidentate coordination play a crucial role in PGM recovery and isolation, while stripping can be efficiently performed using commercially available reagents.

本研究确定了ru、Rh、Pd三种轻pgm相互分离的萃取和反萃取条件。结果表明，含软N和S供体原子的试剂通过溶剂化可以有效地提取和剥离Pd。相比之下，Ru和Rh采用离子对萃取，需要阴离子金属种和阳离子萃取剂才能达到较高的分布比(D)。这些必需的氯化PGM阴离子和具有氨基N原子的质子化萃取剂存在于盐酸介质中。采用四齿配位的硝基三乙酰胺（NTAamide）得到D（Ru）和D（Rh）值分别约为100和10。在250°C的条件下，在3-6 M HCl中回流，促进形成高度氯化的PGM阴离子，增加D（Ru）和D（Rh）。此外，Ru和Rh与s供体萃取剂表现出较低的反应性，允许在HCl介质中使用硫代试剂选择性地从三种pgm混合物中提取Pd。用三齿配体甲基亚胺-二辛基乙酰胺分离Rh提取Ru，然后用乙二胺和乙二胺四乙酸（EDTA）进行剥离。最后，在6 M HCl中回流60 min后，用NTAamide提取三种金属中反应性最低的Rh，然后用乙二胺剥离。基于这些发现，开发了上述三种pgm相互分离的流程图。因此，具有多齿配位的新型氨基酰胺萃取剂在PGM的回收和分离中起着至关重要的作用，而剥离可以使用市售试剂有效地进行。

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引用次数: 0

Experimental validation of the complete scaling fundamental principles in the theory of critical phenomena 临界现象理论中完全标度基本原理的实验验证

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-11-29 DOI: 10.1016/j.molliq.2025.129035

M.Yu. Belyakov , R.G. Batyrovа , N.V. Ibavov , I.M. Abdulagatov

The main theoretical and physical principles of the complete scaling approach have been validated using experimental measurements of the isochoric heat capacity as well as the saturated liquid and vapor densities of CO₂ in the immediate vicinity of the critical point. The physical meaning and theoretical importance of the critical anomaly of

C_{V}

measurements for a microscopic interpretation of critical and supercritical phenomena in CO₂ is discussed. A method to separate the singular diameter behavior of the liquid + gas phase equilibrium curve for the density-temperature projection at the criticality is proposed. It enables the direct confirmation of the complete scaling fundamental principles for the critical phenomena theory based on the reliable experimental data, without statistical data processing. The method has been successfully tested on the well-studied fluids such as CO₂, CH₄, C₂H₆, and SF₆, and can be used for an accurately determining the critical density of single-component molecular liquid.

完全标度法的主要理论和物理原理已经通过等时热容的实验测量以及临界点附近CO2的饱和液体和蒸汽密度得到验证。讨论了CV测量临界异常对CO2中临界和超临界现象的微观解释的物理意义和理论重要性。提出了一种分离液+气相平衡曲线在临界处密度-温度投影的奇异直径行为的方法。它可以根据可靠的实验数据直接确定临界现象理论的完整标度基本原理，而不需要进行统计数据处理。该方法已成功地在CO2、CH4、C2H6、SF6等研究充分的流体上进行了测试，可用于精确测定单组分分子液体的临界密度。

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引用次数: 0

Phase behavior of the thermotropic melt of chiral star-shaped trimer molecules 手性星形三聚体分子热致熔体的相行为

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-11-29 DOI: 10.1016/j.molliq.2025.129064

M.A. Aliev , E.A. Ugolkova

The phase behavior of the melt of the model three–arm star–shaped molecules has been examined within the Landau–de Gennes approach. It is assumed that each particle consists of three rigid arms with different lengths attached to a central core. Each arm is composed of monomer units, and the angles between arms are fixed. It is assumed that particles interact via orientational (Maier-Saupe) and chiral (Goossens) pseudopotentials. The chirality index is proposed based on a set of architectural parameters of particles, including the angles between the arms and the fraction of monomer units in each arm. The phase diagrams have been obtained for the case of equal angles between the arms. Depending on the values of fractions of monomer units of the arms and the angle between them, phase diagrams may contain stability regions for isotropic, chiral nematic, and chiral twist–bend nematic phases. The relationship between the helix pitch and temperature is found to be linear for the uniaxial chiral nematic phase, but nonlinear for the biaxial chiral nematic phase and chiral twist–bend nematic phase.

