Journal of Molecular Liquids最新文献_第5页

Molecular simulation of conformational and surface characteristics of ring and linear polymer nanoparticles with different chain stiffness 不同链刚度的环状和线状聚合物纳米颗粒构象和表面特性的分子模拟

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2026-03-15 Epub Date: 2026-01-12 DOI: 10.1016/j.molliq.2026.129260

Krisana Monklang , Yuya Doi , Visit Vao-soongnern

Monte Carlo (MC) simulations of coarse-grained (CG) polyethylene-like models were developed to investigate the impact of chain topology and chain stiffness on conformational and surface properties of free-standing ring and linear polymer nanoparticles in vacuum. The “forcefield,” to represent the intramolecular and intermolecular interactions, was treated by the Rotational Isomeric State (RIS) model and the Lennard-Jones (LJ) potential energies, respectively. The original RIS statistical weights were multiplied by the chain stiffness parameter (k) to mimic the characteristics of stiffer (k > 1.0) and more flexible (k < 1.0) chains in comparison to polyethylene (k = 1.0). For more flexible chains, bulk densities of polymer nanoparticles generally increase, resulting in sharper surface profiles and more compacted structures. Compared to linear chains, the density of ring polymer nanoparticles tends to be slightly higher, with noticeably sharper surface profiles, especially for more flexible chains. In the bulk region, bonds and chains typically exhibit random orientation; nevertheless, near the surface, particularly for stiffer chains, they show anisotropic arrangement. A lower fraction of trans state is apparent in more flexible polymers, which leads to smaller molecular dimensions.Polymer chains generally have their largest molecular axes aligned parallel to the surface, and a higher degree of this anisotropy is observed for more rigid chains. According to their intramolecular and intermolecular energetics, nanoparticles adopt denser structures with a larger fraction of gauche state for more flexible chains in the bulk region. Near the surface, chains typically adopt more trans conformation, and the reduction in density leads to faster monomer dynamics, which can be seen for linear chains, while monomer dynamics in ring polymers move more slowly due to bond connectivity. The distance of increased dynamics in the surface region is longer than the scale of bond length for both ring and linear polymer nanoparticles.

采用蒙特卡罗（MC）方法模拟了粗粒聚乙烯类模型，研究了真空条件下链拓扑结构和链刚度对独立环形和线性聚合物纳米颗粒构象和表面性能的影响。代表分子内和分子间相互作用的“力场”分别用旋转同分异构体态（RIS）模型和Lennard-Jones （LJ）势能来处理。原始RIS统计权重乘以链刚度参数(k)，以模拟与聚乙烯（k = 1.0）相比，更硬（k > 1.0）和更灵活（k < 1.0）链的特性。对于更灵活的链，聚合物纳米颗粒的体积密度通常会增加，从而导致更清晰的表面轮廓和更紧凑的结构。与线性链相比，环状聚合物纳米颗粒的密度往往略高，表面轮廓明显更清晰，特别是对于更灵活的链。在体区，键和链通常表现为随机取向；然而，在表面附近，特别是对于较硬的链，它们表现出各向异性排列。在更灵活的聚合物中，反态的比例更低，这导致分子尺寸更小。聚合物链的最大分子轴通常与表面平行，刚性链的各向异性程度更高。根据其分子内和分子间的能量学，纳米颗粒采用更致密的结构，具有更大的间扭态，在体区具有更灵活的链。在表面附近，链通常采用更多的反式构象，并且密度的降低导致单体动力学更快，这可以在线性链中看到，而环状聚合物中的单体动力学由于键连通性而移动更慢。无论是环状还是线型聚合物纳米粒子，其表面区域的动力学增加距离都大于键长尺度。

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引用次数: 0

Ferrocene as a non-innocent redox marker in sensors: Unveiling its role in anion binding by electronic structure calculations and experiments 二茂铁在传感器中的非无害氧化还原标记：通过电子结构计算和实验揭示其在阴离子结合中的作用

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2026-03-15 Epub Date: 2026-01-27 DOI: 10.1016/j.molliq.2026.129292

