Journal of Molecular Structure最新文献_第4页

Carboxylate-modulated structural variations and slow magnetic relaxation in mononuclear dysprosium(III) complexes 单核镝（III）配合物中羧酸调制的结构变化和慢磁弛豫

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2025-12-24 DOI: 10.1016/j.molstruc.2025.145148

Hengyu Yang , Botan Li , Wandi Shi , Haibo Zhang , Yiyi Zhang , Lin Sun , Yiquan Zhang , Mingxue Li

We synthesized two Dy^III-based mononuclear complexes, [Dy(L)₂(C₆H₅COO)(H₂O)]·2H₂O (1·2H₂O) and [Dy(L)₂(CH₃COO)(H₂O)]·3H₂O (2·3H₂O), using a Schiff base ligand (HL=N'-(2-hydroxybenzoyl)pyrazine-2-carbohydrazonamide) that feature multiple chelating sites. Single-crystal X-ray diffraction analysis indicates that complexes 1·2H₂O and 2·3H₂O both crystallize in the

P \bar{1}

space group. The Dy^III ions in the two complexes both possess an N₄O₅ coordination sphere. In contrast to the spherical tricapped trigonal prism geometry of the Dy^III ion in 1·2H₂O, the Dy^III center in 2·3H₂O adopts a muffin-shaped configuration. This primarily can be attributed to the use of different carboxylates in synthesis. Magnetic studies demonstrate that intermolecular antiferromagnetic interactions are present in both 1·2H₂O and 2·3H₂O. Pronounced quantum tunneling of magnetization (QTM) suppresses slow magnetic relaxation behavior in 1·2H₂O, while 2·3H₂O displays field-induced single-molecule magnet (SMM) characteristics. Theoretical calculations suggest 2·3H₂O exhibits strong axial magnetic anisotropy, in agreement with experimental results. Magneto-structural correlations analysis reveals that replacing the benzoate ion with acetate ion alters the coordination geometry of the Dy^III ion, which in turn leads to shorter axial Dy-O bonds and a corresponding enhancement in SMM performance. This work presents a viable strategy to modulate the performance of SMM. This strategy hinges on the rational selection of metal salts (electron-withdrawing or electron-donating anions) to induce a transformation in the coordination geometry of the Dy^III ion, ultimately tuning the magnetic properties.

我们利用希夫碱配体（HL=N′-（2-羟基苯甲酰）吡嗪-2-碳腙酰胺）合成了两个具有多个螯合位点的dyii基单核配合物[Dy(L)2(C6H5COO)(H2O)]·2H2O（1·2H2O）和[Dy(L)2(CH3COO)(H2O)]·3H2O（2·3H2O）。单晶x射线衍射分析表明，配合物1·2H2O和2·3H2O均在P1¯空间群中结晶。两种配合物中的DyIII离子均具有N4O5配位球。与1·2H2O中DyIII离子的球面三棱形几何结构不同，2·3H2O中的DyIII中心呈松饼状结构。这主要是由于在合成中使用了不同的羧酸盐。磁性研究表明，分子间的反铁磁相互作用在1·2H2O和2·3H2O中都存在。1·2H2O中明显的磁化量子隧穿（QTM）抑制了慢磁弛豫行为，而2·3H2O中表现出场致单分子磁体（SMM）特征。理论计算表明，2·3H2O具有较强的轴向磁各向异性，与实验结果一致。磁结构相关分析表明，用醋酸盐离子取代苯甲酸盐离子改变了DyIII离子的配位几何形状，从而缩短了轴向Dy-O键，从而提高了SMM性能。这项工作提出了一种可行的策略来调节SMM的性能。这一策略取决于合理选择金属盐（吸电子或供电子阴离子）来诱导DyIII离子的配位几何转变，最终调整磁性能。

