Journal of Molecular Structure最新文献_第10页

2-Methyl-4-nitrophenoxy based thiosemicarbazide, 1,2,4-triazole and 1,3,4-thiadiazole compounds as multitarget enzyme inhibitors: Synthesis, biological and computational studies 基于2-甲基-4-硝基苯氧基硫代氨基脲、1,2,4-三唑和1,3,4-噻二唑的多靶点酶抑制剂：合成、生物学和计算研究

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2026-01-29 DOI: 10.1016/j.molstruc.2026.145513

Tenzile Alagoz , Sunay Yilmaz , Eda Mehtap Ozden , Mehmet Abdullah Alagoz , Mustafa Zengin , Hayriye Genc Bilgicli , Ilhami Gulcin

Novel thiosemicarbazide (3a-d), 1,2,4-triazole (4a-d), and 1,3,4-thiadiazole (5a-d) derivatives were obtained in high total yields of 57–66%, 40–51%, and 40–53%, respectively, and they were evaluated for inhibitor activity against acetylcholinesterase, and human carbonic anhydrase isoforms I and II (hCAs I and II). They were demonstrated to have effective inhibition profiles with K_i values of 20.08±4.80–152.41±66.19 nM against hCA I, 64.57±20.74–356.58±176.92 nM against hCA II and 4.55±1.24–61.30±28.60 nM against AChE. On the other hand, acetazolamide showed K_i value of 30.69±9.31 nM against hCA I, and 40.08±6.38 nM against hCA II isoform. Additionally, Tacrine inhibited AChE and demonstrated K_i values of 3.51±1.56 nM. The affinities of the compounds towards hCA I, hCA II and AChE were evaluated by in silico studies. In molecular docking studies, 3c (-7.453 kcal/mol), 3d (-7.380), 5b (-7.372 kcal/mol) showed high affinity towards AChE. In MD simulation studies with the most active compound 3c, it was observed that the compound remained stable in the active site of AChE for 150 ns (Average RMSD < 3.0 Å). The ADMET properties of the synthesized compounds were evaluated in silico. All compounds exhibited pharmacological properties and did not display adverse toxic effects. The inhibition of CA and AChE is a powerful pharmacological tool with diverse clinical applications. By targeting different CA and AChE, inhibitors can treat eye diseases, neurological disorders, metabolic conditions, Alzheimer’s disease and even cancer, highlighting their broad therapeutic potential. MD simulations of the most active compound, 3c, confirmed its stability in the AChE active site for 150 ns (average RMSD < 3.0 Å). Furthermore, in silico ADMET analysis showed that all compounds had favorable pharmacokinetic profiles without significant toxic effects. These results demonstrate that novel 1,3,4-thiadiazole derivatives have considerable potential as selective and potent multitarget enzyme inhibitors and are promising candidates for further pharmaceutical development.

新的硫代氨基脲（3a-d）、1,2,4-三唑（4a-d）和1,3,4-噻二唑（5a-d）衍生物的总产率分别为57-66%、40-51%和40-53%，并对它们对乙酰胆碱酯酶和人类碳酸酐酶亚型I和II （hCAs I和II）的抑制活性进行了评估。对hCA I的Ki值为20.08±4.80 ~ 152.41±66.19 nM，对hCA II的Ki值为64.57±20.74 ~ 356.58±176.92 nM，对AChE的Ki值为4.55±1.24 ~ 61.30±28.60 nM。另一方面，乙酰唑胺对hCA I型的Ki值为30.69±9.31 nM，对hCA II型的Ki值为40.08±6.38 nM。此外，他克林抑制AChE， Ki值为3.51±1.56 nM。化合物对hCA I， hCA II和AChE的亲和力通过硅研究进行了评估。在分子对接研究中，3c （-7.453 kcal/mol）、3d（-7.380）、5b （-7.372 kcal/mol）对AChE表现出高亲和力。在用活性最高的化合物3c进行的MD模拟研究中，观察到该化合物在AChE的活性位点稳定了150 ns（平均RMSD <； 3.0 Å）。对合成的化合物进行了ADMET性能评价。所有化合物均表现出药理学性质，未表现出不良毒性作用。抑制CA和AChE是一种强大的药理学工具，具有多种临床应用。通过靶向不同的CA和AChE，抑制剂可以治疗眼病、神经系统疾病、代谢疾病、阿尔茨海默病甚至癌症，突出了其广阔的治疗潜力。最活跃的化合物3c的MD模拟证实了其在AChE活性位点的稳定性为150 ns（平均RMSD <； 3.0 Å）。此外，计算机ADMET分析表明，所有化合物都具有良好的药代动力学特征，没有明显的毒性作用。这些结果表明，新型1,3,4-噻二唑衍生物作为选择性和有效的多靶点酶抑制剂具有相当大的潜力，是进一步药物开发的有希望的候选者。

