Journal of Molecular Liquids最新文献_第3页

Investigation of 3,3’-diindolylmethane solubility in 14 solvents from 272.45 to 324.25 K: Experimental measurement, thermodynamic analysis, and molecular simulation 3,3 ' -二吲哚基甲烷在272.45 ~ 324.25 K 14种溶剂中的溶解度研究：实验测量、热力学分析和分子模拟

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2026-01-02 DOI: 10.1016/j.molliq.2026.129234

Bin Ou , Xiaofang Li , Lemei Huang , Yujiang Ke , Chaohui Che , Yanyan Huang , Zhijia Wang , Xiaobing Liu , Yajun Li , Kui Wu

The solubility of 3,3′-Diindolylmethane in 14 different solvents (272.45–324.25 K) was determined using the gravimetric method. The results show that its solubility increases with rising temperature across the studied solvent range. At 298.15 K, the solubility of 3,3′-Diindolylmethane in the solvents follows the order: 2-pentanone > ethyl acetate > methyl acetate > ethyl formate > acetonitrile > n-pentanol > n-butanol > n-propanol > ethanol > isopropanol > isopentanol > methanol > isobutanol > toluene. Five thermodynamic models were employed to correlate the experimental data, among which the modified Apelblat model provided the best fit. In addition, electrostatic potential energy surface analysis was conducted to preliminarily evaluate possible solute solvent interactions. Results from density functional theory calculations and the KAT-LSER model indicate that 3,3′-Diindolylmethane primarily acts as a hydrogen-bond donor, and its solubility is synergistically influenced by the hydrogen-bond acceptor ability, polarity, and hydrophobicity of the solvents. Furthermore, the mixing thermodynamic properties of the dissolution process were calculated using a Wilson-based model, revealing that the dissolution of 3,3′-Diindolylmethane in the studied solvents is a spontaneous, endothermic, and entropy-driven process.

用重量法测定了3,3′-二吲哚基甲烷在14种不同溶剂（272.45 ~ 324.25 K）中的溶解度。结果表明，在研究的溶剂范围内，其溶解度随温度升高而增大。298.15 K时，3,3′-二吲哚甲烷在溶剂中的溶解度顺序为：2-戊酮>；乙酸乙酯>；乙酸甲酯>；甲酸乙酯>；乙腈>；正戊醇>；正丁醇>；正丙醇>；乙醇>；异丙醇>；异戊醇>；甲醇>；异丁醇>；甲苯。采用5种热力学模型对实验数据进行关联，其中修正的Apelblat模型拟合效果最好。此外，还进行了静电势能表面分析，初步评价了可能的溶质溶剂相互作用。密度泛函理论计算和KAT-LSER模型的结果表明，3,3 ' -二吲哚甲烷主要作为氢键供体，其溶解度受溶剂的氢键受体能力、极性和疏水性的协同影响。此外，利用基于wilson的模型计算了溶解过程的混合热力学性质，揭示了3,3 ' -二吲哚基甲烷在所研究溶剂中的溶解是一个自发的吸热熵驱动过程。

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引用次数: 0

Sustainable ultrasonication–acetic acid synergy enables water-soluble chitosan with tunable structure and function 持续的超声-醋酸协同作用使壳聚糖具有可调的结构和功能

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2026-01-02 DOI: 10.1016/j.molliq.2026.129231

Thi Sinh Vo , Pyone Pyone Chit , Thuy-Ngan Dang Thi , Trung Hoang , Tran Thi Bich Chau Vo , Min-hwan Hwang , Kyunghoon Kim

A green and efficient strategy for enhancing the aqueous solubility of chitosan (Chi) was developed by coupling ultrasonication with extremely mild acetic acid (AcA, 0.2–1.0 %). A comprehensive set of characterization techniques, including dynamic light scattering, pH, zeta potential analysis, UV–visible spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and thermogravimetric analyses, was employed to elucidate the physicochemical changes induced by this treatment. Mild AcA primarily facilitated protonation and increased accessibility of amino groups, while ultrasonication generated cavitation forces that disrupted hydrogen bonding and partially relaxed crystalline domains. These combined effects produced Chi with reduced particle size, enhanced amorphous character, increased optical clarity, and improved colloidal stability. Systematic evaluation of AcA concentration and sonication duration revealed an optimal processing window in which structural relaxation and controlled fragmentation enhanced solubility, whereas excessive sonication resulted in over-fragmentation and lower recovery yields. This study provides mechanistic insight into how cavitation-driven disruption synergizes with mild protonation to produce water-dispersible Chi under environmentally benign conditions, offering a sustainable alternative to conventional high-acid or energy-intensive dissolution approaches.

