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MD simulations of UCST liquid-liquid phase separations of [Hbet][Tf2N]/Water mixtures [Hbet][Tf2N]/水混合物UCST液-液分离的MD模拟
IF 5.2 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-03-15 Epub Date: 2026-01-24 DOI: 10.1016/j.molliq.2026.129314
Hussen O. Mohammed , Ronen Zangi
We investigate computationally the upper critical solution temperature (UCST) phase behavior of protonated trimethylglycine (betaine) bis(trifluoromethylsulfonyl)imide, [Hbet][Tf2N], ionic liquid (IL) mixed with water. Literature reports on charge-fixed force-field models of ILs in the neat phase indicate that in order to reproduce experimental data, down-scaling of the ionic charges is necessary, in many cases, by a factor of 0.7–0.9. This reduction in the unit charges of the ions reflects a transfer of charge from anion to cation in the condensed phase of the IL, a phenomenon not accounted for by classical mechanics. In this paper, we find that in order to reproduce the experimentally observed transformation of a liquid-liquid phase-separated (biphasic) state to a homogeneous state by a temperature increase, the charges of the cation and anion of [Hbet][Tf2N] ought to be scaled-down by a factor of 0.95. This scaling factor is closer to 1, compared to typical values found in neat ILs, likely because in water mixtures the anion-to-cation charge transfer is limited. The resulting phase diagram, and in particular, the chemical compositions of the IL-rich and water-rich phases as a function of temperature, displays excellent agreement with experimental data. Exact determination of the simulation’s critical temperature is not decisive, and a plausible temperature range extends from the experimentally determined Tc up to 10 K higher. Furthermore, the viscosities of the system at very low water contents are higher by a factor of 2–6, relative to values reported in experiments. Analyses of the interactions between and within the ions indicate they are governed by electrostatic forces, except for those within the anions, in which case, hydrophobic interactions between the trifluoromethyl groups seem to dominate. In contrast to ion-ion interactions, the effective strength of the ion-water attraction increases with temperature. Given that the UCST behavior of [Hbet][Tf2N]/water mixture has already been exploited to desalinate seawater by forward-osmosis, the results presented here can further assist in designing and fine-tuning more efficient thermoresponsive draw solutes.
本文研究了质子化三甲基甘氨酸(甜菜碱)双(三氟甲基磺酰基)亚胺[Hbet][Tf2N]离子液体(IL)与水混合的上临界溶液温度(UCST)相行为。关于纯相离子离子固定电荷力场模型的文献报道表明,为了再现实验数据,在许多情况下,离子电荷的缩小是必要的,缩小幅度为0.7-0.9。离子单位电荷的减少反映了离子凝聚相中电荷从阴离子向阳离子的转移,这是经典力学无法解释的现象。在本文中,我们发现,为了重现实验观察到的液-液相分离(双相)状态在温度升高时向均匀状态的转变,[Hbet][Tf2N]的正离子和阴离子的电荷应该按0.95的比例缩小。与纯ILs中的典型值相比,该比例因子更接近于1,可能是因为在水混合物中阴离子到阳离子的电荷转移是有限的。所得相图,特别是富白介素相和富水相的化学成分随温度的变化,与实验数据非常吻合。精确确定模拟的临界温度并不是决定性的,合理的温度范围从实验确定的Tc延伸到10 K以上。此外,在非常低的含水量下,系统的粘度比实验中报告的值高2-6倍。对离子之间和离子内部相互作用的分析表明,除了阴离子内部的相互作用外,它们受静电力的支配,在阴离子内部,三氟甲基之间的疏水相互作用似乎占主导地位。与离子-离子相互作用相反,离子-水引力的有效强度随着温度的升高而增加。考虑到[Hbet][Tf2N]/水混合物的UCST行为已经被用于通过正向渗透淡化海水,本文的研究结果可以进一步帮助设计和微调更有效的热响应性吸取溶质。
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引用次数: 0
Flotation separation mechanism of calcium minerals using novel synthesized amino acid based anionic collectors 新型合成氨基酸基阴离子捕收剂浮选分离钙矿物的机理
IF 5.2 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-03-15 Epub Date: 2026-01-24 DOI: 10.1016/j.molliq.2026.129313
Manas Barai , N.S. Venkataramanan