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引用次数: 0

Functional group orientation-dependent conformational polymorphism in 5-fluorocytosine–L-malic acid cocrystals 5-氟胞嘧啶- l -苹果酸共晶中官能团取向依赖的构象多态性

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2026-01-28 DOI: 10.1016/j.molstruc.2026.145506

Meiling Nie , Ting Jiao , Lin Wang , Chiyi Wang , Jiahan Jin , Jialu Hu , Yang Li , Hailu Zhang

The study of pharmaceutical cocrystal polymorphism is attracting increasing interest, as variations in intermolecular interactions and packing arrangements between an active pharmaceutical ingredient (API) and the same cocrystal former (CCF) directly impact the extent to which cocrystals can tailor the API’s properties. However, the number of reported cases of cocrystal polymorphism remains relatively limited. Herein, we propose that orientational variability of hydrogen bond donors or acceptors on either the API or the CCF may drive the formation of cocrystal polymorphs. To substantiate this hypothesis, 5-fluorocytosine (5-FC) and L-malic acid (L-MAL) were selected as the model cocrystallization system, and two distinct 2:1 polymorphs (form Ⅰ and form Ⅱ) were ultimately identified. Crystal structural analysis revealed that the two cocrystals share consistent supramolecular interactions; however, the divergent orientations of carbonyl and hydroxyl groups in L-MAL induce distinguishable hydrogen bonding configurations and molecular stacking patterns, which strongly validates the proposed origin of cocrystal polymorphism. Lattice energy calculations, polymorphic transformation studies, and melting point data collectively confirmed that these two polymorphs exhibit a monotropic thermodynamic relationship, with the high-Z’ form Ⅱ (Z’ = 2) being the thermodynamically stable crystalline phase. Under higher relative humidity condition (90 % RH), an obvious phase transformation of form Ⅰ was observed within one week, whereas form Ⅱ maintains its phase stability for at least four weeks. Such performance difference between these two cocrystals further underscores the practical significance of cocrystal polymorph screening.

药物共晶多态性的研究引起了越来越多的兴趣，因为活性药物成分（API）与相同的共晶前体（CCF）之间的分子间相互作用和包装排列的变化直接影响了共晶对原料药性能的调节程度。然而，报道的共晶多态性病例数量仍然相对有限。在此，我们提出API或CCF上氢键供体或受体的取向变化可能驱动共晶多晶的形成。为了证实这一假设，我们选择5-氟胞嘧啶（5-FC）和l -苹果酸（L-MAL）作为模型共结晶体系，最终确定了两种不同的2:1多态性（形式Ⅰ和形式Ⅱ）。晶体结构分析表明，两种共晶具有一致的超分子相互作用；然而，L-MAL中羰基和羟基的不同取向诱导了不同的氢键构型和分子堆叠模式，这有力地验证了所提出的共晶多态性的起源。晶格能量计算、多晶转变研究和熔点数据共同证实，这两种多晶表现出单向热力学关系，高Z ‘形式Ⅱ（Z ’ = 2）是热力学稳定的结晶相。在较高相对湿度条件下（90% RH），形态Ⅰ在一周内发生了明显的相变，而形态Ⅱ在至少四周内保持了相稳定性。这两种共晶的性能差异进一步强调了共晶多晶筛选的实际意义。

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引用次数: 0

Discovery and characterization of two rare copaene-type norsesquiterpenes: Diapoterpenes A and B 两种罕见的copcopene型去倍半萜的发现和表征：二萜A和二萜B

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2026-01-28 DOI: 10.1016/j.molstruc.2026.145508