以极温和的醋酸（AcA, 0.2 ~ 1.0%）为溶剂，建立了一种绿色高效的提高壳聚糖（Chi）水溶性的方法。采用动态光散射、pH、zeta电位分析、紫外可见光谱、傅里叶变换红外光谱、x射线衍射、扫描电镜和热重分析等综合表征技术，阐明了该处理引起的物理化学变化。温和的AcA主要促进质子化和增加氨基的可及性，而超声波产生的空化力破坏了氢键和部分放松了晶体结构域。这些综合作用产生的Chi具有减小的粒径，增强的无定形特性，增加的光学清晰度和改善的胶体稳定性。对AcA浓度和超声时间的系统评价揭示了一个最佳处理窗口，其中结构松弛和控制破碎增强了溶解度，而过度超声则导致过度破碎和回收率降低。这项研究提供了在环境无害的条件下，空化驱动的破坏如何与轻度质子化协同产生水可分散的Chi的机理，为传统的高酸或高能量溶解方法提供了一种可持续的替代方案。

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引用次数: 0

Dual-interfacial design of mixed matrix membranes using NH2-UiO-66 MOF and choline chloride/urea DES for enhanced gas separation NH2-UiO-66 MOF和氯化胆碱/尿素DES混合基质膜的双界面设计

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2026-01-02 DOI: 10.1016/j.molliq.2026.129233

Hafiza Mamoona Khalid , Afshan Mujahid , Asim Laeeq Khan , Rafi Ullah Khan , Rabya Aslam , Rafael M. Santos

The long-standing permeability–selectivity trade-off in polymeric membranes continues to limit the deployment of energy-efficient CO₂ separation technologies. Here, we report a dual-interfacial design strategy that integrates deep eutectic solvents (DESs) with metal organic frameworks (MOFs) to overcome this constraint. A choline chloride-urea DES (1:2) was rationally engineered as a multifunctional compatibilizer and CO₂-affinitive interphase, enabling strong hydrogen-bonding interactions with both Pebax 1657 and UiO-66-type fillers. DES impregnation into UiO-66 and NH₂-UiO-66 preserved crystalline integrity while introducing additional sorption sites and improving polymer–filler adhesion. The resulting mixed matrix membranes (MMMs) exhibit increase in CO₂ permeability by up to ∼90 % relative to pristine Pebax while maintaining selectivity, reaching CO₂/CH₄ = 40 and CO₂/N₂ = 62 for NH₂-UiO-66/DES membranes. The membranes show stable mixed-gas performance, reduced activation energies for CO₂ transport, and robust operation across temperature and feed-composition variations. Benchmarking against recent Pebax-based MMMs and Robeson's upper bound confirms that these DES-MOF hybrids not only bridge but surpass the conventional trade-off, matching or outperforming top-reported systems while using environmentally benign, low-cost DESs instead of ionic liquids.

长期以来，聚合物膜的渗透性和选择性之间的权衡一直限制着节能CO₂分离技术的应用。在这里，我们报告了一种双界面设计策略，该策略将深共晶溶剂（DESs）与金属有机框架（mof）集成在一起，以克服这一限制。氯化胆碱-尿素DES（1:2）作为多功能相容剂和CO₂亲和间相，可与Pebax 1657和uio -66型填料形成强氢键相互作用。将DES浸渍到UiO-66和NH₂-UiO-66中，可以保持晶体的完整性，同时引入额外的吸附位点，提高聚合物填料的附着力。所得到的混合基质膜（MMMs）在保持选择性的同时，相对于原始Pebax， CO₂渗透率增加了高达90%，NH₂- uui -66/DES膜达到CO₂/CH₄= 40和CO₂/N₂= 62。该膜具有稳定的混合气体性能，降低了CO₂运输的活化能，并且在温度和饲料组成变化中具有强大的运行能力。通过对最近基于pebax的mm mm和Robeson上限的基准测试，证实了这些DES-MOF混合材料不仅可以起到桥梁作用，而且超越了传统的权衡，在使用环保、低成本的DESs而不是离子液体的情况下，可以匹配或优于顶级报道的系统。