Soma Keszei , Rita Skoda-Földes , György Lendvay

Sensing of weakly coordinating anions remains a significant challenge, due to their relatively low basicity. Our theoretical and experimental investigations show that a ferrocene moiety, incorporated into a receptor molecule not only serves as an electrochemical marker, but also able to participate in the binding of weakly coordinating anions, making possible their detection. Geometrical parameters of DFT-optimized structures of complexes, formed by the binding of [BF₄]⁻, [OTf]⁻ and [CF₃CO₂]⁻ anions to the isomers of protonated 1-(4-ferrocenyl-6-phenylpyrimidin-2-yl)-3-phenylurea revealed the formation of C-H---anion hydrogen bonds between ferrocene and the O or F atoms of the coordinated anion, which is supported by bond order, QTAIM, NCI as well as chemical energy component analysis. Importantly, the computational predictions of hydrogen bond formation are corroborated by low-temperature ¹H NMR titration experiments, highlighting the essential role of combined experimental and theoretical investigations in accurately characterizing anion recognition processes.

弱配位阴离子的感应仍然是一个重大的挑战，因为它们的碱度相对较低。我们的理论和实验研究表明，二茂铁片段结合到受体分子中，不仅可以作为电化学标记，还可以参与弱配位阴离子的结合，从而使它们的检测成为可能。由[BF4]−、[OTf]−和[CF3CO2]−阴离子与质子化的1-（4-二茂铁-6-苯基嘧啶-2-基）-3-苯脲异构体结合形成的配合物的几何参数显示，二茂铁与配位阴离子的O或F原子之间形成了C-H-阴离子氢键，键序、QTAIM、NCI和化学能成分分析支持了这一结果。重要的是，氢键形成的计算预测得到了低温1H NMR滴定实验的证实，突出了实验和理论相结合的研究在准确表征阴离子识别过程中的重要作用。

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引用次数: 0

Solid-state emissive small molecules comprising 1,2,4-oxadiazole scaffold: intramolecular charge transfer-driven tunable photophysical properties 包含1,2,4-恶二唑支架的固态发光小分子：分子内电荷转移驱动的可调光物理性质

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2026-03-15 Epub Date: 2026-01-27 DOI: 10.1016/j.molliq.2026.129324

Murat Olutas , Farah I.A. Al-Hayali , Akın Sağırlı , Havva Acar

1,2,4-oxadiazole is a heterocyclic compound rarely preferred as a main scaffold in the organic emitter literature due to its antisymmetric structure and restricted structural conjugation. To provide knowledge for designing new structures, it is essential to understand the emission mechanism of compounds comprising this member of the oxadiazole family as a scaffold. Herein, we report the syntheses and the photophysical properties of a new group of fluorescent small molecules with a 1,2,4-oxadiazole scaffold that features aryl and styryl moieties modified with donor and acceptor groups. The photophysical properties of the compounds, exhibiting fluorescence emission in both solution and solid-state, have been systematically studied, and their emission mechanism was also discussed considering the results. Analyzing steady-state photoluminescence (PL) measurements performed for the dilute solutions of compounds shows that only the donor-acceptor structured compounds exhibit strong fluorescence emission, shifting to the lower-energy side of the spectrum, accompanied by a decreasing PL quantum yield, as the solvent polarity increases. The results indicate that the main mechanism responsible for this strong positive solvatochromic behavior is the dipole-dipole coupling between the molecules of the synthesized compounds with intramolecular charge transfer (ICT) properties and the solvent molecules. The solvatochromic behavior of the compounds was also analyzed using five different solvatochromic shift methods. In addition, the results of the quantum chemical calculations performed for the synthesized molecules reveal a charge-separated distribution for the frontier molecular orbitals of the compounds, confirming their ICT nature. On the other hand, PL spectroscopy studies show that all compounds also exhibit PL emission in solid phases. The results indicate that the solid-state emission of the compounds can be tuned between the blue and red regions of the visible spectrum, depending on the position and type of functional groups attached to the oxadiazole scaffold, without significant changes in conjugation length. Furthermore, the analyses of time-resolved fluorescence measurements conducted to understand their emission kinetics reveal an ICT-driven emission model consisting of a radiative decay pathway from a locally excited (LE) state to an ICT state, then to the ground state.