Specific separation of fluorite and phosphate ores, such as fluorite (CaF2) and apatite (Ca5(PO4)3(OH, F, Cl) from carbonate ores, i.e., dolomite (CaMg(CO3)2), magnesite (Mg(CO3)2), and calcite (CaF2) and individual separation of apatite from fluorite using N-dodecyl glycinate (C12GlyNa), −aminomalonate (C12MalNa2), −aspartate (C12AspNa2), and -glutamate (C12GluNa2) surfaces were recorded by Hallimond tube flotation, ζ potential, UV–Vis absorbance, FTIR, molecular modeling, and DFT calculations. After carbonate mineral dissolution in collector solution, pH values changed from 2 to 7, but values remained unchanged for apatite and fluorite at a fixed 2 × 10−4 (M) concentration. With increasing the pH and concentration, recovery efficacy and negative ζ potential values increased significantly, resulting in spontaneous monolayer adsorptions. Monocarboxylate C12GlyNa exhibited higher but non-selective flotation across all minerals at natural and 10.5 pH. In contrast, the dicarboxylate group of C12MalNa2 is separated by one carbon atom, showing higher recovery for apatite and fluorite, but two and three methylene spacers, C12AspNa2 and C12GluNa2 exhibit approximately two-time higher OO distances than the M-M distance of apatite, but this distance is nicely matched with fluorite, resulting in higher flotation for fluorite than apatite. Calcite-coated C12MalNa2 did not show flotation because one Ca metal electrostatically interacted with one -(COO)− unit; on the other hand, apatite exhibited higher recovery due to the spontaneous monolayer adsorption through electrostatic interactions between CaCa with two -(COO)− units, resulting in apatite separation from calcite. The amount of collector remaining in solution after adsorption values were measured by UV–Vis spectroscopy. With varying concentration and pH at a fixed 2 × 10−4 M, surface adsorption rates were scrutinized by area under the alkyl -(CH2) stretching absorption band at (2993–2967 cm−1) and (2895–2810 cm−1) by FTIR. Molecular modeling and DFT calculations were used to expose the adsorption mechanism of amino acid-based collectors on mineral surfaces to improve recovery efficiency.
采用哈利蒙德管浮选、ζ电位、紫外-可见吸收光谱、红外光谱、分子模拟等方法,记录了氟石(CaF2)和磷灰石(Ca5(PO4)3(OH, F, Cl)从白云石(CaMg(CO3)2)、菱镁矿(Mg(CO3)2)和方解石(CaF2)等碳酸盐矿石中分离萤石和磷灰石(Ca5(PO4)3)和磷灰石(Ca5(PO4)3)以及磷灰石(C12GluNa2)等磷灰石从萤石中分离的过程。和DFT计算。碳酸盐矿物在捕收剂溶液中溶解后,pH值从2变化到7,但磷灰石和萤石的pH值在固定的2 × 10−4 (M)浓度下保持不变。随着pH和浓度的增加,回收效率和负ζ电位值显著增加,导致自发单层吸附。单羧酸盐C12GlyNa在自然和10.5 ph条件下对所有矿物均表现出较高的非选择性浮选。相比之下,C12MalNa2的二羧酸基被一个碳原子分开,对磷灰石和萤石的回收率更高,但两个和三个亚甲基间隔剂C12AspNa2和C12GluNa2的OO距离比磷灰石的M-M距离高约两倍,但这一距离与萤石的M-M距离很好地匹配。结果萤石的浮选率高于磷灰石。方解石包覆的C12MalNa2不表现出浮选,因为一个Ca金属与一个-(COO)−单元静电相互作用;另一方面,由于CaCa与2 -(COO)−单元之间的静电相互作用,导致磷灰石与方解石分离,磷灰石表现出较高的回收率。采用紫外可见光谱法测定了吸附后溶液中捕收剂的残留量。在固定的2 × 10−4 M条件下,在不同的浓度和pH条件下,用FTIR通过(2993-2967 cm−1)和(2895-2810 cm−1)的烷基-(CH2)拉伸吸收带下的面积来观察表面吸附率。通过分子模拟和DFT计算揭示了氨基酸基捕收剂在矿物表面的吸附机理,以提高回收效率。
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引用次数: 0
Thermophysical properties of natural hydrophobic deep eutectic solvents composed of menthol, thymol, and linalool 由薄荷醇、百里香酚和芳樟醇组成的天然疏水深共晶溶剂的热物理性质
IF 5.2 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-03-15 Epub Date: 2025-12-24 DOI: 10.1016/j.molliq.2025.129187
Yueting Xiao, Junliang Liu, Biyao Liu, Jiaqi Cai, Jing Tong
With the rapid development of sustainable chemistry and green industries, Type V natural deep eutectic solvents have demonstrated broad application prospects across multiple fields due to their natural origin, low toxicity, biodegradability, and excellent hydrophobicity. In this study, monoterpenoids such as menthol, thymol, and linalool were selected as starting materials. By precisely adjusting the molar ratio of hydrogen bond donors to acceptors, fifteen hydrophobic deep eutectic solvents (HDESs) with different compositions were successfully prepared. Key thermophysical properties, including density, viscosity, and surface tension, were systematically measured. The results indicate that these properties exhibit a clear dependence on both temperature and composition. Variations in hydrogen bonding strength and molecular packing modes among different components led to distinctly different characteristics in each formulated system. Based on the experimental data, key derived physical parameters such as sound velocity, lattice energy, and activation energy for viscous flow were further calculated, providing theoretical insight into the relationship between the microstructure and macroscopic properties of deep eutectic solvents.