用朗多-德-热纳方法研究了模型三臂星形分子熔体的相行为。假设每个粒子由三个不同长度的刚性臂组成，这些刚性臂连接在一个中心核心上。每条臂由单体单元组成，臂间的角度是固定的。假设粒子通过取向（Maier-Saupe）和手性（Goossens）伪势相互作用。手性指数是基于一组粒子的结构参数，包括臂间的角度和每臂中单体单位的比例。得到了两臂夹角相等情况下的相图。根据臂的单体单元的分数值和它们之间的角度，相图可能包含各向同性、手性向列相和手性扭弯向列相的稳定区域。对于单轴手性向列相，螺旋螺距与温度的关系是线性的，而对于双轴手性向列相和手性扭弯向列相，螺距与温度的关系是非线性的。

引用次数: 0

The investigation of synergism of bio/-synthetic surfactants mixture and their modification by nanoparticles: Application for Enhanced Oil Recovery (EOR) 生物/合成表面活性剂的协同作用及其纳米改性研究——在提高采收率中的应用

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-11-29 DOI: 10.1016/j.molliq.2025.129039

Maryam Baninaam , Ahmad Bagheri , Abbas Khaksar Manshad , Ghasem Zargar

This study explores the wettability change of carbonate rocks using surfactant/biosurfactant mixtures, focusing on the interactions between saponin (in the form of diosgenin) and cationic surfactants (1, 3-didecyl-2-methylimidazolium chloride, DC-IL) and (n-decyltrimethylammonium bromide, DETAB). Surface tension and contact angle measurements were employed to evaluate micellar behavior and wettability modification for enhanced oil recovery (EOR) applications. In order to investigate the effect of hydrocarbon chain number in interaction between components and reducing the contact angle, the surfactants with a cationic head group but with one and two alkyl chains (C10) were selected (DETAB: one and DC-IL: two). Different parameters such as the mole fraction of saponin in mixed micelle (

X_{1}^{m}

) and at interface (

X_{1}^{σ}

), interaction parameter between components in the mixed micelle (

β^{m}

) and at interface (

β^{σ}

), surface excess concentration (Γ_max), minimum area per amphiphile molecule at the saturated interface (A_min) and thermodynamic parameters have been calculated and discussed using Clint's, Rubingh's and Rosen's models. The evaluated values of

X_{1}^{m}

, signifying the considerable contribution of DC-IL in saponin(1)/DC-IL(2) mixed system. Finally, a novel parameter φ (wettability performance at CMC) was introduced, which provides a standardized approach to evaluate surfactant performance in changing carbonate rock wettability at CMC point in the absence/presence of nanoparticle. This advancement enhances the assessment and selection of optimal surfactants for enhanced oil recovery (EOR).