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引用次数: 0

Synthesis, characterization, structural elucidation, and biological evaluation of Zn(II) carboxylate complexes: Supramolecular drug delivery mechanism, and ADMET study 锌（II）羧酸配合物的合成、表征、结构解析和生物学评价：超分子给药机制和ADMET研究

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2025-12-24 DOI: 10.1016/j.molstruc.2025.145137

Amir Karim , Sheeba Shabnam , Najeeb Ullah , Muhammad Iqbal , Rahime Eshaghi Malekshah , Jebiti Haribabu , Sodio C.N. Hsu

In this study, a series of new Zn(II) carboxylate complexes were successfully synthesized and characterized using various spectroscopic techniques and single-crystal X-ray diffraction (SC-XRD) analysis. The UV–Vis spectra revealed both ligand-to-metal charge transfer (LMCT) bands and characteristic π–π* transitions of the aromatic moieties, while FTIR data confirmed the structural integrity and coordination behavior of the ligands upon complexation. The ¹H/¹³C NMR spectra further supported coordination, exhibiting notable chemical shift variations relative to the free ligands. The crystal structure of complex C2, determined by SC-XRD, validated the proposed coordination geometry around the Zn(II) center. All the synthesized complexes showed moderate to significant antimicrobial activity, with C2 exhibiting the highest antifungal potential, likely due to its cyclohexyl moiety. Antibacterial tests revealed greater efficacy against Gram-positive than Gram-negative bacteria. Molecular docking showed that C2 had the strongest binding affinity toward bacterial β-lactamases (PDB: 4HBT, 1MWU), correlating with its higher lipophilicity from ADMET predictions. DFT-D and Monte Carlo simulations provided insights into electronic structure and drug-loading interactions with 2HPβCD. Together, experimental, biological, and computational results highlight the structural features, coordination behavior, and pharmaceutical potential of the synthesized Zn(II) carboxylate complexes.

本研究成功合成了一系列新的锌（II）羧酸配合物，并利用各种光谱技术和单晶x射线衍射（SC-XRD）分析对其进行了表征。紫外可见光谱显示了配体到金属的电荷转移（LMCT）带和芳香基团的特征π -π *跃迁，FTIR数据证实了配体的结构完整性和配位行为。1H/13C核磁共振谱进一步支持配位，显示出相对于自由配体的显著化学位移变化。用SC-XRD测定了配合物C2的晶体结构，证实了Zn（II）中心周围的配位几何结构。所有合成的配合物都显示出中等到显著的抗菌活性，其中C2表现出最高的抗菌潜力，可能是由于其环己基部分。抗菌试验显示对革兰氏阳性菌比革兰氏阴性菌更有效。分子对接表明，C2对细菌β-内酰胺酶（PDB: 4HBT, 1MWU）具有最强的结合亲和力，这与ADMET预测的较高的亲脂性有关。DFT-D和蒙特卡罗模拟提供了2HPβCD的电子结构和药物负载相互作用的见解。总之，实验、生物学和计算结果突出了合成的锌（II）羧酸配合物的结构特征、配位行为和药物潜力。

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引用次数: 0

Unveiling broad-spectrum antimicrobial potential of novel pyrazole-embedded enaminonitrile derivatives: Insights from synthesis, SAR, and molecular docking studies 揭示新型吡唑包埋的氨基腈衍生物的广谱抗菌潜力：来自合成，SAR和分子对接研究的见解

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2025-12-24 DOI: 10.1016/j.molstruc.2025.145152

Hayfa H. Almutairi , Jihan Qurban , Nadiyah M. Alshammari , Hossa F. Alshareef , Mohammed S. Alshammari , Maryam M. Alnoman , Hanadi A. Katouah , Nashwa M. El-Metwaly