Heng Guo , Hongjie Shen , Yining Xu , Lan Liu , Zhenger Wu , Senhua Chen

Two new copaene-type norsesquiterpenes, diapoterpenes A (1) and B (2), along with one new biogenetically related cadinane-type sesquiterpenoid, diapoterpene C (3), were isolated from ascidian-derived fungus Diaporthe sp. SYSU-MS4722 collected from the South China Sea. Compounds 1 and 2 represented the first example of copaene-derived norsesquiterpenes, characterized by unique tricyclo[4.4.0.0²^,⁷]decane¹^,²–3-one skeleton. Their structures were elucidated by a combination of spectroscopic analyses (1D/2D NMR, HR-ESIMS, NMR, or ECD calculation) and X-ray crystallography. The unique structure resulted in severe proton signal overlap in the NMR spectra of 1, which significantly complicated the determination of its planar structure and absolute configuration. By applying the modified Mosher’s method, the overlapping proton signals were successfully resolved, enabling the unambiguous assignment of the absolute configuration for 1. Additionally, anti-inflammatory and anti-glioma activities of 1−3 were evaluated, with diapoterpene C (3) showing moderate inhibition of nitric oxide production in LPS-stimulated RAW264.7 cells. Overall, this research not only identifies norsesquiterpenes with novel structure from ascidian-derived fungus but also provides an effective strategy for the structural characterization of complex natural products facing challenges related to proton signal overlap in NMR analysis.

从南海海asciine来源的真菌Diaporthe sp. SYSU-MS4722中分离到两个新的copcopene型去倍半萜A(1)和B(2)，以及一个新的生物相关的二苯胺型倍半萜C(3)。化合物1和2是首个由copcopene衍生的去倍半萜类化合物，具有独特的三环[4.4.0.02,7]癸烷1,2 - 3- 1骨架。它们的结构通过光谱分析（1D/2D NMR, HR-ESIMS， NMR或ECD计算）和x射线晶体学的组合来阐明。独特的结构导致1的核磁共振波谱中质子信号严重重叠，使其平面结构和绝对构型的确定变得非常复杂。应用改进的Mosher方法，成功地解决了重叠的质子信号，使1的绝对构型的明确分配成为可能。此外，对1−3的抗炎和抗胶质瘤活性进行了评估，在lps刺激的RAW264.7细胞中，二萜烯C(3)显示出适度抑制一氧化氮的产生。总的来说，本研究不仅从海鞘类真菌中鉴定出具有新结构的去甲倍半萜，而且为在核磁共振分析中面临质子信号重叠挑战的复杂天然产物的结构表征提供了有效的策略。

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引用次数: 0

Design, crystal structure and anticancer activities of a novel bimetallic organotin and copper(I) cyanide with dipyridyl ketone supramolecular coordination polymer 新型二吡啶酮双金属有机锡铜(I)氰超分子配位聚合物的设计、晶体结构和抗癌活性

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2026-01-28 DOI: 10.1016/j.molstruc.2026.145512

Doaa Domyati , Ranya A. Al-Zahrani , Ehab M.M. Ali , Bambar Davaasuren , Mariusz Jaremko , Mohamed M. El-bendary

The room-temperature self-assembly of Me₃SnCl and 2,2′-dipyridyl ketone (dpk) with K₃[Cu(CN)₄] resulted in a new organotin–copper bimetallic supramolecular coordination polymer, denoted as [Me₃SnCu(CN)₂·dpk], (SCP 1). SCP 1 crystallized as yellow prismatic crystals from an aqueous acetonitrile solution. SCP 1 was comprehensively characterized using elemental analysis, IR spectroscopy, electronic absorption measurements, and ¹H/¹³C NMR spectroscopy. The structure of SCP 1 was unambiguously confirmed by single-crystal X-ray diffraction. SCP 1 consists of infinite 1D zigzag chains formed by [Me₃Sn]⁺ cations linking the anionic [Cu(CN)₂]⁻ units, with dpk ligands bridging between chains. Adjacent chains are further connected through π–π stacking between the pyridine rings of dpk, generating a 2D layered arrangement. Hydrogen bonding between cyanide groups and dpk lignads in neighboring layers further reinforces the assembly, ultimately giving rise to a three-dimensional (3D) honeycomb-like framework. The photoluminescence characteristics of SCP 1 were analyzed and compared with those of the uncoordinated dpk ligand. The newly synthesized bimetallic organotin–copper cyanide SCP 1 was evaluated for its anticancer activity against several cancer cell lines, including liver (HepG2), colon (HCT116), and triple-negative breast cancer (MDA-MB-231). SCP 1 exhibited marked selectivity and potent cytotoxicity, with particularly low IC₅₀ values toward MDA-MB-231 cells (selectivity index, SI = 5.57). Its therapeutic promise is further supported by evidence of necrosis and late-stage apoptosis, along with S-phase and sub-G1 cell-cycle arrest observed in HCT116 colon cancer cells.