1,2,4-恶二唑是一种杂环化合物，由于其反对称结构和有限的结构共轭性，在有机发射极文献中很少被用作主要支架。为了提供设计新结构的知识，有必要了解由这个恶二唑家族成员组成的化合物作为支架的发射机制。在此，我们报道了一组具有1,2,4-恶二唑支架的新型荧光小分子的合成及其光物理性质，其特征是芳基和苯乙烯基被供体和受体基团修饰。系统地研究了化合物在溶液和固态下均具有荧光发射的光物理性质，并结合结果对其发射机理进行了探讨。对化合物的稀释溶液进行的稳态光致发光（PL）测量分析表明，随着溶剂极性的增加，只有供体-受体结构的化合物表现出强烈的荧光发射，向光谱的低能侧转移，并伴随着PL量子产率的降低。结果表明，具有分子内电荷转移（ICT）性质的化合物分子与溶剂分子之间的偶极-偶极耦合是导致这种强正溶剂致变色行为的主要机制。用五种不同的溶剂化变色方法分析了化合物的溶剂化变色行为。此外，对合成分子进行的量子化学计算结果揭示了化合物前沿分子轨道的电荷分离分布，证实了它们的ICT性质。另一方面，PL光谱研究表明，所有化合物在固相中也表现出PL发射。结果表明，化合物的固态发射可以根据附着在恶二唑支架上的官能团的位置和类型在可见光谱的蓝色和红色区域之间进行调节，而共轭长度没有明显变化。此外，为了解其发射动力学而进行的时间分辨荧光测量分析揭示了ICT驱动的发射模型，该模型包括从局部激发（LE）状态到ICT状态，然后到基态的辐射衰减途径。

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引用次数: 0

Integrating DFT and experiments to elucidate Pb2+–surfactant interactions for micelle-enhanced water remediation 结合DFT和实验阐明Pb2+ -表面活性剂在胶束强化水修复中的相互作用

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2026-03-15 Epub Date: 2026-01-31 DOI: 10.1016/j.molliq.2026.129331

Abdelhakim Bourouba , Redha Alouaoui , Samira Ferhat , Tomasz Janek

Lead ions (Pb²⁺) are highly toxic, bioaccumulative, and non-biodegradable, making their removal from contaminated environments a critical global challenge. In this work, an integrated quantum–experimental framework was developed to investigate Pb²⁺ adsorption by two anionic surfactants N-lauroylsarcosine (LS) and sodium dodecyl sulfate (SDS) and a nonionic surfactant (Tween 80). Density Functional Theory (DFT) calculations of molecular electrostatic potential, Mulliken charge distribution, and adsorption energy (ΔEₐdₛ) revealed that LS exhibited the strongest affinity for Pb²⁺, followed by SDS, while Tween 80 showed negligible binding. Experimental validation through surface tension isotherms (Szyszkowski and Szyszkowski–Frumkin model fitting) and dynamic light scattering (DLS) measurements confirmed these trends. Pb²⁺ complexation significantly reduced micellar aggregation numbers (from 73 to 18 for LS and from 78 to 29 for SDS), while Tween 80 displayed minimal variation. The strong agreement between theoretical and experimental results demonstrates that Pb²⁺ ions destabilize micelles by reducing their aggregation capacity, with LS showing the most efficient Pb²⁺ removal. This study provides a systematic correlation between DFT-predicted adsorption energetics and experimental interfacial behavior in Pb²⁺–surfactant systems, establishing a predictive strategy for the rational design of eco-friendly, surfactant-assisted remediation technologies for heavy metal pollutants.

铅离子（Pb2+）具有剧毒、生物蓄积性和不可生物降解性，因此将其从污染环境中清除是一项重大的全球性挑战。在这项工作中，建立了一个集成的量子实验框架来研究两种阴离子表面活性剂n -月桂酰肌氨酸（LS）和十二烷基硫酸钠（SDS）以及非离子表面活性剂Tween 80对Pb2+的吸附。密度泛函数理论（DFT）计算了分子静电势、Mulliken电荷分布和吸附能（ΔE dₛ），结果表明LS对Pb2+的亲和力最强，其次是SDS，而Tween 80的结合能力可以忽略。通过表面张力等温线（Szyszkowski和Szyszkowski - frumkin模型拟合）和动态光散射（DLS）测量的实验验证证实了这些趋势。Pb2+络合显著降低了胶束聚集数（LS从73降至18，SDS从78降至29），而Tween 80的变化最小。理论和实验结果的一致性表明，Pb2+离子通过降低胶束的聚集能力来破坏胶束的稳定，其中LS去除Pb2+的效率最高。本研究提供了dft预测Pb2+ -表面活性剂体系中吸附能量与实验界面行为之间的系统相关性，为合理设计表面活性剂辅助的环保型重金属污染物修复技术建立了预测策略。