A new series of pyrazole-based enaminonitrile derivatives was synthesized through cyclization of a crucial intermediate and characterized by IR, NMR, elemental analysis, and MS. The antibacterial activity of the compounds against Candida albicans, Escherichia coli, and Staphylococcus aureus was assessed. Among these, compounds 14, 15, and particularly 19 displayed significant broad-spectrum action, obtaining MIC values as low as 3.125 µg/mL comparable to or exceeding chloramphenicol and cycloheximide. Analysis of the structure–activity relationship showed that fused heterocyclic systems and electron-withdrawing substituents greatly increased potency. Molecular docking (PDB: 3FV5) supported these findings, showing strong and stable binding, with compound 19 displaying the highest affinity (–7.74 kcal/mol). These results suggest compound 19 as a viable lead for further antibacterial modification and development. Moreover, in silico ADME profiling utilizing the SwissADME tool on the synthesized compounds to find their pharmacokinetic profile. While some of the synthesized derivatives showed decreased permeability or increased molecular complexity that resulted in decreased solubility, the majority of them demonstrated strong GI absorption and water solubility. CYP inhibition was variable, with exact substances indicating potential inhibitory efficacy against CYP2C9, CYP2C19, and CYP3A4.

通过一个重要中间体的环化合成了一系列新的吡唑基氨基腈衍生物，并通过IR、NMR、元素分析和ms对其进行了表征。其中化合物14、15、特别是19表现出显著的广谱作用，MIC值低至3.125µg/mL，与氯霉素和环己亚胺相当或超过。构效关系分析表明，融合杂环体系和吸电子取代基大大提高了化合物的效价。分子对接（PDB: 3FV5）证实了这一发现，化合物19的亲和力最高（-7.74 kcal/mol）。这些结果表明化合物19是进一步抗菌修饰和开发的可行先导物。此外，利用SwissADME工具对合成化合物进行ADME分析，以找到它们的药代动力学特征。虽然一些合成的衍生物表现出渗透性降低或分子复杂性增加导致溶解度降低，但大多数衍生物表现出很强的GI吸收和水溶性。CYP的抑制作用是可变的，有确切的物质表明对CYP2C9、CYP2C19和CYP3A4有潜在的抑制作用。

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引用次数: 0

Microwave-assisted novel synthesis and structural confirmation of Pyrido[1,2-a]pyrazin-5-ium (N-Oxide) Salts 微波辅助吡啶多[1,2-a]吡嗪-5-ium （n-氧化物）盐的新合成及结构证实

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2025-12-24 DOI: 10.1016/j.molstruc.2025.145150

Yousef M. Hijji , Rajeesha Rajan , Haw-Li Su , Amjad Shraim , Said Mansour , Anas Abutaha , Raymond Butcher , Fasil Abebe

Pyrido[1,2-a]pyrazin-5-ium (2-oxide) salts are an interesting class of compounds that contain unique moieties: a bridgehead quaternary nitrogen, an amino group, and an N-oxide functionality. These compounds were efficiently constructed in a one-pot reaction within minutes, yielding good yields. The microwave-assisted reaction of 2-pyridinecarboxaldehyde oxime with bromoacetonitrile yields these unique structures. The compounds were characterized, and their structures confirmed, by single-crystal XRD, NMR, FTIR, and other spectroscopic techniques. ¹H-¹⁵N HMQC for directly bonded ¹H to N clearly shows the presence of an amino group in both compounds. These compounds crystallize in the triclinic p-1 and Cc space groups, revealing the presence of several intermolecular interactions.

Pyrido[1,2-a]pyrazin-5-ium （2-oxide）盐是一类有趣的化合物，含有独特的基团：桥头堡季氮、氨基和n-氧化物官能团。这些化合物在几分钟内在一锅反应中有效地构建，产率很高。微波辅助下，2-吡啶甲醛肟与溴乙腈反应生成了这些独特的结构。通过单晶XRD， NMR， FTIR和其他光谱技术对化合物进行了表征，并证实了它们的结构。1H与N直接键合的1H- 15n HMQC清楚地表明两个化合物中都存在一个氨基。这些化合物在三斜的p-1和Cc空间群中结晶，揭示了一些分子间相互作用的存在。