随着可持续化学和绿色工业的快速发展,V型天然深共晶溶剂因其天然来源、低毒性、生物降解性和优异的疏水性在多个领域展现出广阔的应用前景。本研究以薄荷醇、百里香酚、芳樟醇等单萜类化合物为起始原料。通过精确调整氢键给体与受体的摩尔比,成功制备了15种不同组成的疏水深共晶溶剂(hess)。系统地测量了关键的热物理性质,包括密度、粘度和表面张力。结果表明,这些性质对温度和成分都有明显的依赖性。不同组分之间的氢键强度和分子堆积模式的差异导致每种配方体系的特性有明显差异。在实验数据的基础上,进一步计算了黏性流动的声速、晶格能、活化能等关键导出物理参数,为深入了解深共晶溶剂的微观结构与宏观性能之间的关系提供了理论依据。
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引用次数: 0
Investigating the bimodality of liquid water via chemical bond descriptors and k-means clustering analysis 通过化学键描述符和k-means聚类分析研究液态水的双峰性
IF 5.2 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-03-15 Epub Date: 2026-01-21 DOI: 10.1016/j.molliq.2026.129306
Mateus Quintano , Ayesh Madushanka , Carlos V. Santos Jr , Francielle C. Machado , Elfi Kraka , Ricardo L. Longo , Renaldo T. Moura Jr.
Liquid water exhibits anomalous behavior, with several of its physical and chemical properties deviating from those of ordinary liquids. Some of these anomalies stem from a bimodality observed in macroscopic properties such as density, isothermal compressibility, and specific heat, as well as the radial distribution function and vibrational spectra, which reflect the collective structural dynamics of liquid water. The infrared spectrum is particularly sensitive to hydrogen-bonded arrangements, thus it could be a crucial link between macroscopic properties and microscopic interactions. This study utilizes structural models that align with the experimental infrared spectrum of liquid water, offering a novel proof of concept. It bridges a critical gap by demonstrating how the bimodality of liquid water can be revealed through fully localized chemical bond descriptors. These descriptors are derived from local vibrational mode theory, the chemical bond overlap model and its topological extension, as well as the quantum theory of atoms in molecules. Key findings reveal that the local force constant, intra-overlap Coulomb repulsion, and Cremer and Kraka’s energy density associated with hydrogen bonds exhibit bimodal behavior. Notably, by employing the unsupervised machine learning algorithm K-means for clustering analysis, we identified distinct regimes of hydrogen-bond strength, revealing systematic patterns that differentiate the low-density liquid and high-density liquid networks. Overall, this study reinforces the concept that liquid water consists of two distinct types of local structures, providing new insights into its bimodal nature and advances in this field.