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引用次数: 0

Optimized Hansen solubility parameters method for pharmaceutical solids: O-HSP-pharm 药物固体的Hansen溶解度参数优化方法：O-HSP-pharm

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2026-03-15 Epub Date: 2026-01-14 DOI: 10.1016/j.molliq.2026.129267

Julian Ticona-Chambi , Erivelton N. Carvalho , Edvaldo A. Almeida , Ana M.E. Santo , Lourdes Infantes , Silvia L. Cuffini

Solubility is a key physical chemical property of pharmaceutical compounds, relevant not only for research studies but also for industrial processes. Therefore, solvent selection represents a critical step in the development of new pharmaceutical formulations and in the manufacturing of pharmaceutical products. According to the International Conference on Harmonization (ICH), solvent selection in these processes must be carefully evaluated and scientifically justified, highlighting the requirement for efficient methods to assist in this process. The Hansen Solubility Parameters (HSP) and its corresponding solubility sphere provide a theoretical framework for understanding the solubility behavior of compounds in different solvents. Although HSP were originally developed for polymer systems, their application to small molecules often requires adjustments or complementary experimental validation to achieve accurate predictions. For this reason, this study aimed to develop and evaluate an optimized method based on the HSP theory and experimental measurements, applied in small molecules drug. A set of eighteen molecules, including APIs, bioactive molecules, and coformers, were analyzed. The theoretical HSP and Hansen solubility sphere values were calculated using the Group Contribution method through the HSPmol software. Then, qualitative solubility information of forty-five representative solvents commonly used in the pharmaceutical industry, was input into HSPmol software, to optimize the HSP and solubility sphere values, using a desirability function. The results demonstrated that the O-HSP-pharm method reduced the overall error and improved the representativeness of the dissolved sphere. The Total Error value obtained with the optimization method was lower than that of the theoretical model, indicating higher predictive accuracy. Moreover, the results indicate that it is necessary to provide qualitative solubility information for at least 25 solvents to HSPmol in order to obtain a robust and representative solubility sphere. The optimized method provided useful solubility data, clearly identifying the best solvents for dissolving small molecules. These findings underscore the strong potential of the O-HSP-pharm method as a robust and reliable tool to guide experimental procedures and formulation design within the pharmaceutical field.

溶解度是药物化合物的关键物理化学性质，不仅与研究有关，而且与工业生产有关。因此，溶剂选择是开发新药物配方和制造药品的关键步骤。根据国际协调会议（ICH），这些过程中的溶剂选择必须经过仔细评估和科学论证，强调需要有效的方法来协助这一过程。汉森溶解度参数（HSP）及其相应的溶解度球为理解化合物在不同溶剂中的溶解度行为提供了理论框架。虽然HSP最初是为聚合物系统开发的，但它们在小分子中的应用通常需要调整或补充实验验证才能获得准确的预测。因此，本研究旨在开发和评估一种基于热休克蛋白理论和实验测量的优化方法，并应用于小分子药物。分析了18个分子，包括原料药、生物活性分子和共构象。通过HSPmol软件，采用基团贡献法计算理论HSP值和Hansen溶解度球值。然后，将制药行业常用的45种代表性溶剂的定性溶解度信息输入到HSPmol软件中，利用期望函数优化HSP和溶解度球值。结果表明，O-HSP-pharm方法降低了总体误差，提高了溶解球的代表性。优化方法得到的总误差值小于理论模型，表明预测精度较高。此外，结果表明，有必要提供至少25种溶剂对HSPmol的定性溶解度信息，以获得一个可靠且具有代表性的溶解度球。优化后的方法提供了有用的溶解度数据，清楚地确定了溶解小分子的最佳溶剂。这些发现强调了O-HSP-pharm方法作为一种强大而可靠的工具来指导制药领域的实验程序和配方设计的强大潜力。

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引用次数: 0

Engineering the viscoelastic and adhesive properties of mucosa-mimetic poly(vinyl alcohol)/mucin hydrogels to model the small intestinal mucosa 设计模拟粘膜的聚乙烯醇/粘蛋白水凝胶的粘弹性和粘附性能来模拟小肠粘膜