引用次数: 0

Comparing the inhibitory effects of phosphaneyl derivatives based on pyrrole and imidazole on C-steel in an acidic setting: Theoretical, surface morphological and experimental methodologies 比较吡咯和咪唑基磷酰衍生物在酸性环境下对c -钢的抑制效果：理论、表面形貌和实验方法

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2025-12-24 DOI: 10.1016/j.molstruc.2025.145155

Hissah Saedoon Albaqawi , Fekhra Hedhili , Shereen M. Al-Shomar , Nwuyer A. Al-Shammari , Mohamed Gandouzi , Ahmed A. Farag , Khaled M. Abdel-Azim , N.S. Abdelshafi

The effectiveness of phosphaneyl Schiff bases based on structures in preventing corrosion on carbon steel (CSt) in a 1 M HCl solution is investigated and compared in this work using gravimetrical, electrochemical, surface inspection, and computational techniques. The motive of this study is to compare imidazole and pyrrole to assess the conjugation effect of imidazole's extra nitrogen atom, in addition to the diphenylphosphaneyl and imine groups, on corrosion prevention efficiency. Both inhibitors have imidazole and pyrrole better inhibitory efficiency than the majority of equivalent inhibitor types reported in the literature. Imidazol-Sc and Pyrrol-Sc showed the best inhibitory efficiency, 95.0% and 93.4%, at 303 K with a dosage of 0.001 M. They also maintained excellent results, 83.5% and 71.3%, at 333 K. Imidazole inhibitor is more efficient than pyrrole because one of its two N atoms has an accessible lone pair that is not involved in aromaticity, which allows for σ-donation and protonation. While the lone pair of N atom in pyrrole is part of the aromatic π-system, which limits its interaction with the CSt surface. Imidazol-Sc and Pyrrol-Sc both showed mixed inhibitory action when adsorbed over the CSt surface via a blend adsorption mechanism that adheres to the Langmuir isotherm. Investigations employing AFM, contact angle, and XRD measurements have indicated that the inhibitors have generated a protective layer that is responsible for the corrosion prevention observed at the CSt substrate. Computational molecular modelling (DFT, Fukui, and molecular dynamic simulation) studies supported the experimental results. Therefore, industrial acidic environments may find application for the inhibitors under study.

本文采用重量测量、电化学、表面检测和计算技术，研究并比较了磷酰席夫碱在1 M盐酸溶液中对碳钢（CSt）的防腐效果。本研究的动机是比较咪唑和吡咯，以评估咪唑除二苯基磷酰基和亚胺基外，多出的氮原子对防腐效率的偶联作用。这两种抑制剂都具有咪唑和吡咯比文献中报道的大多数等效抑制剂更好的抑制效率。Imidazol-Sc和pyroll - sc在303 K、0.001 m时的抑菌效果最好，分别为95.0%和93.4%，在333 K时也保持了良好的抑菌效果，分别为83.5%和71.3%。咪唑抑制剂比吡咯更有效，因为它的两个N原子中的一个有一个可接近的孤对，而孤对不参与芳香性，这允许σ给能和质子化。而吡咯中的孤对N原子是芳π体系的一部分，这限制了它与CSt表面的相互作用。咪唑- sc和吡咯- sc通过符合Langmuir等温线的混合吸附机制吸附在CSt表面时均表现出混合抑制作用。采用原子力显微镜、接触角和x射线衍射测量的研究表明，抑制剂在CSt基体上形成了一层保护层，负责防止腐蚀。计算分子模型（DFT， Fukui和分子动力学模拟）研究支持实验结果。因此，研究中的抑制剂在工业酸性环境中可能会有应用。

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引用次数: 0

Abnormal size reduction and enhancement in upconversion emission of tetragonal LaVO4:Yb3+/Er3+ nanocrystals by surface modification with ZrOCl2 ZrOCl2表面改性对四角形LaVO4:Yb3+/Er3+纳米晶体上转换发射的异常减小和增强