液态水表现出反常的行为,它的一些物理和化学性质与普通液体不同。其中一些异常源于观察到的宏观性质的双峰性,如密度、等温压缩率、比热,以及反映液态水集体结构动力学的径向分布函数和振动谱。红外光谱对氢键排列特别敏感,因此它可能是宏观性质和微观相互作用之间的关键联系。本研究利用与液态水实验红外光谱一致的结构模型,提供了一种新的概念证明。它通过展示如何通过完全定位的化学键描述符揭示液态水的双峰性,弥合了一个关键的差距。这些描述符来源于局部振动模理论、化学键重叠模型及其拓扑扩展,以及分子中原子的量子理论。关键发现表明,局部力常数、重叠内库仑斥力以及与氢键相关的Cremer和Kraka能量密度表现出双峰行为。值得注意的是,通过采用无监督机器学习算法K-means进行聚类分析,我们确定了不同的氢键强度机制,揭示了区分低密度液体和高密度液体网络的系统模式。总的来说,这项研究强化了液态水由两种不同类型的局部结构组成的概念,为其双峰性质和该领域的进展提供了新的见解。
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引用次数: 0
Unraveling the potential of zinc oxide nanosheets as conveyor of Flucytosine antifungal medication 揭示氧化锌纳米片作为氟胞嘧啶抗真菌药物输送的潜力
IF 5.2 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-03-15 Epub Date: 2026-01-20 DOI: 10.1016/j.molliq.2026.129294
Anjaly Baiju Krishna , Arjun Suvilal , Rakhesh Vamadevan , Jeetu Satheesh Babu
This study depicts in-silico interaction mechanisms of Flucytosine (5-FC) on two-dimensional (2-D) Zinc Oxide nanosheets (ZnONs), aiming a new antifungal drug delivery system. The adsorption analysis indicates that the complexes achieve stable configurations through exothermic reactions, with C-1 (−1.82 eV) showing strong chemisorption, while C-2 (−0.93 eV) and C-3 (−0.94 eV) exhibit near-chemisorption, reflecting a balance between secure drug attachment and efficient release. Interaction energy and Mulliken charge analyses reveal that C-1 is the most energetically favorable complex, characterized by significant O(5-FC)–Zn (ZnO) bonding and distinct electron transfer patterns that enhance complex stability. The calculated formation energy (−4.54 eV/atom) confirms the thermodynamic stability of ZnONs, and minimal alterations in 5-FC structural parameters upon adsorption ensure the retention of pharmacological activity. Electronic structure analyses demonstrate reductions in band gaps (23.77–13.69%) and shifts in total density of states, underscoring strong drug–carrier interactions through charge transfer and orbital hybridization. Solvation studies and recovery time analysis confirm aqueous stability and controlled release behavior. Further, pH sensitivity studies indicate that protonation at the adsorption site weakens the interaction, facilitating targeted drug release in acidic environments. Overall, ZnONs display structural robustness, electronic versatility, and responsive adsorption, making them effective and reliable carriers for 5-FC.
本研究描述了氟胞嘧啶(5-FC)在二维氧化锌纳米片(ZnONs)上的硅相互作用机制,旨在建立一种新的抗真菌药物递送系统。吸附分析表明,配合物通过放热反应获得稳定构型,其中C-1 (- 1.82 eV)表现出较强的化学吸附,而C-2 (- 0.93 eV)和C-3 (- 0.94 eV)表现出接近化学吸附,反映了药物安全附着和有效释放之间的平衡。相互作用能和Mulliken电荷分析表明,C-1是能量最有利的配合物,其特征是明显的O(5-FC) -Zn (ZnO)键和不同的电子转移模式,增强了配合物的稳定性。计算的形成能(−4.54 eV/原子)证实了ZnONs的热力学稳定性,并且吸附时5-FC结构参数的最小变化确保了药理活性的保留。电子结构分析表明,带隙减小(23.77% - 13.69%),总态密度变化,强调了通过电荷转移和轨道杂化进行的强药物载流子相互作用。溶剂化研究和恢复时间分析证实了水稳定性和控释行为。此外,pH敏感性研究表明,吸附位点的质子化削弱了相互作用,促进了药物在酸性环境中的靶向释放。总体而言,ZnONs具有结构坚固性,电子通用性和响应性吸附,使其成为5-FC的有效可靠的载体。
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引用次数: 0
From solvation thermodynamics to polarity scales and universalities 从溶剂化热力学到极性尺度和普遍性
IF 5.2 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-03-15 Epub Date: 2026-01-14 DOI: 10.1016/j.molliq.2026.129259
Costas Tsioptsias , William Acree Jr , Costas Panayiotou
Reliable information on intermolecular interactions is crucial for molecular thermodynamic modeling and in a vast range of practical applications, including solvent screening. A wealth of such information may be extracted from experimental data on solvation quantities by consistent use of Solvation Thermodynamics. This is facilitated when a holistic approach is adopted involving large number of systems of diverse character and their specific and non-specific interactions are treated on a common basis. The present work combines quantum chemical information on over 1400 solute molecules and experimental information on solvation enthalpy and free energy in common solvents in order to extract information on dispersion, (di)polar, and hydrogen-bonding (HB) interactions from over 190,000 solute – solvent systems. The widely used Abraham's LSER (linear solvation energy relationship) model has been restructured for handling this information and for the development of new polarity scales as well as acidity (HB donor capacity) and basicity (HB acceptor capacity) scales. The number of solvent systems with known LSER-type solvent-specific parameters has been increased significantly along with its predictive capacity. Self-solvation quantities over a broad range of external conditions have been explored as well and their universalities at the boiling point and the (vapor – liquid) critical point have been identified. Solvation parameters facilitating the exchange of thermodynamic information between diverse polarity scales have been developed. The significance and perspectives of these developments are discussed.