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2026-03-15 Epub Date: 2026-01-15 DOI: 10.1016/j.molliq.2026.129266

Kata Szayly , Gergely Stankovits , András Szilágyi, Benjámin Gyarmati

Mucoadhesive formulations can improve the bioavailability of active ingredients in a patient-friendly manner compared to conventional, non-adhesive dosage forms. However, evaluating mucoadhesive performance is highly challenging on ex vivo samples due to the natural variability and storage difficulties of biological samples, thus mucosa-mimetic materials are becoming increasingly important for the robust, in vitro prediction of mucoadhesive properties. In this work, we prepared mucosa-mimetic hydrogels with closer resemblance in adhesive and viscoelastic properties to those of porcine small intestinal mucosa compared to previous models. To this end, we re-designed our previously developed mucin-containing poly(vinyl alcohol) (muc/PVA) hydrogel model, synthesized via the freeze-thaw method. Our approach has two key elements: minimizing the number of freeze-thaw cycles and tailoring the mechanical properties by the mucin content in the hydrogels. The adhesion on the mucosa-mimetic hydrogels was tested by using tablets of mucoadhesive excipients with highly dissimilar physicochemical properties: hydroxypropyl methylcellulose, slightly cross-linked poly(acrylic acid), and chitosan. The model hydrogels were able to differentiate the tablets in terms of their adhesion, and it was also possible to control the strength of adhesion by changing the mucin content of the hydrogels. Furthermore, muc/PVA hydrogels with a specific mucin content (6.5 wt%) displayed satisfactory similarity in viscoelasticity and adhesion towards all polymer tablets to small intestine, thus the studied range of muc/PVA hydrogels can be useful models in early development steps of novel mucoadhesive dosage forms.

与传统的非粘性剂型相比，黏附制剂可以以患者友好的方式提高活性成分的生物利用度。然而，由于生物样品的自然变异性和储存困难，在离体样品上评估黏附性能是极具挑战性的，因此模拟粘膜材料对于黏附性能的体外预测变得越来越重要。在这项工作中，我们制备了与猪小肠粘膜的黏附性和粘弹性更接近的模拟粘膜水凝胶。为此，我们重新设计了之前开发的含有黏液的聚乙烯醇（muc/PVA）水凝胶模型，通过冻融法合成。我们的方法有两个关键要素：最大限度地减少冻融循环的次数，并根据水凝胶中的粘蛋白含量来调整机械性能。采用物理化学性质差异较大的三种黏附辅料：羟丙基甲基纤维素、微交联聚丙烯酸和壳聚糖片，考察其在模拟粘膜水凝胶上的黏附性。模型水凝胶能够区分不同的片剂的粘附性，并且可以通过改变水凝胶的粘蛋白含量来控制粘附强度。此外，具有特定粘蛋白含量（6.5 wt%）的muc/PVA水凝胶对所有聚合物片剂的粘弹性和粘附性表现出令人满意的相似性，因此，所研究的muc/PVA水凝胶范围可以作为新型黏附剂型早期开发阶段的有用模型。

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引用次数: 0

Feаtures оf the interасtiоn оf sulfо derivаtives оf mоnоheteryl-substituted pоrphyrins with BSА аt different pH 具有不同pH值的相互间的、磺化的、衍生的、杂基取代的、具有BSА不同pH值的

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2026-03-15 Epub Date: 2026-01-15 DOI: 10.1016/j.molliq.2026.129265

Nаtаlyа Sh. Lebedevа , Elenа S. Yurinа , Sаbir S. Guseinоv , Аleksey N. Kiselev , Mikhаil А. Lebedev , Irinа А. Skоrоbоgаtkinа , Sergey А. Syrbu

The prасtiсаl useful prоperties оf sulfо derivаtives оf pоrphyrins depend signifiсаntly оn pH. Fоr exаmple, саnсer сells hаve а mоre асidiс envirоnment (pH = 5.5) соmpаred tо nоrmаl сells (pH = 7.2). The effeсt оf pH (5.5 ≤ pH ≤ 6.5 аnd 7.4) оn the соmplexing аbility tоwаrds BSА аnd the phоtосаtаlytiс асtivity оf sulfо-substituted pоrphyrins соntаining а hydrоphоbiс peripherаl substituent (а residue оf benzоthiаzоle, benzimidаzоle аnd benzоxаzоle) wаs studied.