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2025-12-24 DOI: 10.1016/j.molstruc.2025.145154

Xiangcheng Wang , Xiong Wang , Lingwei Zeng , Mengjia Chen , Hu Zhou , Jianxian Zeng , Guoqing Liu , Tao Pang , Zhouxi Li , Shijie Zhang , Jianfeng Tang , Daqin Chen

It is well-known that upconversion nanocrystals usually have a low efficiency. Over the past years, much attention has been paid to fluorides, and less is focused on lanthanide orthovanadates. Herein, we intend to adopt the impurity doping strategy to enhance upconversion luminescence (UCL). In this work, the size and UCL (Er³⁺:⁴S_3/2, ⁴F_9/2→⁴I_15/2 transitions) property of tetragonal host LaVO₄:Yb³⁺/Er³⁺ are regulated by varying the ZrOCl₂ concentration. It is found that the sizes decrease along with the ZrOCl₂ addition. Interestingly, this result is quite different from previous investigation, where the introduction of higher-valance cations facilitates crystal growth and lower-valance cations reduces the grain size. By optimizing the ZrOCl₂ content to 7.5 mol%, the UCL intensities (green and red emissions) are enhanced considerably. Furthermore, the mechanisms for size reduction and UCL augment are analyzed detailedly. It provides a promising way for UCL improvement and enriches the approach to growth mechanism in solution particularly induced by surface modification.

众所周知，上转换纳米晶体的效率通常很低。在过去的几年里，人们对氟化物给予了很大的关注，而对镧系正钒酸盐的关注却很少。在此，我们打算采用杂质掺杂策略来增强上转换发光（UCL）。在本研究中，通过改变ZrOCl2的浓度，可以调节LaVO4:Yb3+/Er3+的大小和UCL （Er3+:4S3/2, 4F9/2→4I15/2跃迁）性质。随着ZrOCl2的加入，晶粒尺寸逐渐减小。有趣的是，这一结果与之前的研究结果大不相同，之前的研究发现，高价阳离子的引入促进了晶体的生长，而低价阳离子的引入减小了晶粒尺寸。通过优化ZrOCl2含量为7.5 mol%， UCL强度（绿色和红色排放）显著增强。此外，还详细分析了尺寸减小和UCL增大的机理。这为UCL的改进提供了一条有希望的途径，并丰富了研究溶液中特别是表面改性诱导生长机理的方法。

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引用次数: 0

Impact of coordinated anions on field-induced slow magnetic relaxation in mononuclear Cobalt(II) compounds 配位阴离子对单核钴（II）化合物场致慢磁弛豫的影响

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2025-12-23 DOI: 10.1016/j.molstruc.2025.145142

Zheng Tang , Qiman Che , Yingying Zhang , Junfei Fan , Shuang Jin , Xiao-Peng Sun , Pengtao Ma , Zi-Shuo Yao , Jingping Wang , Jingyang Niu , Jun Tao

Contrasting coordinated ligands in isostructural compounds provide a powerful strategy for tuning slow magnetic relaxation. Herein, we report two new mononuclear Co(II) compounds, [Co(H₂L)Cl₂]·0.5H₂O (1, H₂L = 6, 6’-bis(benzimidazole-2-yl)-2, 2’-bipyridine) and [Co(H₂L)(NCS)₂] (2), featuring the identical equatorial ligand but differing in axial ligands. Molecular structural analysis revealed the Co(II) center in 1 adopted a hexacoordinate geometry, coordinated by four N atoms from H₂L ligand in the equatorial plane and two Cl⁻ anions in the axial positions. In contrast, the axial sites in compound 2 were occupied by two NCS⁻ anions. The varying axial anionic ligands gave rise to an elongated {CoN₄Cl₂} octahedron in 1 and a compressed {CoN₆} octahedron in 2. Alternating-current magnetic susceptibility measurements confirmed that both compounds were field-induced single-ion magnets (SIMs), exhibiting different effective energy barriers. Fitting with the temperature dependence of the relaxation time expression indicated their relaxation dynamics were primarily governed by Orbach, Direct and Raman processes. This work underscores the crucial role of coordinated ligands in design of Co(II)-based SIMs.