本研究探讨了表面活性剂/生物表面活性剂混合物对碳酸盐岩润湿性的影响，重点研究了皂苷（以dioosgenin的形式）与阳离子表面活性剂（1,3 -二癸基-2-甲基咪唑氯，DC-IL）和（n-癸基三甲基溴化铵，DETAB）之间的相互作用。采用表面张力和接触角测量来评估胶束行为和润湿性改性，以提高采收率（EOR）。为了研究烃类链数对组分间相互作用和降低接触角的影响，选择了带有阳离子头基但有一个和两个烷基链（C10）的表面活性剂（DETAB: 1和DC-IL: 2）。采用Clint、Rubingh和Rosen模型计算并讨论了混合胶束中皂苷的摩尔分数（X1m）和界面处的摩尔分数（X1σ）、混合胶束组分之间的相互作用参数（βm）和界面处的相互作用参数（βσ）、表面过量浓度（Γmax）、饱和界面处两亲分子的最小面积（Amin）和热力学参数等参数。X1m的评价值表明DC-IL在皂苷(1)/DC-IL(2)混合体系中有相当大的贡献。最后，引入了一个新的参数φ （CMC润湿性性能），该参数提供了一种标准化的方法来评估表面活性剂在没有/存在纳米颗粒的情况下对CMC点碳酸盐润湿性的影响。这一进展为提高采收率（EOR）的最佳表面活性剂的评估和选择提供了便利。

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引用次数: 0

Flotation separation of chalcopyrite from sphalerite and pyrite using a benzothiazole-based collector 用苯并噻唑类捕收剂浮选分离闪锌矿和黄铁矿中的黄铜矿

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-11-29 DOI: 10.1016/j.molliq.2025.129053

Mohammed Kabashi , Ruihua Fan , Xu Jiang , Zhongxu Qi , Wanjia Zhang

Efficient copper recovery is crucial for sustainable development, yet selective separation of chalcopyrite from sphalerite and pyrite is challenging due to their similar surface properties. This study introduced a novel heterocyclic benzothiazole-based collector, 4-benzylthiazolidine-2-thione (CS-3), featuring a sulfur heterocycle with strong coordination capability and an extended alkyl chain linking polar/nonpolar moieties–enhances molecular polarity, improving both collecting power and selectivity. Single mineral flotation of CS-3 exhibited enhanced performance at 5 × 10⁻⁵ mol/L and pH 8, outperforming SEX, with recovery differences: 80.4% vs 23.0% for chalcopyrite-sphalerite and 65.8% vs 32.5% for chalcopyrite–pyrite. For run-of-mine ores, CS-3 achieved a high chalcopyrite recovery of 87.7% and a grade of 6.1%. This result is reinforced by a higher separation efficiency (SE = 37.7%) at a collector dosage of 100 g/t. Mechanistic studies reveal zeta potential shifts confirm selective adsorption on chalcopyrite, while XPS analysis indicates characteristic peaks evidencing combined chemisorption and physisorption. DFT calculations establish significant thermodynamic adsorption differences (chalcopyrite: −43.48 kcal/mol > pyrite: −28.84 kcal/mol > sphalerite: −15.14 kcal/mol), driven by strong CuS coordination and weak NH···S interactions. Selective affinity originates from: (1) specific Cu-site bonding on chalcopyrite, and (2) differential hydration-layer resistance governed by mineral-specific water adsorption modes. Chalcopyrite's weakly hydrogen-bonded H₂O molecules are readily displaced by CS-3's hydrophobic groups, whereas strongly chemisorbed H₂O via ZnO/FeO bonds on sphalerite/pyrite (especially pronounced in sphalerite) creates greater desolvation barriers. This benzothiazole-based collector achieves optimized performance through engineered molecular design, offering a novel strategy for green beneficiation of complex copper-bearing sulfide ores.