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引用次数: 0

Characterization of Solutol® HS15 and Labrasol® mixed micellar system: Insights into their combined effects on ophthalmic drug delivery systems Solutol®HS15和Labrasol®混合胶束体系的表征：它们在眼科给药系统中的联合作用

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2026-01-02 DOI: 10.1016/j.molliq.2025.129229

Gaurang Dalsaniya , Sugam Kumar , Vinod K. Aswal , Sadafara A. Pillai

In ophthalmology, considerable attention has been directed toward the development of micellar carriers to improve ocular drug delivery. The present study investigates the influence of Labrasol® on the physicochemical properties of Solutol® HS15 micellar systems with relevance to ocular drug delivery. Mixed micelles were systematically characterized using small-angle neutron scattering (SANS), dynamic light scattering (DLS), cloud point (CP) measurements, viscosity analysis, and UV–visible spectroscopy. Results revealed that Labrasol® significantly reduced the CP of Solutol® HS15, indicating altered micellar stability. SANS and DLS analyzes further demonstrated a marked decrease in micellar size, suggestive of demicellization. Additionally, UV–visible spectroscopy and high-performance liquid chromatography (HPLC) using norfloxacin confirmed enhanced drug solubility in the presence of Labrasol®. Collectively, these findings demonstrate that Labrasol® strongly modulates the morphology, size distribution, and hydration of Solutol® HS15 micelles. This work highlights the critical role of surfactant interactions in determining the behavior of mixed micellar systems and provides valuable insights for designing advanced micellar nanocarriers in ocular drug delivery.

在眼科学中，胶束载体的发展已经引起了相当大的关注，以改善眼部药物输送。本研究探讨Labrasol®对Solutol®HS15胶束系统的理化性质与眼部给药相关的影响。采用小角中子散射（SANS）、动态光散射（DLS）、云点（CP）测量、粘度分析和紫外可见光谱对混合胶束进行了系统表征。结果显示Labrasol®显著降低了Solutol®HS15的CP，表明胶束稳定性发生了改变。SANS和DLS分析进一步表明胶束大小明显减小，提示脱胶。此外，使用诺氟沙星的紫外可见光谱和高效液相色谱（HPLC）证实，在Labrasol®存在下，药物溶解度增强。总的来说，这些发现表明Labrasol®强烈调节溶解醇®HS15胶束的形态、大小分布和水合作用。这项工作强调了表面活性剂相互作用在决定混合胶束系统行为中的关键作用，并为设计先进的胶束纳米载体在眼部给药中提供了有价值的见解。

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引用次数: 0

Nitro functionalization of pyrrole-based bisurea molecular tweezers for enhanced Fe(110) surface protection: A first-principles study 吡咯基双尿素分子钳的硝基功能化对增强铁（110）表面保护的第一性原理研究

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2026-01-01 DOI: 10.1016/j.molliq.2025.128841

Ahmed Hazem Abdelhay , Aymen S. Abu Hatab , Mazen Khaled , Mohanad Shkoor , Raed M. Al-Zoubi , Abdulilah Dawoud Bani-Yaseen

Iron corrosion is a major industrial and economic problem that calls for effective and sustainable corrosion inhibitors. This work uses first-principles density functional theory to evaluate a nitro-substituted pyrrole-based bisurea tweezer, BUP-NO₂, as a potential inhibitor for the iron (110) surface. Key electronic and thermodynamic results are reported: for BUP-H the HOMO and LUMO are −4.96 eV and − 0.72 eV (gap 4.24 eV), the calculated charge transfer ΔN is −0.98, and the adsorption energy E_o ads is −4.05 eV. For BUP-NO₂ the HOMO and LUMO are −5.17 eV and − 3.00 eV (gap 2.17 eV), ΔN is −1.34, and E_o ads is −7.76 eV. The NO₂ substitution therefore lowers the HOMO–LUMO gap, increases charge transfer, and strengthens adsorption by about 3.7 eV. BUP-NO₂ further exhibits reduced hardness (η = 0.63 eV vs. 1.55 eV for BUP-H), enhanced softness (S = 1.59 vs. 0.65 eV⁻¹), and a much higher electrophilicity index (ω = 18.03 vs. 4.11 eV). Its dipole moment and polarizability also rise markedly (26.8 D vs. 5.9 D), favoring stronger electrostatic stabilization and surface blocking. Charge density difference and partial density of states analysis show higher electronic coupling and interfacial polarization for BUP-NO₂, consistent with a strong chemisorption mechanism. These electronic and thermodynamics findings validate that nitro group lowers the HOMO–LUMO gap but raises the adsorption strength, charge redistribution, and inhibitor stability as well. These results highlight how targeted electron-withdrawing substitutions can tune surface interactions and point to BUP-NO₂ as a promising candidate for practical, greener corrosion inhibition.