在同构化合物中对比配位体为调节慢磁弛豫提供了一种强有力的策略。本文报道了两个新的单核Co（II）化合物，[Co(H2L)Cl2]·0.5H2O （1,h2l = 6,6′-双（苯并咪唑-2-基）- 2,2′-联吡啶）和[Co(H2L)(NCS)2](2)，它们具有相同的平伏配体，但轴向配体不同。分子结构分析表明，1中的Co（II）中心呈六坐标结构，由H2L配体中的4个N原子在赤道面配位，两个Cl−阴离子在轴向位置配位。相反，化合物2的轴位被两个NCS -阴离子占据。不同的轴向阴离子配体在1中产生拉长的{CoN4Cl2}八面体，在2中产生压缩的{CoN6}八面体。交流磁化率测量证实，这两种化合物都是场致单离子磁体（SIMs），表现出不同的有效能垒。对弛豫时间表达式的温度依赖性拟合表明，它们的弛豫动力学主要受Orbach、Direct和Raman过程控制。这项工作强调了配体在Co（II）基SIMs设计中的关键作用。

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引用次数: 0

Exfoliated Mn-MOF nanowires with enhanced charge separation for high-performance solar-driven oxygen evolution reaction 剥离Mn-MOF纳米线与增强电荷分离的高性能太阳能驱动析氧反应

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2025-12-23 DOI: 10.1016/j.molstruc.2025.145149

Bo Liu, Meng-Qi Tuo, Yu-Jie Xie, Song Zhang, Rui-Zi Xue, Er-Nu Liu, Liu-Xin Zhang, Jiu-Fu Lu

Addressing the global energy crisis and environmental challenges requires the development of efficient, sustainable electrocatalysts for the oxygen evolution reaction (OER). Herein, we report the exfoliation of a one-dimensional Mn(II)-based metal–organic framework, SNUT-39-SC, into nanowires (SNUT-39-NW) via a rapid thermal quenching and ultrasonication strategy. The nanowire structure significantly enhances the electrochemical surface area, promotes charge carrier separation, and improves mass transport, resulting in superior electrocatalytic OER performance. Under simulated solar irradiation, SNUT-39-NW achieves a current density of 10 mA·cm⁻² at an overpotential of only 124 mV in 0.5 M Na₂SO₄, outperforming the bulk crystal (161 mV) and demonstrating excellent stability over 24 h. Mechanistic studies reveal reduced charge transfer resistance and suppressed carrier recombination, highlighting the advantages of nanostructural engineering in optimizing MOF-based electrocatalysts. This work provides valuable insights for the design of high-performance, non-noble metal catalysts for solar-driven water splitting.

解决全球能源危机和环境挑战需要开发高效、可持续的析氧反应电催化剂。在此，我们报道了通过快速热淬火和超声波策略将一维Mn（II）基金属有机骨架SNUT-39-SC剥离成纳米线（SNUT-39-NW）。纳米线结构显著提高了电化学表面积，促进了载流子分离，改善了质量输运，从而获得了优异的电催化OER性能。在模拟太阳辐照下，snut39 - nw在0.5 M Na₂SO₄中过电位仅为124 mV时电流密度达到10 mA·cm⁻²，优于体晶（161 mV），并在24 h内表现出优异的稳定性。机理研究表明，该晶体降低了电荷转移阻力，抑制了载流子重组，突出了纳米结构工程在优化mof基电催化剂方面的优势。这项工作为设计用于太阳能驱动水分解的高性能非贵金属催化剂提供了有价值的见解。