铜的高效回收对可持续发展至关重要，但黄铜矿与闪锌矿和黄铁矿的表面性质相似，因此对其进行选择性分离具有挑战性。本研究介绍了一种新型杂环苯并噻唑类捕收剂- 4-苄基噻唑烷-2-硫酮（CS-3），该捕收剂具有强配位能力的硫杂环和连接极性/非极性基团的延伸烷基链，增强了分子极性，提高了捕收能力和选择性。CS-3单矿物浮选在5 × 10−5 mol/L和pH 8条件下表现出较好的浮选效果，优于SEX，黄铜矿—闪锌矿的回收率分别为80.4%和23.0%，黄铜矿—黄铁矿的回收率分别为65.8%和32.5%。未选矿石中，CS-3黄铜矿回收率高达87.7%，品位达6.1%。当捕收剂用量为100 g/t时，分离效率为37.7%。机理研究表明，zeta电位变化证实了黄铜矿的选择性吸附，而XPS分析表明特征峰表明了化学吸附和物理吸附的结合。DFT计算表明，由于cu的强配位和NH···S的弱相互作用，吸附热力学差异显著（黄铜矿：−43.48 kcal/mol >；黄铁矿：−28.84 kcal/mol >；闪锌矿：−15.14 kcal/mol）。选择性亲和源于：(1)黄铜矿上特定的Cu-site键合；(2)由矿物特异性水吸附模式控制的水化层差异阻力。黄铜矿的弱氢键H₂O分子很容易被CS-3的疏水性基团取代，而通过ZnO/FeO键在闪锌矿/黄铁矿上的强化学吸附H₂O（在闪锌矿中尤其明显）产生更大的脱溶障碍。这种基于苯并噻唑的捕收剂通过工程分子设计实现了性能的优化，为复杂含铜硫化矿的绿色选矿提供了一种新的策略。

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引用次数: 0

On the dipole moment of helium solvated molecules 关于氦溶剂化分子的偶极矩

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-11-29 DOI: 10.1016/j.molliq.2025.129046

Paul L. Raston

The Stark spectra of OCS embedded in liquid helium droplets in the OC stretching fundamental is reported. We find that the effective dipole moment in the vibrational ground and excited states are reduced by a small amount (∼4 %) in liquid helium in comparison to their gas phase values. This is similar to what was reported for helium solvated HCN and HCCCN, for which Higasi's elliptical cavity model was found to quantitatively reproduce the helium solvated dipole moments, as long as model parameter(s) were adjusted [P. Stiles et al., Phys. Rev. Lett. 90, 135301 (2003)]. We applied the same model to all three linear rotors (HCN, HCCCN, and OCS), and find that the level of adjustment is significantly less than originally determined, suggesting that the elliptical cavity model can be directly applied to molecules embedded in liquid helium [without adjusting model parameter(s)].

报道了在OC拉伸基面上嵌入液氦液滴的OCS的Stark光谱。我们发现，与气相值相比，液氦中振动基态和激发态的有效偶极矩减少了少量（~ 4%）。这与报道的氦溶剂化HCN和HCCCN相似，Higasi的椭圆腔模型被发现可以定量地再现氦溶剂化偶极矩，只要调整模型参数[P. 1]。斯泰尔斯等人，物理学。[j].科学通报，2009,(1):1 - 3。我们将相同的模型应用于所有三个线性转子（HCN， HCCCN和OCS），发现调整水平明显低于最初确定的水平，这表明椭圆腔模型可以直接应用于嵌入液氦中的分子[无需调整模型参数]。

引用次数: 0

Colloidal lignin particles for eco-friendly and fully emulsified Pickering emulsions: physical stability and interfacial properties 胶体木质素颗粒环保和完全乳化皮克林乳剂：物理稳定性和界面性能

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-11-29 DOI: 10.1016/j.molliq.2025.129038

Giovana Colucci , Liandra Gracher-Teixeira , Samara Cristina Silva-Pituco , Barbara Miqueletti de Oliveira , Andreia Ribeiro , Arantzazu Santamaria-Echart , Alírio Egídio Rodrigues , Maria Filomena Barreiro