分子间相互作用的可靠信息对于分子热力学建模和广泛的实际应用至关重要,包括溶剂筛选。通过持续使用溶剂化热力学,可以从溶剂化量的实验数据中提取出丰富的此类信息。如果采取一种涉及大量不同性质的系统的整体办法,并在共同基础上处理它们的具体和非具体相互作用,就会促进这一点。本工作结合了1400多个溶质分子的量子化学信息和普通溶剂中溶剂化焓和自由能的实验信息,以便从190,000多个溶质-溶剂系统中提取有关分散,(二)极性和氢键(HB)相互作用的信息。广泛使用的亚伯拉罕LSER(线性溶剂化能量关系)模型已经被重新构建,以处理这些信息,并用于开发新的极性尺度以及酸性(HB供体容量)和碱性(HB受体容量)尺度。具有已知lser型溶剂特异性参数的溶剂体系的数量随着其预测能力的提高而显著增加。研究了在各种外部条件下的自溶剂化量,并确定了它们在沸点和(汽液)临界点处的普遍性。溶剂化参数促进了不同极性尺度间热力学信息的交换。讨论了这些发展的意义和前景。
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引用次数: 0
Exploring the molecular mechanisms of Nanoplastic interactions with blood proteins by molecular dynamics and docking simulations 通过分子动力学和对接模拟探索纳米塑料与血液蛋白相互作用的分子机制
IF 5.2 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-03-15 Epub Date: 2026-01-20 DOI: 10.1016/j.molliq.2026.129304
Benedikt J. Lohnes , Jonas Woller , Udo F. Hartwig , Nitesh K. Poddar
Plastic pollution represents a growing concern for human health, as micro- and nanosized particles can interfere with protein structure and function, potentially contributing to various physiological disorders. Nanosized plastics are particularly relevant due to their enhanced bioactivity, driven by their high surface-to-volume ratio, which promotes interactions with biomolecules. Here, we investigated the interaction of essential blood proteins, including human serum albumin (HSA), transthyretin (TTR), amyloid-β (Aβ1–40), and α-Synuclein (α-Syn), with computational nanoparticle models of common plastics exhibiting spherical (PE, PP, PVC, PEG) and elongated (PS, PET) morphologies.
Molecular dynamics (MD) and docking simulations revealed non-site-specific, high-affinity interactions, predominantly driven by hydrophobic contacts, with binding strengths modulated by polymer surface chemistry, particle shape, and protein structural properties. MM/PBSA calculations revealed protein-specific binding preferences, with α-Syn and HSA exhibiting a high affinity for PS and PVC, respectively, while TTR showed a preference for PVC. Moreover, calculated binding free energies ranged from generally moderate (Aβ1–40) to very strong (PS–HSA) interactions. Furthermore, RMSD analysis demonstrated that nanoplastic binding markedly reduces backbone mobility across all proteins, with the most pronounced effects observed in flexible, intrinsically disordered proteins Aβ1–40 and α-Syn compared to globular transport proteins HSA and TTR, highlighting their susceptibility to diffuse, non-site-specific adsorption onto heterogeneous polymer surfaces.
These results suggest that plastic nanoparticles strongly interact with blood proteins, potentially impacting their structure and function. Furthermore, the binding may promote aggregation-prone states by restricting conformational mobility, providing a potential mechanistic link between plastic pollution and the development of neurodegenerative and cardiovascular pathologies.