Ассоrding tо аbsоrptiоn аnd fluоresсenсe speсtrоsсоpy, it wаs fоund thаt аt pH = 7.4, pоrphyrins in mоnоmeriс fоrm bind tо prоtein. The lосаlizаtiоn оf pоrphyrins inside the prоtein glоbule wаs prоven by IR speсtrоsсоpy, thermосhemiсаl аnаlysis, stаtiоnаry аnd time-resоlved fluоrimetry. It wаs fоund thаt the соmplexаtiоn оf pоrphyrins with BSА leаds tо аn inсreаse in the prоpоrtiоn оf disоrdered struсtures аnd β-sheets аnd а deсreаse in the thermаl resistаnсe оf prоtein. Phоtоirrаdiаtiоn оf соmplexes оf BSА with pоrphyrins led tо оxidаtiоn оf prоtein struсtures.

In the rаnge оf 5.5 ≤ pH ≤ 6.5 pоrphyrins exist in the fоrm оf H-self-аssосiаtes thаt аre nоt destrоyed when interасting with BSА; pоrphyrins dо nоt саuse сhаnges in the seсоndаry struсture оf the prоtein, but inсreаse its thermаl resistаnсe by 10°С. Аnаlysis оf phоtосаtаlytiс асtivity shоwed thаt pоrphyrin lоses its аbility tо phоtо-оxidize prоteins in weаkly асidiс envirоnments.

公关асtiсаl有用公关о明显f sulfоо引出аtife f pооrphyrins取决于明显саntооn博士f r前аmple,саn hасerс公尺veаmо再保险ас伊迪сenvirоnment (pH = 5.5)со议员а红t l nооrmас咒语(pH = 7.2)。研究了effestref pH值（5.5≤pH≤6.5）和7.4)，其中， (), （（或）），（或），（或），（），（），（），（），（），（），（），（）Ассоrding tvir, bve, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp, rtp。lосаlizаti f p nоооrphyrins内部公关о爱因斯坦glо蓝wаs公关由红外speсоven trо年代соpy千卡ос半саlаnа消散,圣аtiоnаryаnd time-resооlv流感rimetry。这是一个非常神奇的地方，在这个神奇的地方，在这个神奇的地方，在这个神奇的地方，在这个神奇的地方，在这个神奇的地方，在这个神奇的地方，在这个神奇的地方，在这个神奇的地方，在这个神奇的地方，在这个神奇的地方。Ph值tооirrаdiаti f nоосоmplexes与pооf BSАrphyrins领导tооxidаti nооf公关о爱因斯坦结构с温度。在rvv5.5≤pH≤6.5的情况下，在与BSА互用的情况下，在vvvv_h -self- ssv_100,000 - vv_100,000中存在pv_rphyrins；pооrphyrins d n tосас使用hа中国大陆在seсоnd结构са变化中得到真正的f公关оо爱因斯坦,但在с再保险аse千卡l n抵制асаe 10°С。Аnаlysis driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver driver。

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引用次数: 0

Elucidating the inhibitory potential of berberine chloride against PIM-1 kinase for anticancer therapeutics 阐明氯化小檗碱对PIM-1激酶抗癌治疗的抑制潜力

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2026-03-15 Epub Date: 2026-01-26 DOI: 10.1016/j.molliq.2026.129302

Aanchal Rathi , Mohammad Saddam Khan , Zehra , Saba Noor , Tanzeel Khan , Faheem Ahmad , Md. Imtaiyaz Hassan , Mohammad Mahfuzul Haque