Colloidal lignin particles (CLPs) are emerging as eco-friendly alternatives to molecular fossil-based emulsifiers, also offering an effective way to incorporate lignin's multifunctionality. In this context, this work aims to demonstrate the role of CLPs in effectively stabilizing Pickering emulsions, thereby expanding the potential use of lignin in high-performance delivery systems, such as cosmetic formulations. For this, softwood kraft lignin CLPs (10–50 g/L) were used to create oil-in-water Pickering emulsions with an oil volume fraction of 0.3–0.7. Optimization was performed by response surface methodology with the emulsified layer (EL) and the emulsion droplet size selected as the objective responses to be maximized and minimized, respectively. The increase in CLPs concentration and oil volume fraction has enhanced the EL magnitude and reduced the oil droplet size, resulting in fully emulsified and stable systems. The optimized formulation was evaluated for storage stability, stabilization mechanism, and rheological behavior. The emulsion exhibited excellent long-term stability, with no significant changes in droplet size, morphology, or homogeneity observed over one month. Confocal microscopy and Cryo-Scanning electron microscopy revealed that CLPs bridged between droplets, resulting in highly efficient packing of oil droplets. Furthermore, the emulsion exhibited a gel-like behavior, which is favorable for applications requiring enhanced stability and ease spreading. Overall, the obtained results provide insights into the formulation of completely emulsified systems using lignin-based stabilizers, highlighting favorable attributes for applications in eco-friendly cosmetic and personal care products.

胶体木质素颗粒（CLPs）正在成为分子化石乳化剂的环保替代品，也为木质素的多功能性提供了有效的途径。在这种情况下，这项工作旨在证明CLPs在有效稳定皮克林乳剂中的作用，从而扩大木质素在高性能递送系统（如化妆品配方）中的潜在用途。为此，采用软木硫酸盐木质素CLPs （10-50 g/L）制备油体积分数为0.3-0.7的水包油Pickering乳剂。采用响应面法，以乳化层（EL）和乳滴尺寸分别作为目标响应的最大化和最小化进行优化。CLPs浓度和油体积分数的增加提高了EL量级，减小了油滴尺寸，形成了完全乳化的稳定体系。对优化后的配方进行了贮存稳定性、稳定机理和流变性能评价。乳状液表现出优异的长期稳定性，在一个多月的时间里没有观察到液滴大小、形态或均匀性的显著变化。共聚焦显微镜和冷冻扫描电镜显示，CLPs在油滴之间桥接，导致油滴的高效填充。此外，乳液表现出类似凝胶的行为，这有利于需要增强稳定性和易于扩散的应用。总的来说，获得的结果为使用木质素基稳定剂的完全乳化体系的配方提供了见解，突出了在环保化妆品和个人护理产品中的应用的有利属性。

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引用次数: 0

Preparation and luminescent mechanism of dual-emissive red carbon dots for Pb2+/Fe3+ ion sensing and water content detection 用于Pb2+/Fe3+离子传感和水含量检测的双发射红碳点的制备及其发光机理

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-11-29 DOI: 10.1016/j.molliq.2025.129067

Chunli Li , Zikai Zheng , Shiren Huang , Sujin Zheng , Linyun Zeng , Masrur Khodiev , Utkirjon Holikulov , Mekhrdod S. Kurboniyon , Chunyan Zhou , Jialiang Pan , Xinguo Zhang

Carbon dots (CDs), as emerging fluorescent carbon nanomaterials, own exceptional optical properties and hold significant potential for various applications. In this study, novel dual-emissive red carbon dots (R-CDs) were synthesized from o-phenylenediamine (oPD) and 2, 2′-dithiobisbenzoic acid (DTSA) in ethanol, exhibiting emission wavelengths at 600 and 650 nm and a high photoluminescence quantum yield (QY) of 30.64 %. Notably, R-CDs exhibit excellent photostability, solvent-dependent fluorescence, and excitation wavelength-independent fluorescence properties. Based on liquid chromatography-mass spectrometry (LC-MS) and the ¹H nuclear magnetic resonance spectra (¹H NMR), the luminescent mechanism of R-CDs was systematically investigated to verify that 5,14-dihydroquinoxalinolo[2,3-b] phenazine (DHQP) is the fluorophore of R-CDs and a possible structural formation pathway has been proposed. For application testing, R-CDs demonstrated high sensitivity and selectivity toward Pb²⁺ and Fe³⁺, exhibiting good linearity in the concentration ranges of 0–40 μM and 0–60 μM, with the detection limits (LOD) of 0.086 μM and 0.265 μM, respectively. Due to their polarity sensitivity, R-CDs can function as fluorescent sensors for detecting water content in organic solvents. Meanwhile, according to the sensitivity of R-CDs to Fe³⁺, an on-off-on fluorescent sensor was developed to detect F⁻, L-cys and EDTA with LOD of 9.446, 0.413 and 0.078 μM, respectively. Therefore, this study not only develops novel dual-emissive red carbon dots, but also establishes the foundation for the subsequent advancement of fluorescent sensors.