塑料污染对人类健康的影响越来越大,因为微纳米颗粒会干扰蛋白质的结构和功能,可能导致各种生理障碍。纳米塑料由于其高表面体积比而具有增强的生物活性,从而促进了与生物分子的相互作用,因此具有特别重要的意义。在这里,我们研究了必需的血液蛋白,包括人血清白蛋白(HSA),转甲状腺素(TTR),淀粉样蛋白-β (a -β 1 - 40)和α-突触核蛋白(α-Syn),与普通塑料的计算纳米粒子模型的相互作用,这些塑料具有球形(PE, PP, PVC, PEG)和细长(PS, PET)的形态。分子动力学(MD)和对接模拟揭示了非位点特异性的高亲和相互作用,主要由疏水接触驱动,结合强度由聚合物表面化学、颗粒形状和蛋白质结构特性调节。MM/PBSA计算显示了蛋白质特异性结合偏好,α-Syn和HSA分别对PS和PVC表现出高亲和力,而TTR则对PVC表现出高亲和力。此外,计算的结合自由能范围从一般中等(Aβ1-40)到很强(PS-HSA)相互作用。此外,RMSD分析表明,纳米塑料结合显著降低了所有蛋白质的骨架迁移率,与球形转运蛋白HSA和TTR相比,在柔性的、内在无序的蛋白Aβ1-40和α-Syn中观察到的影响最为明显,突出了它们对扩散、非位点特异性吸附在非均相聚合物表面的敏感性。这些结果表明,塑料纳米颗粒与血液蛋白强烈相互作用,可能影响其结构和功能。此外,这种结合可能通过限制构象移动来促进易于聚集的状态,从而在塑料污染与神经退行性和心血管疾病的发展之间提供了潜在的机制联系。
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引用次数: 0
Insights into the crystallization kinetics of lithium 12-hydroxystearate in lubricating oil from differential scanning calorimetry 差示扫描量热法研究12-羟基硬脂酸锂在润滑油中的结晶动力学
IF 5.2 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-03-15 Epub Date: 2026-01-25 DOI: 10.1016/j.molliq.2026.129315
Bing Li, Bingbing Lai, Wenjing Lou, Gaiqing Zhao, Qian Jia, Xiaobo Wang
Lithium 12-hydroxystearate (Li12HS) and its derivatives serve as primary thickeners in grease formulations; however, the mechanistic pathway governing thickener network scaffolding via crystallization remains incompletely elucidated. This study systematically investigates the non-isothermal crystallization kinetics of Li12HS in synthetic ester oil using differential scanning calorimetry (DSC). Results demonstrate that the Avrami model adequately describes the melt-recrystallization process, revealing a two-dimensional flake-like growth mechanism followed by agglomeration into macrocrystalline assemblies. Notably, base oil molecules significantly constrain the conformational mobility of Li12HS molecular chains, thereby inducing crystallization retardation within the grease matrix. Jeziorny kinetic analysis of DSC thermograms and scanning electron microscopy (SEM) further reveals that the fibrillar growth mechanism—characterized by the progressive assembly and elongation of fibrils into bundled fibers—is the key process governing the formation of the lithium-grease network.
12-羟基硬脂酸锂(Li12HS)及其衍生物作为润滑脂配方的主要增稠剂;然而,通过结晶控制增稠剂网络脚手架的机制途径仍未完全阐明。采用差示扫描量热法(DSC)系统地研究了合成酯油中Li12HS的非等温结晶动力学。结果表明,Avrami模型充分描述了熔体-再结晶过程,揭示了一个二维片状生长机制,随后聚集成大晶组件。值得注意的是,基础油分子显著地限制了Li12HS分子链的构象迁移率,从而在油脂基体内引起结晶阻滞。DSC热像图和扫描电镜(SEM)的动力学分析进一步揭示了原纤维的生长机制——其特征是原纤维的逐渐组装和伸长成束状纤维——是控制锂脂网络形成的关键过程。
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引用次数: 0
Topological hydrogen-bond saturation as a design route to type V deep eutectics 拓扑氢键饱和作为V型深共晶的设计途径
IF 5.2 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-03-15 Epub Date: 2026-01-17 DOI: 10.1016/j.molliq.2026.129285
Alessandro Triolo , Emanuela Mangiacapre , Vitaly V. Chaban , Fabrizio Lo Celso , Franca Castiglione , László Almásy , Carlo Ottaviani , Martin Brehm , Olga Russina
Type V deep eutectic solvents (DES), formed by combination of neutral hydrogen-bonding molecules, remain difficult to predict and engineer. The recent proposal that the asymmetric nature of hydrogen bonding (HB) donor and acceptor capability of precursors might be a key approach for their formulation requires validation. Here we show that the emergence of a topologically saturated hydrogen-bond network provides a mechanistic route to formulate such systems, exemplified by the carvacrol–dimethyl sulfoxide (DMSO) mixture. COSMO-RS screening predicts a profoundly deep eutectic (about 110 K depression) arising from donor-free, strong HB acceptor DMSO when paired with asymmetric HB donor carvacrol.