将Me₃SnCl和2,2′-二吡啶酮（dpk）与K₃[Cu（CN）₄]在室温下自组装，得到了一种新的有机锡-铜双金属超分子配位聚合物，命名为[Me₃SnCu（CN）₂·dpk], （SCP 1）。SCP 1在乙腈水溶液中结晶为黄色棱柱状晶体。利用元素分析、红外光谱、电子吸收测量和1H/13C核磁共振光谱对SCP 1进行了全面表征。单晶x射线衍射明确证实了SCP 1的结构。SCP 1由[Me₃Sn] +阳离子连接阴离子[Cu(CN) 2]⁻单位形成的无限一维之字形链组成，dpk配体在链之间架桥。相邻链通过dpk的吡啶环之间的π -π堆叠进一步连接，形成二维层状排列。相邻层中氰化物基团和dpk木质素之间的氢键进一步加强了组装，最终形成了三维（3D）蜂窝状框架。分析了SCP 1的光致发光特性，并与未配位的dpk配体进行了比较。新合成的双金属有机锡-氰化铜SCP 1对肝癌（HepG2）、结肠癌（HCT116）和三阴性乳腺癌（MDA-MB-231）的抗癌活性进行了评价。SCP 1表现出明显的选择性和强大的细胞毒性，对MDA-MB-231细胞具有特别低的IC₅0值（选择性指数，SI = 5.57）。在HCT116结肠癌细胞中观察到的坏死和晚期凋亡，以及s期和亚g1细胞周期阻滞的证据进一步支持了其治疗前景。

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引用次数: 0

Structural, spectroscopic and microbiological characterization of a Zn(II) complex based on a 1,3,4-thiadiazole derivative – experimental and computational studies 基于1,3,4-噻二唑衍生物的Zn（II）配合物的结构、光谱和微生物学表征——实验和计算研究

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2026-01-28 DOI: 10.1016/j.molstruc.2026.145498

Joachim Grzybowski , Iwona Budziak-Wieczorek , Klaudia Rząd , Izabela Korona-Glowniak , Małgorzata Figiel , Dariusz Karcz , Monika Srebro-Hooper , Arkadiusz Matwijczuk

A novel resorcynyl-1,3,4-thiadiazole-based Zn(II) complex NTBD-Zn was synthesized and characterized via both experimental and computational studies. The research involved detailed absorption and emission properties measurements and simulations, combined with geometric and electronic structure analyses considering different coordination modes of the metal to the ligand. These studies were further complemented by an assessment of the complex’s potential microbiological activity. The additional UV-Vis absorption intensity centered at ca. 370 nm along with the corresponding emission signal at ca. 460 nm observed for NTBD-Zn vs. NTBD attests to a successful complexation of Zn(II) to the resorcynyl-thiadiazole ligand, which, as confirmed by the calculations, occurs preferentially through one of the nitrogen atoms in the thiadiazole ring and the deprotonated ortho-hydroxyl group in the resorcynyl fragment, with the planar arrangement of the resorcynyl-thiadiazole and an only slightly more favored tetrahedral/pyramidal Zn(II) coordination sphere, preference for which increases upon inclusion of a water molecule in NTBD-Zn. The absorption and emission wavelengths computed for such model solution-phase structures agree with the experimental data in a reasonably satisfactory manner, although an overall blue-shift was observed, and the excitations analysis showed a resorcynyl-thiadiazole-ligand-centered π–π* origin of the dominant electronic transitions with no involvement of the metal orbitals. The experimentally observed appearance of the low-energy absorption intensity and the red-shift of the emission signal for the complex compared to the ligand correlates well with a decrease in the HOMO/LUMO gap occurring upon the complexation. Finally, compared to NTBD, NTBD-Zn demonstrates enhanced biological activity against Gram-positive bacteria, including staphylococci, micrococci, and bacilli, while showing no effect against Gram-negative strains.