Berberine chloride, a natural isoquinoline alkaloid, has been investigated as a potential inhibitor of PIM-1 kinase, an oncogenic target implicated in drug resistance and cancer progression. ADMET and bioactivity profiling demonstrated high gastrointestinal absorption, favorable physicochemical properties, adherence to the Lipinski rule of five, and a bioavailability score above 50%, supporting its drug-like potential. Molecular docking study revealed a strong binding of berberine chloride within the binding pocket of PIM-1, which possesses an affinity of −9.1 kcal/mol, stabilized by hydrogen bonds, van der Waals interactions, and pi contacts with key catalytic residues. Kinase inhibition assay confirmed activity with an IC₅₀ of 57.2 μM. Binding affinity was further validated through fluorescence quenching (Ka = 1.7 × 10⁶ M⁻¹) and isothermal titration calorimetry, which indicated spontaneous, enthalpy-driven interactions. A proliferation assay in MCF-7 breast cancer cells demonstrated concentration-dependent inhibition, with an IC₅₀ of 162.3 ± 17 μM, underscoring its anticancer potential. Molecular dynamics simulations over 200 ns showed minimal structural deviations, stable compactness, and consistent hydrogen-bond patterns in the PIM-1-berberine chloride complex. Secondary-structure dynamics and principal component analysis confirmed the preservation of structural integrity and stabilized conformational states. MMPBSA analysis further indicated a favorable binding free energy (−14.91 kJ/mol), reflecting stable and energetically favorable interactions. Together, these results demonstrate that berberine chloride exhibits consistent computational and experimental evidence of PIM-1 inhibition and anticancer activity, supporting its role as a promising scaffold for future drug development.

氯化小檗碱是一种天然的异喹啉生物碱，已被研究为PIM-1激酶的潜在抑制剂，PIM-1激酶是一种与耐药和癌症进展有关的致癌靶点。ADMET和生物活性分析显示其高胃肠道吸收，良好的物理化学特性，符合Lipinski规则5，生物利用度评分超过50%，支持其药物样潜力。分子对接研究表明，在PIM-1的结合囊内，氯化小檗碱的亲和力为−9.1 kcal/mol，通过氢键、范德华相互作用和与关键催化残基的π接触稳定。激酶抑制试验证实了IC₅0为57.2 μM的活性。通过荧光猝灭（Ka = 1.7 × 106 M−1）和等温滴定量热法进一步验证了结合亲和力，这表明了自发的、焓驱动的相互作用。MCF-7乳腺癌细胞中的增殖试验显示出浓度依赖性抑制，IC₅0为162.3±17 μM，强调了其抗癌潜力。在超过200 ns的分子动力学模拟中，pim -1-小檗碱氯化配合物的结构偏差最小，致密性稳定，氢键模式一致。二级结构动力学和主成分分析证实了结构的完整性和构象状态的稳定性。MMPBSA分析进一步显示了良好的结合自由能（- 14.91 kJ/mol），反映了稳定和能量有利的相互作用。总之，这些结果表明，氯化小檗碱具有一致的PIM-1抑制和抗癌活性的计算和实验证据，支持其作为未来药物开发的有希望的支架的作用。

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引用次数: 0

Facile fabrication of poly(tricholorotriazine-tannic acid) nanosphere and its rapid removal feature towards lead ions 聚三氯三嗪-单宁酸纳米球的制备及其对铅离子的快速去除性能

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2026-03-15 Epub Date: 2026-01-22 DOI: 10.1016/j.molliq.2026.129308

Kun Zhao , Jianxue Li , Ke Meng , Lei Tan , Zhimin Chen , Jiafu Chen , Shaohua Liu , Jianwei Fu

The presence of Pb²⁺ in water systems poses potential dangers to the environment and public health, and developing efficient adsorbents is a feasible solution to the predicament. Herein, a cross-linked poly(tricholorotriazine-tannic acid) (TCA) nanosphere has been facilely prepared through one-step precipitation polymerization. The microstructure of TCA was well analyzed by TEM, SEM, FT-IR, XRD, TGA and N₂ sorption and its adsorption performance for aqueous Pb²⁺ was systematically evaluated. Results showed that TCA owned a hard spherical structure with size of about 250 nm and specific surface area of 22.3 m² g⁻¹. The adsorption capacity of TCA for Pb²⁺ in 50 mg L⁻¹ lead nitrate solution could be up to 136.3 mg g⁻¹ at pH = 5 and 298 K. The adsorption rate is extremely fast, completing 91% of the equilibrium adsorption capacity within one minute. After five cycles of adsorption-desorption, the TCA nanospheres still maintained a high adsorption capacity of 109 mg g⁻¹ for Pb²⁺. Adsorption kinetics and isotherm analysis suggested that the removal of Pb²⁺ by TCA followed the pseudo-second-order dynamics model and the Langmuir isotherm model. Thermodynamic parameters revealed that the Pb²⁺ removal process was spontaneous and endothermic in nature. The plausible removal mechanism could be attributed to coordination, chemical bonding and ion exchange between TCA and Pb²⁺.