铁腐蚀是一个重大的工业和经济问题，需要有效和可持续的缓蚀剂。本研究使用第一性原理密度泛函理论评估了一种基于硝基取代吡咯的双尿素镊子，BUP-NO2，作为铁（110）表面的潜在抑制剂。结果表明：BUP-H的HOMO和LUMO分别为−4.96 eV和−0.72 eV（间隙为4.24 eV），计算电荷转移ΔN为−0.98，吸附能Eo ads为−4.05 eV。对于BUP-NO2， HOMO和LUMO分别为−5.17 eV和−3.00 eV（间隙为2.17 eV）， ΔN为−1.34，Eo ads为−7.76 eV。因此，NO2取代降低了HOMO-LUMO间隙，增加了电荷转移，并增强了约3.7 eV的吸附。BUP-NO2进一步表现出硬度降低（η = 0.63 eV，而BUP-H为1.55 eV），柔软度增强（S = 1.59 vs. 0.65 eV−1），亲电性指数更高（ω = 18.03 vs. 4.11 eV）。偶极矩和极化率也显著上升（26.8 D vs. 5.9 D），有利于更强的静电稳定性和表面阻塞。电荷密度差和态偏密度分析表明，BUP-NO2具有较高的电子耦合和界面极化，具有较强的化学吸附机制。这些电子和热力学研究结果证实，硝基降低了HOMO-LUMO间隙，同时提高了吸附强度、电荷再分配和抑制剂的稳定性。这些结果强调了有针对性的吸电子取代如何调节表面相互作用，并指出BUP-NO2是实用的、更环保的腐蚀抑制的有希望的候选者。

{"title":"Nitro functionalization of pyrrole-based bisurea molecular tweezers for enhanced Fe(110) surface protection: A first-principles study","authors":"Ahmed Hazem Abdelhay , Aymen S. Abu Hatab , Mazen Khaled , Mohanad Shkoor , Raed M. Al-Zoubi , Abdulilah Dawoud Bani-Yaseen","doi":"10.1016/j.molliq.2025.128841","DOIUrl":"10.1016/j.molliq.2025.128841","url":null,"abstract":"<div><div>Iron corrosion is a major industrial and economic problem that calls for effective and sustainable corrosion inhibitors. This work uses first-principles density functional theory to evaluate a nitro-substituted pyrrole-based bisurea tweezer, BUP-NO<sub>2</sub>, as a potential inhibitor for the iron (110) surface. Key electronic and thermodynamic results are reported: for BUP-H the HOMO and LUMO are −4.96 eV and − 0.72 eV (gap 4.24 eV), the calculated charge transfer Δ<em>N</em> is −0.98, and the adsorption energy <em>E</em><sub>o</sub> ads is −4.05 eV. For BUP-NO<sub>2</sub> the HOMO and LUMO are −5.17 eV and − 3.00 eV (gap 2.17 eV), Δ<em>N</em> is −1.34, and <em>E</em><sub>o</sub> ads is −7.76 eV. The NO<sub>2</sub> substitution therefore lowers the HOMO–LUMO gap, increases charge transfer, and strengthens adsorption by about 3.7 eV. BUP-NO<sub>2</sub> further exhibits reduced hardness (<em>η</em> = 0.63 eV vs. 1.55 eV for BUP-H), enhanced softness (<em>S</em> = 1.59 vs. 0.65 eV<sup>−1</sup>), and a much higher electrophilicity index (ω = 18.03 vs. 4.11 eV). Its dipole moment and polarizability also rise markedly (26.8 D vs. 5.9 D), favoring stronger electrostatic stabilization and surface blocking. Charge density difference and partial density of states analysis show higher electronic coupling and interfacial polarization for BUP-NO<sub>2</sub>, consistent with a strong chemisorption mechanism. These electronic and thermodynamics findings validate that nitro group lowers the HOMO–LUMO gap but raises the adsorption strength, charge redistribution, and inhibitor stability as well. These results highlight how targeted electron-withdrawing substitutions can tune surface interactions and point to BUP-NO<sub>2</sub> as a promising candidate for practical, greener corrosion inhibition.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"441 ","pages":"Article 128841"},"PeriodicalIF":5.2,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880425","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}