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引用次数: 0

New antibacterial polyketides from the plant endophytic f ungi Talaromyces pinophilus AF-02 and their molecular modelling studies 植物内生真菌嗜松Talaromyces pinophilus AF-02的新型抗菌聚酮及其分子模拟研究

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2025-12-23 DOI: 10.1016/j.molstruc.2025.145144

Ge-Ge Yang , Xing-Wei Luo , Qiao-Xia Zhong , Han-Mou Yu , Desire Girimpuhwe , Jia Wu , Jian-Jin Guo , Yun-Hao Ma , Hao Ren , Dan Xu , Jia-Ling Li , Peng Chen , Quan-Xiang Wu

To exhumate unusual antibacterial natural products, four new polyketides, including a novel spirocyclic polyketide featuring a 1-oxaspiro[4.4]non-6-ene core with a long chain, talaromylactone A (1), a δ-lactone polyketide, talaromylactone B (2), two aromatic polyketides sharing a diphenyl ether framework (3 and 4), and nine known diphenyl ether derivatives (5 − 13) were isolated from the culture of endophytic fungi Talaromyces pinophilus AF-02 of Chinese Allium fistulosum via LC-MS/MS-based GNPS molecular networking analysis. The structures were thoroughly elucidated by comprehensive spectroscopic analysis, X-ray diffraction analysis and quantum mechanical calculations. All the compounds were evaluated for their antibacterial activities. 1, 3, 4, 6, 10, and 13 inhibited the growth of gram-negative bacteria (Klebsiella pneumoniae, Escherichia coli , Salmonella typhimurium , Salmonella heidelberg, and Proteus mirabilis) and gram-positive bacteria (Staphylococcus aureus GDQ6P012P, Bacillus subtilis, and Bacillus thuringiensis), with MIC values ranging from 6.25 to 25 μg/mL. Specifically, the activities of 3 and 4 were significant against K. pneumoniae and S. heidelberg, with MICs of 6.25 and 12.5 μg/mL, respectively, similar to those of the positive controls chloramphenicol and levofloxacin, respectively. Molecular docking, dynamics simulations, and the DNA gyrase inhibitor assay confirmed the DNA gyrase subunit A as a potential target for diphenyl ether polyketides, with 3 showing the strongest binding energy of −7.7 kcal/mol and a potent inhibition effect of DNA gyrase, with an IC₅₀ of 1.55 μM, comparable to levofloxacin, with a binding energy of −7.8 kcal/mol and an IC₅₀ of 0.56 μM, respectively, indicating its promise as a lead compound for the development of antibiotics.

为了发掘不同寻常的抗菌天然产物，研究了四种新的聚酮，包括一种具有长链1- oxspiro[4.4]非6-烯核的新型螺旋环聚酮、一种δ-内酯聚酮、一种talaromylactone a(1)、一种δ-内酯聚酮、talaromylactone B(2)、两种共享二苯基醚框架的芳香聚酮（3和4）。通过LC-MS/MS-based GNPS分子网络分析，从中国Allium fistulosum内生真菌Talaromyces pinophilus AF-02培养物中分离出9个已知的二苯醚衍生物（5 ~ 13个）。通过综合光谱分析、x射线衍射分析和量子力学计算，对其结构进行了详细的分析。对所有化合物的抗菌活性进行了评价。1、3、4、6、10、13对革兰氏阴性菌（肺炎克雷伯菌、大肠杆菌、鼠伤寒沙门菌、海德堡沙门菌、奇异变形杆菌）和革兰氏阳性菌（金黄色葡萄球菌GDQ6P012P、枯草芽孢杆菌、苏云金芽孢杆菌）的生长均有抑制作用，MIC值为6.25 ~ 25 μg/mL。其中，3和4对肺炎克雷伯菌和海德堡链球菌的抑菌活性显著，mic值分别为6.25和12.5 μg/mL，与阳性对照氯霉素和左氧氟沙星的mic值相近。分子对接，动力学模拟和DNA回旋酶抑制剂测定证实了DNA回旋酶亚基A是二苯基醚聚酮的潜在靶标，其中3显示出最强的结合能- 7.7 kcal/mol和DNA回旋酶的有效抑制作用，IC₅0为1.55 μM，与左氧氟沙星相当，结合能为- 7.8 kcal/mol和IC₅0为0.56 μM，分别表明其有望作为开发抗生素的先导化合物。