合成了一种新型间苯氰-1,3,4-噻二唑基Zn（II）配合物NTBD-Zn，并通过实验和计算对其进行了表征。该研究包括详细的吸收和发射特性测量和模拟，结合几何和电子结构分析，考虑金属与配体的不同配位模式。这些研究得到了复合体潜在微生物活性评估的进一步补充。NTBD-Zn和NTBD分别在约370 nm处观察到额外的紫外-可见吸收强度，并在约460 nm处观察到相应的发射信号，证明Zn（II）与间苯二唑配体成功络合，通过计算证实，锌（II）优先通过噻二唑环上的一个氮原子和间苯二唑片段上去质子化的邻羟基发生络合。间炔基-噻二唑的平面排列和稍偏向于四面体/锥体Zn（II）配位球，在NTBD-Zn中加入水分子后，对Zn（II）配位球的偏好增加。该模型溶液-相结构的吸收和发射波长计算结果与实验数据相当满意，尽管观察到整体蓝移，并且激发分析表明，优势电子跃迁的起源为间环基-噻二唑-配体中心π -π *，没有金属轨道的参与。实验观察到，与配体相比，配合物的低能量吸收强度和发射信号的红移现象与配合物发生时HOMO/LUMO间隙的减小有很好的相关性。最后，与NTBD相比，NTBD- zn对革兰氏阳性菌（包括葡萄球菌、微球菌和杆菌）的生物活性增强，而对革兰氏阴性菌没有作用。

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引用次数: 0

Design, synthesis, and evaluation of artesunate-benzofuran hybrids as dual anticancer and anti-inflammatory candidates: In silico profiling and in vitro validation in Caco-2, HepG2, Ishikawa, and RAW 264.7 cell lines 青蒿素-苯并呋喃复合物作为抗癌和抗炎双重候选物的设计、合成和评价：硅片分析和Caco-2、HepG2、Ishikawa和RAW 264.7细胞系的体外验证

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2026-01-28 DOI: 10.1016/j.molstruc.2026.145507

Bassam A. Najri , Katia Mohand Saidi , Cemal Kozansoy , Abdelmadjid Guendouzi , Sevki Arslan , Arif Kivrak

Colorectal, liver, and uterine cancers remain major clinical challenges due to their high prevalence and mortality. In this study, a series of artesunate-benzofuran hybrid compounds (5A-5E) were designed and synthesized through a multistep approach and structurally characterized by ¹H/¹³C NMR, FTIR, and LC-MS/MS analyses. Their anticancer and anti-inflammatory potential was evaluated using complementary in silico and in vitro methodologies. Drug-likeness and ADMET predictions indicated favorable pharmacokinetic behavior and low toxicity. Molecular docking studies demonstrated strong binding affinities toward key cancer-related targets, DNA polymerase β (POLB), caspase-8 (CASP8), and protein kinase A (PKA), with binding energies ranging from -91.66 to -170.97 a.u., exceeding those of tamoxifen (TAM) (-88.40 to -114.88 a.u.) and 5-fluorouracil (5FU) (-52.27 to -53.79 a.u.). Molecular dynamics simulations further confirmed the stability of the ligand-protein complexes. In vitro cytotoxicity assays against Caco-2, HepG2, and Ishikawa cell lines revealed selective anticancer activity with minimal toxicity. Compounds 5A and 5C displayed the most pronounced effects, with half maximal inhibitory concentration (IC₅₀) values of 51.48 µM (Caco-2) and 35.16 µM (HepG2) for 5A, and 58.32 µM (Caco-2) and 50.98 µM (HepG2) for 5C. Mechanistic investigations showed apoptosis induction via caspase activation, inhibition of cell migration, G0/G1 cell-cycle arrest, and suppression of colony formation. In addition, compounds 5A-5C significantly reduced lipopolysaccharide-induced nitric oxide production in RAW 264.7 macrophages. These results support artesunate-benzofuran hybrids as promising multitarget candidates for the development of anticancer agents with concurrent anti-inflammatory activity.