引用次数: 0

Corrigendum to “Selective detection of aqueous and cellular copper (II) ion via Coumarin-based AIEgen through aggregation shift” [J. Mol. Liquids 440 (2025) 128973] “基于香豆素的AIEgen通过聚集移位选择性检测水和细胞铜（II）离子”的更正[J]。Mol.液体440 (2025)128973]

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2026-01-01 DOI: 10.1016/j.molliq.2025.129030

Narayan Murmu , Kalpanarani Dash , Sukanya Mandal , Monalisa Mishra , Gokarneswar Sahoo , Satya Narayan Sahu

引用次数: 0

Retraction notice to “Core-shell structured Ag-HAp@Bi2S3 as effective S-scheme heterojunction photocatalyst: Induced with internal polarization electric field effect and co-catalyst fashions” [J. Mol. Liquids 399 (2024) 124423] “核壳结构Ag-HAp@Bi2S3作为有效的s型异质结光催化剂：由内极化电场效应和共催化剂方式诱导”的撤回通知[J]。Mol.液体399 (2024)124423]

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2026-01-01 DOI: 10.1016/j.molliq.2025.129088

Mohammad Chahkandi , Mahboobeh Zargazi , Khadijeh Boland Ghiasabadi , Jin Suk Chung

引用次数: 0

Why 1,3,5-Trichloro-2,4-dinitrobenzene (TCDNB) is more soluble in nitric acid than in sulfuric acid: Thermodynamic analysis and molecular dynamics simulation 为什么1,3,5-三氯-2,4-二硝基苯（TCDNB）在硝酸中比在硫酸中更容易溶解：热力学分析和分子动力学模拟

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-12-31 DOI: 10.1016/j.molliq.2025.129185

Xinyue Chen , Wei Feng , Zhengyue Liang , Zichao Guo , Liping Chen , Wanghua Chen

1,3,5-Trichloro-2,4-dinitrobenzene (TCDNB) is an important intermediate for energetic materials. This study determined the solubility of TCDNB in binary solvent systems (nitric acid + water, sulfuric acid + water) over the temperature range of 293.15 to 323.15 K under atmospheric pressure. The solubility of TCDNB was observed to increase with both rising nitric acid concentration and elevated temperature. Its dissolution behavior was examined within the temperature ranges of 293.15–323.15 K and 293.15–363.15 K, respectively. In both systems studied, solubility exhibited a marked increase with rising temperature. The mole fraction solubility rose from 3.86 × 10⁻² at 293.15 K to 7.45 × 10⁻² at 323.15 K—representing an approximately 1.93-fold increase over the 30 K temperature interval. Solubility data were well correlated by the modified Apelblat equation, Yaws equation and Jouyban-Acree model, and the modified Apelblat equation achieved the best fitting results (ARD = 1.68 × 10⁻², RMSD = 3.87 × 10⁻²). Furthermore, the mechanisms through which intermolecular interactions influence the solubility of TCDNB in mixed solvents were probed applying Density Functional Theory (DFT) calculations and Molecular Dynamics (MD) simulations. Both nitric acid and sulfuric acid molecules are capable of engaging with TCDNB through OH-ON hydrogen bonding, an interaction that constitutes the key factor in promoting its dissolution. Furthermore, the robust OH-OH hydrogen bonding between nitric acid and water molecules reduces TCDNB solubility in the mixed solvent. Meanwhile, Sulfuric acid molecules form stable three-dimensional network structures via strong OH-OS hydrogen bonds, which are difficult to disrupt, significantly diminishing TCDNB solubility in sulfuric acid. This work offers a microscopic perspective for subsequent studies on the correlation between TCDNB's solubility and its molecular structure, which is instrumental in advancing its industrial-scale manufacturing and utilization.