碳点作为一种新兴的荧光碳纳米材料，具有优异的光学性能，具有广阔的应用前景。本研究以邻苯二胺（oPD）和2,2′-二硫代苯甲酸（DTSA）为原料，在乙醇中合成了新型双发射红碳点（R-CDs），其发射波长分别为600 nm和650 nm，光致发光量子产率（QY）高达30.64%。值得注意的是，R-CDs具有优异的光稳定性、依赖溶剂的荧光和不依赖激发波长的荧光特性。基于液相色谱-质谱（LC-MS）和1H核磁共振（1H NMR），系统研究了R-CDs的发光机理，验证了5,14-二氢喹啉[2,3-b]非那嗪（DHQP）是R-CDs的荧光团，并提出了可能的结构形成途径。应用测试表明，R-CDs对Pb2+和Fe3+具有较高的灵敏度和选择性，在0 ~ 40 μM和0 ~ 60 μM的浓度范围内呈良好的线性关系，检出限分别为0.086 μM和0.265 μM。由于其极性敏感性，R-CDs可以作为荧光传感器检测有机溶剂中的水含量。同时，根据R-CDs对Fe3+的灵敏度，开发了一种检测F−、L-cys和EDTA的on-off-on荧光传感器，其LOD分别为9.446、0.413和0.078 μM。因此，本研究不仅开发了新型双发射红碳点，也为荧光传感器的后续发展奠定了基础。

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引用次数: 0

Transport and rupture dynamics of the Pickering emulsion in oil-filled nanopore throats 含油纳米孔喉中Pickering乳状液的输运与破裂动力学

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-11-29 DOI: 10.1016/j.molliq.2025.129036

Yuanhao Chang , Senbo Xiao , Yuequn Fu , Hanzhou Li , Xiang Li , Rui Ma , Jianying He

Pickering emulsions stabilized by Janus nanoparticles (JNPs) have demonstrated great potential in enhanced oil recovery (EOR). However, the fundamental transport mechanism of these emulsions through pore throats, particularly their stability under oil-rich conditions, remains elusive. In this study, molecular dynamics (MD) simulations were employed to investigate the transport behavior of individual Pickering emulsions with varying JNP surface coverage (

ϕ

) through oil-filled nanopore throats. The results show that when the throat diameter is smaller than the emulsion size, all emulsions undergo rupture during transport. Emulsions with higher

ϕ

values rupture at later stages due to enhanced mechanical shielding by the JNP shell. Nevertheless, the post-rupture accumulation of JNPs within the throat leads to elevated local pressure, especially in systems with larger

ϕ

. In contrast, classical emulsions with comparable size and surface coverage rupture earlier and display markedly lower transport stability. Moreover, the demulsification dynamics differ significantly between Pickering and classical emulsions, owing to distinct adsorption behaviors of JNPs and surfactants under hydrodynamic forces. Notably, the local wettability alteration and oil film remobilization induced by JNPs in Pickering emulsions demonstrate highly advantageous features for EOR applications. When passing through wider throats, Pickering emulsions exhibit reduced deformation, weakened Jamin effects, and significantly lower flow resistance. Under these conditions, emulsions with

ϕ

values exceeding a critical threshold can successfully traverse the channel without rupture. The findings not only enhance the understanding of the transport stability of Pickering emulsions in oil-bearing regions but also provide guidance for the rational design of emulsion-based EOR strategies.