结直肠癌、肝癌和子宫癌由于其高患病率和死亡率仍然是主要的临床挑战。本研究采用多步法设计合成了一系列青蒿素-苯并呋喃杂化化合物（5A-5E），并通过1H/13C NMR、FTIR和LC-MS/MS对其结构进行了表征。它们的抗癌和抗炎潜能用互补的硅和体外方法进行了评估。药物相似和ADMET预测表明良好的药代动力学行为和低毒性。分子对接研究表明，该药物与癌症相关的关键靶点DNA聚合酶β (POLB)、CASP8 （CASP8）和蛋白激酶A （PKA）具有较强的结合亲和力，结合能范围为-91.66 ~ -170.97 a.u，超过了他莫西芬（TAM）（-88.40 ~ -114.88 a.u）和5-氟尿嘧啶（5FU）（-52.27 ~ -53.79 a.u）。分子动力学模拟进一步证实了配体-蛋白复合物的稳定性。对Caco-2、HepG2和Ishikawa细胞系的体外细胞毒性实验显示，其具有选择性的抗癌活性，毒性很小。化合物5A和5C的半数最大抑制浓度（IC50）值分别为51.48µM （Caco-2）和35.16µM (HepG2)， 5C的一半最大抑制浓度（IC50）值分别为58.32µM （Caco-2）和50.98µM （HepG2）。机制研究表明，通过激活caspase，抑制细胞迁移，G0/G1细胞周期阻滞和抑制集落形成诱导凋亡。此外，化合物5A-5C显著降低脂多糖诱导的RAW 264.7巨噬细胞一氧化氮的产生。这些结果支持青蒿琥酯-苯并呋喃混合物作为有希望的多靶点候选物，用于开发具有抗炎活性的抗癌药物。

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引用次数: 0

Characterization of calcium malic acid complex synthesized from Rhus coriaria and its protective effects on retinal pigment epithelial cells 马尾草合成苹果酸钙复合物的性质及其对视网膜色素上皮细胞的保护作用

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2026-01-28 DOI: 10.1016/j.molstruc.2026.145486

Bilge Alli , Gökhan Ceyhan , Akif Hakan Kurt , Âdem Doğaner

Malic acid, a prominent organic acid in Rhus coriaria (sumac), a plant widely distributed in Türkiye and traditionally consumed as a food additive, serves as a key raw material across various industries. This study explores the structural features of a calcium complex derived from malic acid extracted from sumac leaves and evaluates its potential to mitigate oxidative damage caused by hydrogen peroxide (H₂O₂) in retinal pigment epithelial (RPE) cells. Characterization techniques include Spectroscopy, Nuclear Magnetic Resonance, Thermal Analysis, and Mass Spectrometry. Additional assessments covered electrochemical behavior, photoluminescence, and thermal stability. Furthermore, the complex's impact on AMD (Age-Related Macular Degeneration) was investigated using ARPE-19 cell lines, with results analyzed statistically. Our findings reveal that the naturally sourced calcium malic acid complex not only exhibits a well-defined structure but also confers protective effects against H₂O₂-mediated oxidative stress in RPE cells, suggesting its potential as a therapeutic agent for retinal disorders.

苹果酸是一种重要的有机酸，是一种广泛分布于泰国的漆树植物，传统上作为食品添加剂食用，是许多行业的关键原料。本研究探讨了从漆树叶中提取的苹果酸衍生的钙复合物的结构特征，并评估了其减轻过氧化氢（H₂O₂）对视网膜色素上皮（RPE）细胞造成的氧化损伤的潜力。表征技术包括光谱学、核磁共振、热分析和质谱。附加的评估包括电化学行为，光致发光和热稳定性。此外，利用ARPE-19细胞系研究该复合物对AMD（年龄相关性黄斑变性）的影响，并对结果进行统计学分析。我们的研究结果表明，天然来源的苹果酸钙复合物不仅具有明确的结构，而且对RPE细胞中h2o2介导的氧化应激具有保护作用，这表明它有可能成为视网膜疾病的治疗剂。

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引用次数: 0

Pressure-induced near-infrared emission in a plastic organic crystal via ordered lattice densification 通过有序晶格致密化的塑料有机晶体中压力诱导的近红外发射

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2026-01-28 DOI: 10.1016/j.molstruc.2026.145505

Yuanyuan Liu , Huining Liu , Jing Yang , Yazhen Zhang , Linxia Shi , Jiakun Bai , Kai Wang , Jiang Peng , Aisen Li