Pb2+在水系统中的存在对环境和公众健康造成了潜在的危害，开发高效的吸附剂是解决这一困境的可行方法。本文采用一步沉淀聚合法制备了交联聚三氯三嗪-单宁酸（TCA）纳米球。采用TEM、SEM、FT-IR、XRD、TGA、N2吸附等方法分析了TCA的微观结构，并对其对Pb2+的吸附性能进行了系统评价。结果表明，TCA具有坚硬的球形结构，尺寸约为250 nm，比表面积为22.3 m2 g−1。在50mg L−1硝酸铅溶液中，当pH = 5，温度为298 K时，TCA对Pb2+的吸附量高达136.3 mg g−1。吸附速度极快，1分钟内完成91%的平衡吸附量。经过5次吸附-解吸循环后，TCA纳米球对Pb2+的吸附量仍保持在109 mg g−1。吸附动力学和等温线分析表明，TCA对Pb2+的去除符合拟二阶动力学模型和Langmuir等温线模型。热力学参数表明，Pb2+的去除过程是自发的、吸热的。TCA与Pb2+之间的配位、化学键和离子交换是去除Pb2+的主要机制。

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引用次数: 0

2,1,3-benzothiadiazole-based probe exhibits inverted fluorosolvatochromism and aggregation-induced emission 2,1,3-苯并噻唑基探针表现出倒置的氟溶剂变色和聚集诱导发射

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids

Pub Date : 2026-03-15 Epub Date: 2026-01-14 DOI: 10.1016/j.molliq.2026.129270

Samara de Quadros , Gleiston G. Dias , Daniel F. Pietezak , Robson S. Oliboni , Vanderlei G. Machado

Fluorosolvatochromic compounds are widely employed as probes for analyzing pure and mixed solvents, as their fluorescence emission wavelength and intensity vary with solvent environment. The 2,1,3-benzothiadiazole (BTD) nucleus is an attractive fluorophore for designing such probes, yet its fluorosolvatochromic behavior has not been systematically explored. Here, we report the synthesis and photophysical characterization of a novel BTD-based donor–π–acceptor probe (compound 1), featuring a triphenylamino (TPA) substituent and a terminal alkynyl group. Optical properties were examined in a broad set of pure organic solvents and alcohol–water mixtures. The probe displays reverse fluorosolvatochromism, with an initial bathochromic shift in less polar solvents followed by a hypsochromic shift as polarity increases. This reversal is influenced by the terminal alkynyl group, which interacts with oxygenated solvents through hydrogen bonding, modulating excited-state stabilization and the emission response. Theoretical calculations indicate that the visible band arises from π–π* electronic transitions. The probe is fluorescent in the solid state, shows negligible emission in ethanol, is insoluble in water, and exhibits strong fluorescence in ethanol/water mixtures. These features support the aggregation-induced emission (AIE), promoted by the TPA unit. These findings provide new insights into the interplay between solvent environment, molecular structure, and aggregation in BTD-based systems, highlighting their potential for sensing, imaging, and materials science applications.

氟溶剂致变色化合物由于其荧光发射波长和强度随溶剂环境的变化而变化，被广泛用作分析纯溶剂和混合溶剂的探针。2,1,3-苯并噻唑（BTD）核是设计此类探针的一个有吸引力的荧光团，但其氟溶剂变色行为尚未被系统地探索。本文报道了一种以三苯胺（TPA）取代基和末端炔基为特征的新型btd基给体- π -受体探针（化合物1）的合成和光物理表征。在广泛的纯有机溶剂和酒精-水混合物中研究了光学性质。探针显示反荧光溶剂变色，在极性较低的溶剂中具有初始的深变色，随后随着极性的增加而发生次变色。这种逆转受到末端炔基的影响，炔基通过氢键与含氧溶剂相互作用，调节激发态稳定和发射响应。理论计算表明，可见光波段是由π -π *电子跃迁产生的。该探针在固体状态下具有荧光，在乙醇中可以忽略不计，不溶于水，在乙醇/水混合物中具有强荧光。这些特性支持由TPA单元促进的聚集诱导发射（AIE）。这些发现为溶剂环境、分子结构和btd系统聚集之间的相互作用提供了新的见解，突出了它们在传感、成像和材料科学应用方面的潜力。

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引用次数: 0