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引用次数: 0

Influence and mechanism of inorganic ions on Cr(VI) adsorption from wastewater by zinc-based metal-organic framework 无机离子对锌基金属-有机骨架吸附废水中Cr（VI）的影响及机理

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2025-12-23 DOI: 10.1016/j.molstruc.2025.145141

Shixiong Li , Chuqing Zhang , Xianzong Wu , Pei Luo

The application of metal-organic frameworks (MOFs) for adsorbing pollutants from real wastewater requires consideration of the influence of coexisting inorganic ions. In this study, a zinc-based MOF, {[(HDMA)₂][Zn₂(DMA)₂(L)₃]·H₂O·DMF}_n (where DMA = dimethylamine) (Zn-MOF) was synthesized by reacting terephthalic acid (H₂L) with Zn(NO₃)₂·6H₂O in N,N-dimethylformamide (DMF). This framework features hexagonal pores with dimensions of approximately 18.36 × 18.36 Å. A nano-adsorbent version, Zn-MOF-N, with an average particle diameter of 100 nm, was also prepared. Zn-MOF-N exhibited a high maximum equilibrium adsorption capacity for Cr(VI) of 257.9 mg/g at 20°C and pH 6.50 (its isoelectric point), outperforming most reported MOF-based adsorbents. However, the presence of coexisting metal cations (Na⁺, K⁺, Ca²⁺, Mg²⁺) and inorganic anions (Cl^-, NO₃^-, SO₄^2-, PO₄^3-) was found to inhibit Cr(VI) adsorption. The metal cations increase the ionic strength of the solution, compressing the electrical double layer and thereby weakening the electrostatic attraction between Zn-MOF-N and Cr(VI). In contrast, inorganic anions compete with Cr(VI) for adsorption sites on the surface of Zn-MOF-N, leading to a significant reduction in uptake. The inhibitory effect of anions followed the order: PO₄^3- > SO₄^2- > NO₃^- > Cl^-. This study clarifies how coexisting inorganic ions affect the adsorption performance of MOFs, supporting their potential application in real wastewater treatment.

应用金属-有机骨架（mof）吸附实际废水中的污染物需要考虑共存无机离子的影响。在n， n-二甲基甲酰胺（DMF）中，对苯二甲酸（H2L）与Zn(NO3)2·6H2O反应，合成了锌基MOF {[(HDMA)2][Zn2(DMA)2(L)3]·H2O·DMF}n （DMA =二甲胺）（Zn-MOF）。该框架具有六边形孔隙，尺寸约为18.36 × 18.36 Å。制备了平均粒径为100 nm的纳米吸附Zn-MOF-N。Zn-MOF-N在20℃、pH值6.50（等电点）条件下对Cr（VI）的最大平衡吸附量为257.9 mg/g，优于大多数mof基吸附剂。然而，共存的金属阳离子（Na+, K+, Ca2+, Mg2+）和无机阴离子（Cl-, NO3-, SO42-, PO43-）的存在抑制了Cr（VI）的吸附。金属阳离子增加了溶液的离子强度，压缩了双电层，从而减弱了Zn-MOF-N和Cr（VI）之间的静电吸引力。相反，无机阴离子与Cr（VI）竞争Zn-MOF-N表面的吸附位点，导致吸收显著减少。阴离子的抑制作用顺序为：PO43- >； SO42- > NO3- > Cl-。该研究阐明了共存的无机离子如何影响mof的吸附性能，支持其在实际废水处理中的潜在应用。

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