Flexible organic crystals exhibiting pressure-induced near-infrared (NIR, 650–900 nm) emission are extremely rare. Herein, we report a plastic organic molecular crystal based on a 2-cyanoacrylate derivative, methyl (E)-2-cyano-3-(4-(piperidin-1-yl)phenyl)acrylate (MCPPA). Under hydrostatic pressure, the maximum fluorescence emission of MCPPA continuously redshifts from 570 to 701 nm (Δλ = 131 nm), entering the NIR region. Theoretical calculations reveal that increasing pressure significantly enhances intermolecular interactions, accompanied by shortened contact distances and progressive lattice densification, which collectively drive the redshift of both absorption and emission spectra. In contrast, mechanical grinding primarily induces a crystal-to-amorphous transition, resulting in only a minor redshift of 11 nm. These results demonstrate that pressure-induced ordered densification plays a decisive role in achieving pronounced piezochromic redshifts and NIR emission in MCPPA. This work provides a new material platform and design strategy for constructing flexible organic crystals with pressure-tunable NIR emission.

具有压力诱导近红外（NIR, 650-900 nm）发射的柔性有机晶体是非常罕见的。在此，我们报道了一种基于2-氰基丙烯酸酯衍生物甲基(E)-2-氰基-3-（4-（胡椒苷-1-基）苯基）丙烯酸酯（MCPPA）的塑料有机分子晶体。在静水压力下，MCPPA的最大荧光发射从570 nm持续红移至701 nm （Δλ = 131 nm），进入近红外区。理论计算表明，压力的增加显著增强了分子间的相互作用，伴随着接触距离的缩短和晶格密度的增加，这共同驱动了吸收光谱和发射光谱的红移。相比之下，机械磨削主要诱导晶体到非晶态的转变，只导致11 nm的微小红移。这些结果表明，压力诱导有序致密化在实现明显的压致变色红移和近红外发射中起决定性作用。本研究为构建具有压力可调近红外发射的柔性有机晶体提供了新的材料平台和设计策略。

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引用次数: 0

From coordination-induced tautomerism to therapeutics: Structural, supramolecular, and antimicrobial insights into a Hg(II)-thiosemicarbazone complex 从配位诱导的互变异构到治疗：Hg(II)-硫代氨基脲络合物的结构、超分子和抗菌见解

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2026-01-28 DOI: 10.1016/j.molstruc.2026.145504

Rizwana Begum Choudhury , Toufique Shahnowaz , Souryadeep Mukherjee , Nabajyoti Baildya , Onur Sahin , Nurul Alam Choudhury , Subhadip Roy , Sibel Demir Kanmazalp , Suman Adhikari

A new Hg(II) complex 1 was synthesised from a 3-methoxysalicylaldehyde-4-methylthiosemicarbazone ligand (H₂L) via one-pot reaction and characterized by FT-IR, ¹H NMR, mass spectroscopy, elemental analysis, and single-crystal X-ray diffraction analysis. The complex 1 adopts a distorted seesaw [HgN₂S₂] coordination geometry. Coordination to Hg(II) promotes a thione–thiol tautomeric conversion in the ligand (H₂L), forming a deprotonated thiolate donor. Structural analysis, combined with Hirshfeld surface and enrichment ratio evaluations, unveiled that O⋯H and C⋯C contacts play dominant roles in supramolecular stabilization. Density Functional Theory (DFT) analysis suggests a substantial amount of charge transfer from H₂L to Hg(II). These results highlight how the interplay between coordination-induced tautomerism and noncovalent forces governs the molecular organization of the Hg(II) complex. Furthermore, the antibacterial efficacies of Hg(II) complex 1 and the free ligand (H₂L) towards Gram-positive bacterial strains (viz. Staphylococcus cohnii, Mammaliicoccus lentus, Bacillus cereus, and Corynebacterium stationis) and Gram-negative bacterial strains (viz. Klebsiella pneumoniae, Enterobacter cloacae, Salmonella enterica, and Shigella sonnei) have been evaluated. Moreover, to explore the mechanism of the antibacterial action of 1, time-kill kinetic assay, deoxyribonucleic acid (DNA) cleavage potential, and molecular docking studies are performed.