1,3,5-三氯-2,4-二硝基苯（TCDNB）是含能材料的重要中间体。本研究测定了TCDNB在二元溶剂体系（硝酸+水、硫酸+水）中的溶解度，温度范围为293.15 ~ 323.15 K，常压下。TCDNB的溶解度随硝酸浓度的升高和温度的升高而增加。分别在293.15 ~ 323.15 K和293.15 ~ 363.15 K的温度范围内考察了其溶解行为。在研究的两种体系中，溶解度都随着温度的升高而显著增加。摩尔分数溶解度从293.15 K时的3.86 × 10−2上升到323.15 K时的7.45 × 10−2，在30 K温度区间内增加了约1.93倍。修正后的Apelblat方程、Yaws方程和Jouyban-Acree模型对溶解度数据的拟合效果较好，其中修正后的Apelblat方程拟合效果最佳（ARD = 1.68 × 10−2,RMSD = 3.87 × 10−2）。此外，应用密度泛函理论（DFT）计算和分子动力学（MD）模拟，探讨了分子间相互作用影响TCDNB在混合溶剂中溶解度的机理。硝酸和硫酸分子都能通过OH-ON氢键与TCDNB发生作用，这是促进TCDNB溶解的关键因素。此外，硝酸和水分子之间牢固的OH-OH氢键降低了TCDNB在混合溶剂中的溶解度。同时，硫酸分子通过强OH-OS氢键形成稳定的三维网络结构，难以破坏，显著降低了TCDNB在硫酸中的溶解度。本研究为后续研究TCDNB的溶解度与其分子结构之间的关系提供了微观视角，有助于推进其工业规模的制造和利用。

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引用次数: 0

Nickel complex of camphor-substituted tetrapyrazinoporphyrazine as an inducer of helical liquid crystalline phase 樟脑取代的四吡嗪卟啉镍配合物作为螺旋液晶相的诱导剂

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-12-31 DOI: 10.1016/j.molliq.2025.129193

Vladimir Burmistrov, Igor Novikov, Viktor Aleksandriiskii, Alina Budanova, Alexandr Semeikin

In this study, the ability of the chiral tetracamphor derivative of tetrapyrazinoporphyrazine (Ni(−)TСPyzPz) to induce a helical liquid crystalline phase in a nematic mixture of alkoxycyanobiphenyls is investigated. Based on quantum chemistry and UV/Vis CD spectroscopy, it was shown that the chirality of (Ni(−)TCPyzPz) in chloroform solutions depends significantly on its association, leading to the appearance of a noticeable dipole moment. The H-dimer («face-to-face») is the most stable. Using polarisation microscopy, the formation of the fingerprint texture and Newton interference rings was recorded after the introduction of (Ni(−)TСPyzPz) into the nematic mixture of alkoxycyanobiphenyls CB-2. Clearing temperatures, helical pitch, and helical twisting power (HTP) were measured. The high efficiency of helix induction under the action of (Ni(−)TСPyzPz) (maximum HTP value 87.7 μm⁻¹) was found, decreasing with increasing dopant concentration due to its association. The dichroic ratio of Q-band absorption and the order parameter of (Ni(−)TСPyzPz) were measured by polarisation spectroscopy. The CD spectra of the dopant in the CB-2 mixture were obtained, the values of the molar circular dichroism coefficient and the g-factor of the Q-band dissymmetry were calculated. The g value in LC was shown to be 147 times greater than in the chloroform solution as a result of the amplification of chirality in the anisotropic medium. An increase in circular dichroism with a rise in the number of nematic LC molecules in the solvation shell was shown by the quantum chemistry method.

在这项研究中，研究了四吡嗪卟啉（Ni(−)TСPyzPz）的手性四脑衍生物在烷氧基氰联苯的向列相混合物中诱导螺旋液晶相的能力。基于量子化学和紫外/可见CD光谱，表明（Ni(−)TCPyzPz）在氯仿溶液中的手性主要取决于其缔合，导致出现明显的偶极矩。h二聚体（“面对面”）是最稳定的。利用偏光显微镜，将（Ni(−)TСPyzPz）引入到烷氧基氰联苯CB-2的向列相混合物中，记录了指纹纹理和牛顿干涉环的形成。测量了清洗温度、螺旋节距和螺旋扭转力（HTP）。在（Ni(−)TСPyzPz）作用下，螺旋感应效率较高（HTP最大值为87.7 μm−1），但随着掺杂浓度的增加，HTP随掺杂浓度的增加而降低。用偏振光谱法测定了q波段吸收的二向色比和（Ni(−)TСPyzPz）的序参量。得到了掺杂剂在CB-2混合物中的CD光谱，计算了掺杂剂的摩尔圆二色系数和q带不对称性的g因子。由于各向异性介质中手性的放大，LC中的g值比氯仿溶液中的大147倍。量子化学方法表明，随着溶剂化壳中向列相LC分子数量的增加，圆二色性增加。