To our knowledge, this is the first example of a type V DES whose precursors are liquid at ambient conditions, thus enabling a detailed exploration of chemical physical properties and their excess values to be probed across the whole composition window.
This approach is fundamental to describe the complex structural and dynamical organization of carvacrol–DMSO mixtures across composition and relate hydrogen-bond topology to the onset of deep eutectic behaviour, on the basis of complementary thermophysical measurements, neutron scattering, NMR and classical molecular dynamics simulations.
The work addresses two main points: i) can present knowledge be used to custom engineer type V DES?; ii) how does the shifting interplay between intra- and interspecies interactions across composition translate into the deep eutectic nature of Type V mixtures?
V型深共晶溶剂(DES)是由中性氢键分子结合形成的,目前仍难以预测和设计。最近提出的前体氢键(HB)供体和受体能力的不对称性质可能是其配方的关键方法需要验证。在这里,我们展示了拓扑饱和氢键网络的出现为形成这样的系统提供了一种机制途径,例如香芹酚-二甲基亚砜(DMSO)混合物。cosmos - rs筛选预测,当与不对称HB供体carvacrol配对时,无供体、强HB受体DMSO产生深度共熔(约110k凹陷)。据我们所知,这是第一个V型DES的例子,其前体在环境条件下是液态的,因此可以在整个组成窗口中对化学物理性质及其过量值进行详细探索。基于互补的热物理测量、中子散射、核磁共振和经典分子动力学模拟,该方法是描述carvacrol-DMSO混合物的复杂结构和动态组织的基础,并将氢键拓扑与深度共晶行为的开始联系起来。这项工作解决了两个主要问题:i)目前的知识是否可以用于定制工程师V型DES?ii)跨成分的种内和种间相互作用如何转化为V型混合物的深共晶性质?
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引用次数: 0
Ferroelectric nematic phase at a photosensitive polymer substrate: comparing thermo-mechanical effect with photo-reorientation 光敏聚合物衬底上的铁电向列相:比较热机械效应和光定向
IF 5.2 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-03-15 Epub Date: 2026-01-19 DOI: 10.1016/j.molliq.2026.129288
Tibor Tóth-Katona , Ameer R.K. Nassrah , Péter Salamon , Antal Jákli , István Jánossy
The average direction of the molecules (director) of nematic liquid crystals (LCs) can be easily oriented by light using photosensitive surfaces (photoalignment). Recently, it was shown that in polar nematic (NF) liquid crystals the director field can be manipulated by a laser light induced temperature gradient. Here we investigate how the photoalignment compares to the thermo-mechanical effect in the NF phase. For that we study photo-reorientation phenomena on a photosensitive polymer substrate in the prototype ferroelectric nematic liquid crystal compound DIO. It is found that, while in the nonpolar nematic and antiferroelectric mesophases the photoalignment is observed, in the ferroelectric nematic phase the thermo-mechanical (TM) coupling determines the director alignment.
向列液晶(lc)分子的平均方向(指向性)可以很容易地通过光敏表面(光取向)进行定向。最近研究表明,在极性向列型液晶中,激光诱导的温度梯度可以控制指向场。在这里,我们研究了光取向如何与NF相的热机械效应相比较。为此,我们研究了铁电向列液晶化合物DIO原型中光敏聚合物衬底上的光定向现象。研究发现,在非极性向列相和反铁电介相中存在光取向,而在铁电向列相中,热-机械耦合决定了定向器的取向。
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Journal of Molecular Liquids
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