由Janus纳米颗粒（JNPs）稳定的Pickering乳剂在提高石油采收率（EOR）方面显示出巨大的潜力。然而，这些乳剂通过孔喉的基本运输机制，特别是它们在富油条件下的稳定性，仍然是难以捉摸的。在本研究中，采用分子动力学（MD）模拟来研究具有不同JNP表面覆盖（φ）的单个皮克林乳剂通过充满油的纳米孔喉的输运行为。结果表明：当喉道直径小于乳状液粒径时，乳状液在输运过程中均发生破裂；由于JNP壳增强了机械屏蔽，具有较高φ值的乳剂在后期破裂。然而，破裂后喉内JNPs的积累导致局部压力升高，特别是在φ较大的系统中。相比之下，具有相同尺寸和表面覆盖率的经典乳剂破裂更早，并且表现出明显较低的运输稳定性。此外，由于JNPs和表面活性剂在水动力作用下的不同吸附行为，Pickering乳剂与经典乳剂的破乳动力学存在显著差异。值得注意的是，在Pickering乳状液中，JNPs引起的局部润湿性改变和油膜再活化对提高采收率具有非常有利的特点。当通过较宽的喉道时，Pickering乳剂表现出较小的变形，减弱了Jamin效应，并显着降低了流动阻力。在这些条件下，ϕ值超过临界阈值的乳剂可以成功地穿过通道而不会破裂。研究结果不仅加深了对油区Pickering乳化液输运稳定性的认识，而且为合理设计乳化液基提高采收率策略提供了指导。

{"title":"Transport and rupture dynamics of the Pickering emulsion in oil-filled nanopore throats","authors":"Yuanhao Chang , Senbo Xiao , Yuequn Fu , Hanzhou Li , Xiang Li , Rui Ma , Jianying He","doi":"10.1016/j.molliq.2025.129036","DOIUrl":"10.1016/j.molliq.2025.129036","url":null,"abstract":"<div><div>Pickering emulsions stabilized by Janus nanoparticles (JNPs) have demonstrated great potential in enhanced oil recovery (EOR). However, the fundamental transport mechanism of these emulsions through pore throats, particularly their stability under oil-rich conditions, remains elusive. In this study, molecular dynamics (MD) simulations were employed to investigate the transport behavior of individual Pickering emulsions with varying JNP surface coverage (<span><math><mi>ϕ</mi></math></span>) through oil-filled nanopore throats. The results show that when the throat diameter is smaller than the emulsion size, all emulsions undergo rupture during transport. Emulsions with higher <span><math><mi>ϕ</mi></math></span> values rupture at later stages due to enhanced mechanical shielding by the JNP shell. Nevertheless, the post-rupture accumulation of JNPs within the throat leads to elevated local pressure, especially in systems with larger <span><math><mi>ϕ</mi></math></span>. In contrast, classical emulsions with comparable size and surface coverage rupture earlier and display markedly lower transport stability. Moreover, the demulsification dynamics differ significantly between Pickering and classical emulsions, owing to distinct adsorption behaviors of JNPs and surfactants under hydrodynamic forces. Notably, the local wettability alteration and oil film remobilization induced by JNPs in Pickering emulsions demonstrate highly advantageous features for EOR applications. When passing through wider throats, Pickering emulsions exhibit reduced deformation, weakened Jamin effects, and significantly lower flow resistance. Under these conditions, emulsions with <span><math><mi>ϕ</mi></math></span> values exceeding a critical threshold can successfully traverse the channel without rupture. The findings not only enhance the understanding of the transport stability of Pickering emulsions in oil-bearing regions but also provide guidance for the rational design of emulsion-based EOR strategies.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"441 ","pages":"Article 129036"},"PeriodicalIF":5.2,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145692133","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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