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引用次数: 0

Exploring the molecular recognition between FpvA and colicin E9 immunity protein for disrupting FpvA-mediated Iron uptake in Pseudomonas aeruginosa: an advanced computational study 探索FpvA和colicin E9免疫蛋白之间的分子识别，以破坏铜绿假单胞菌中FpvA介导的铁摄取：一项先进的计算研究

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2025-12-31 DOI: 10.1016/j.molliq.2025.129216

Rihaf Alfaraj, Fai Alkathiri

Confronted with the challenge of antibiotic resistance in the opportunistic pathogen Pseudomonas aeruginosa (P. aeruginosa), this study explores a novel anti-virulence strategy targeting the bacterium's critical iron-acquisition machinery. This study hypothesizes that a protein ligand based on the Colicin E9 immunity protein (Im9) scaffold can specifically target the extracellular face of P. aeruginosa's ferripyoverdine receptor A (FpvA), blocking pyoverdine uptake or inhibiting its transport, thereby disrupting receptor function. Plausible binding could hinder ferripyoverdine binding or lock the receptor, preventing the TonB-dependent conformational changes needed for iron translocation. A comprehensive workflow encompassing docking, molecular dynamics (MD) simulation, and binding energy assessment was implemented to elucidate the interaction mechanism. The docking results showed differences in binding stability and orientation and were further evaluated through 500 ns MD simulations, which illustrated the dynamic behavior of the complexes. The best blind and directed molecular docking approaches were found to show strong affinity, with GOAP scores of −94,908.37 and −95,060.13, respectively. Moreover, the binding affinities calculated by the MMGBSA method from PRODIGY and MD simulations were −12.80 and −14.54 kcal/mol for best blind docking, and −14.60 and −9.27 kcal/mol for best directed docking, respectively. A higher binding affinity on the negative scale strongly suggests a significant association in both static and dynamic states. Hence, this study enhances the understanding of bacterial iron uptake, aids antimicrobial strategy development, provides an atomic model of the FpvA-Im9 complex, identifies key binding factors, and evaluates its stability, serving as a blueprint for designing new therapeutics against P. aeruginosa.

面对机会致病菌铜绿假单胞菌（P. aeruginosa）的抗生素耐药性挑战，本研究探索了一种针对细菌关键铁获取机制的新型抗毒策略。本研究假设基于Colicin E9免疫蛋白（Im9）支架的蛋白质配体可以特异性靶向P. aeruginosa的铁吡啶受体a （FpvA）的细胞外表面，阻断pyoverdine摄取或抑制其运输，从而破坏受体功能。合理的结合可能会阻碍铁嘧啶结合或锁定受体，从而阻止铁易位所需的tonb依赖性构象变化。通过对接、分子动力学（MD）模拟和结合能评估等综合工作流程来阐明相互作用机制。对接结果显示了结合稳定性和取向的差异，并通过500 ns MD模拟进一步评估了配合物的动力学行为。结果表明，最佳的盲分子对接和定向分子对接方法具有较强的亲和性，GOAP得分分别为- 94,908.37和- 95,060.13。此外，根据PRODIGY和MD模拟，MMGBSA方法计算出的最佳盲对接结合亲和度分别为- 12.80和- 14.54 kcal/mol，最佳定向对接的结合亲和度分别为- 14.60和- 9.27 kcal/mol。在负尺度上较高的结合亲和力强烈表明在静态和动态状态下都有显著的关联。因此，本研究增强了对细菌铁摄取的理解，有助于抗菌策略的开发，提供了FpvA-Im9复合物的原子模型，确定了关键结合因子，并评估了其稳定性，为设计针对铜绿假单胞菌的新疗法提供了蓝图。

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