以3-甲氧基水杨醛-4-甲基硫代氨基脲配体（H2L）为原料，通过一锅反应合成了一种新的Hg（II）配合物1，并用FT-IR、1H NMR、质谱、元素分析和单晶x射线衍射对其进行了表征。配合物1采用畸变跷跷板[HgN2S2]配位几何。与Hg（II）的配位促进了配体（H2L）中硫-硫醇互变异构的转化，形成去质子化的硫酸盐供体。结构分析，结合Hirshfeld表面和富集比评估，揭示了O⋯H和C⋯C接触在超分子稳定中起主导作用。密度泛函理论（DFT）分析表明，大量的电荷从H2L转移到Hg（II）。这些结果强调了配位诱导的互变异构和非共价力之间的相互作用如何控制Hg（II）配合物的分子组织。此外，Hg（II）复合物1和游离配体（H2L）对革兰氏阳性菌株（即柯氏葡萄球菌、乳杆菌、蜡样芽孢杆菌和静止棒状杆菌）和革兰氏阴性菌株（即肺炎克雷伯菌、阴沟肠杆菌、肠沙门氏菌和索内志贺氏菌）的抗菌效果也进行了评估。此外，为了探索抗菌作用的机制，进行了时间杀伤动力学测定、脱氧核糖核酸（DNA）切割电位和分子对接研究。

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引用次数: 0

Synthesis of new Alkyl-Aryl ether derivatives via Mitsunobu coupling: Structural characterization and insight into substituent-dependent photochemical behaviour 通过Mitsunobu偶联合成新的烷基-芳基醚衍生物：结构表征和对取代基依赖的光化学行为的洞察

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure

Pub Date : 2026-01-27 DOI: 10.1016/j.molstruc.2026.145500

Nitin Srivastava, Amita Mahapatra, Abhineet Verma, Krishanu Bandyopadhyay, Satyen Saha

Understanding how aryl substitution governs the photophysical and photochemical behavior of alkyl-aryl ethers is essential for tailoring their functional properties. Herein, three new ether compounds, Phenyl-1-butyl ether (HPBP), 4-Methoxy-1-phenylbutyl ether (MPBP), and 4-Nitrophenyl-1-phenylbutyl ether (NPBP) were synthesized via a Mitsunobu coupling using 1-phenyl-1-butanol as the key precursor under mild conditions (PPh₃/DIAD/THF) at room temperature. The structural characterization was accomplished by Nuclear Magnetic Resonance (NMR) and single-crystal X-ray diffraction (SCXRD) studies. UV–visible absorption and fluorescence studies conducted in solvents of varying polarity reveal distinct substituent-dependent optical behavior, with electron-donating (-OCH₃) and electron-withdrawing groups (-NO₂) significantly influencing both absorption and emission characteristics. Importantly, time-resolved infrared (TRIR) spectroscopy, employed here for the first time to this class of ethers, provides direct mechanistic insight into their excited-state reactivity. Upon photoexcitation, HPBP and MPBP undergo a photo-Claisen rearrangement via a cage-escape radical recombination pathway involving singlet-state phenoxy radicals. In contrast, NPBP bearing a strong electron-withdrawing (-NO₂) group remains photochemically inactive supressing the homolytic photochemical cleavage. These findings establish a clear structure-property relationship in alkyl-aryl ethers and illustrate the profound role of aryl substituents in modulating photophysical responses and photochemical pathways.

了解芳基取代如何控制烷基芳基醚的光物理和光化学行为，对于调整其功能性质至关重要。本文以1-苯基-1-丁醇为主要前体，在室温温和条件下（PPh₃/DIAD/THF），通过Mitsunobu偶联法合成了3个新的醚类化合物：苯基-1-丁基醚（HPBP）、4-甲氧基-1-苯基丁基醚（MPBP）和4-硝基苯基-1-苯基丁基醚（NPBP）。通过核磁共振（NMR）和单晶x射线衍射（SCXRD）研究完成了结构表征。在不同极性溶剂中进行的紫外可见吸收和荧光研究揭示了不同的取代基依赖光学行为，给电子基团（-OCH3）和吸电子基团（-NO2）显著影响吸收和发射特性。重要的是，时间分辨红外光谱（TRIR）首次应用于这类醚，为其激发态反应性提供了直接的机理见解。在光激发下，HPBP和MPBP通过涉及单重态苯氧基自由基的笼型逃逸自由基重组途径进行光- clisen重排。相反，具有强吸电子基团（-NO2）的NPBP在光化学上保持非活性，抑制了均溶光化学裂解。这些发现建立了烷基芳基醚清晰的结构-性质关系，说明了芳基取代基在调节光物理反应和光化学途径中的重要作用。

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引用次数: 0