Polyhedron最新文献_第5页

To thread or not to thread: Reaction of uranyl (UO22+) with two Aza-crown macrocycles1 穿与不穿：铀酰（UO22+）与两个氮杂冠大环的反应

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-12-15 DOI: 10.1016/j.poly.2025.117935

Gabriella S. Godinho, Kevin K. Lee, Qien Feng, Guang Wu, Justin J. Wilson, Trevor W. Hayton

The complexation of the uranyl ion (UO₂²⁺) by macrocyclic ligands is hindered by the rigidly enforced trans orientation of its oxo ligands. To further investigate this coordination chemistry challenge, here we investigate the reactivity of UO₂²⁺ with two different 18-membered aza-crown macrocycles, diaza-dibenzo-18-crown-6 (DADBC) and 7,16-bis(N-methylacetamide)diaza-18-crown-6 (BAM). The reaction of uranyl triflate, [UO₂(OTf)₂(THF)₃], with DADBC in toluene afforded [UO₂(DADBC)][OTf]₂, in which the UO₂²⁺ ion is fully encapsulated by the macrocycle. This conclusion was supported by NMR, UV–Vis, IR, and Raman spectroscopies, as well as single-crystal X-ray crystallography. Attempts to form the in-macrocycle complex of BAM, however, were unsuccessful. The reaction of BAM with [UO₂(OTf)₂(THF)₃] in THF/CH₂Cl₂ unexpectedly afforded crystals of [H₂BAM][OTf]₂, where the protons are derived from solvate water in the BAM crystal lattice. In contrast, reaction of BAM with UO₂(NO₃)₂·6H₂O resulted in formation of the coordination polymer, [UO₂(κ²-NO₃)₂(μ-BAM)]_∞. The crystal structure of this compound revealed that the BAM ligand is coordinated to UO₂²⁺ via its pendent carboxamide donors, while the donor atoms within the macrocyclic cavity remained unbound. The X-ray crystal structure of the free BAM ligand was also obtained, which showed that it exists in an identical conformation to that seen in the structure of [UO₂(κ²-NO₃)₂(μ-BAM)]_∞, where the pendent carboxamide donors are engaged in an intramolecular hydrogen-bonding interaction with the donor atoms within the macrocycle. These results suggest that the enthalpic penalty of breaking these intramolecular hydrogen bonds prevents UO₂²⁺ from “threading the needle.” In contrast, DADBC, which lacks such intramolecular hydrogen-bonding interactions, can readily accommodate UO₂²⁺. This comparison demonstrates how subtle modifications to the macrocycle, such as cavity size, rigidity, and pendant donor groups, can affect its affinity for UO₂²⁺, and provide insights into macrocycle chelator design for this ion for applications in separations, medicine, and energy.

大环配体对铀酰离子（UO22+）的络合作用受到氧基配体强制反取向的阻碍。为了进一步研究这种配位化学挑战，我们研究了UO22+与两个不同的18元氮杂冠大环，二氮杂-二苯并-18冠-6 （DADBC）和7,16-双（n-甲基乙酰胺）二氮杂-18冠-6 （BAM）的反应性。三酸铀酰[UO2(OTf)2(THF)3]与甲苯中的DADBC反应得到[UO2(DADBC)][OTf]2，其中UO22+离子被大环完全包裹。这一结论得到了核磁共振、紫外可见、红外和拉曼光谱以及单晶x射线晶体学的支持。然而，试图形成BAM的大环内复合物是不成功的。BAM与[UO2(OTf)2(THF)3]在THF/CH2Cl2中反应，意外地产生了[H2BAM][OTf]2晶体，其中质子来源于BAM晶格中的溶剂化水。BAM与UO2(NO3)2·6H2O反应生成配位聚合物[UO2(κ2-NO3)2(μ-BAM)]∞。该化合物的晶体结构表明，BAM配体通过其悬置的羧酰胺给体与UO22+配位，而大环腔内的给体原子保持未结合状态。得到了游离BAM配体的x射线晶体结构，结果表明其结构与[UO2(κ2-NO3)2(μ-BAM)]∞结构相同，其中悬置的羧酰胺给体在大环内与给体原子发生分子内氢键相互作用。这些结果表明，破坏这些分子内氢键的焓惩罚阻止了UO22+“穿针”。相比之下，DADBC缺乏这种分子内氢键相互作用，可以很容易地容纳UO22+。这一比较表明了对大环的细微修改，如腔大小、刚度和挂载供体基团，如何影响其对UO22+的亲和力，并为该离子在分离、医学和能源应用中的大环螯合剂设计提供了见解。

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引用次数: 0

New silver N-heterocyclic carbene (NHC) complexes containing fluoro and acetyl groups: design, characterization, molecular docking studies, and inhibition properties against several metabolic enzymes 含氟和乙酰基的新型银n -杂环卡宾（NHC）配合物：设计、表征、分子对接研究和对几种代谢酶的抑制特性

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-12-11 DOI: 10.1016/j.poly.2025.117931

Yetkin Gök , Yeliz Demir , Muhammad Haroon , Zaroon Sajid , Burcu Tezcan , Aydın Aktaş , Özlem Demirci , İlhami Gülçin , Irmak İçen Taşkın , Sevim Gürbüz

This study presents the synthesis of acetyl- and fluorinated group-containing imidazol-2-ylidene silver complexes. The structures of the complexes obtained via deprotonation method were elucidated using spectroscopic techniques such as NMR, FTIR, and MS, as well as elemental analysis. In addition, the enzyme inhibition profiles of the synthesized Ag(I)-NHC complexes were thoroughly investigated against human carbonic anhydrase isoforms I and II (hCAs I and II), as well as acetylcholinesterase (AChE). Notably, compound 2f, bearing 2-chloro and 4-fluoro groups, exhibited superior inhibition potency against hCA I and AChE enzymes, with K_i values outperforming the reference inhibitors acetazolamide (AZA) and tacrine (TAC). These findings suggest that the dual halogenation pattern enhances both electrostatic and hydrophobic interactions within enzyme active sites. In addition, the cytotoxic activity of compound 2f was determined using MTT assays in SH-SY5Y (neuroblastoma), HCT-116 (colorectal carcinoma), and MCF-7 (breast adenocarcinoma) cell lines, yielding IC₅₀ values of 35.63 ± 0.84 μM, 49.37 ± 0.97 μM, and 54.92 ± 1.94 μM, respectively. Further, we examined the inhibition potential of three most potent compounds (2a, 2e and 2f) with in silico molecular docking with three target proteins (hCA I, hCA II, and AChE). The binding energy score and ligand-protein interactions were indicating excellent inhibition potential of examined compounds. Overall, these results highlight the multi-target enzyme-blocking ability of 2f as a promising candidate for suppressing tumor growth.

研究了含乙酰基和含氟基的咪唑-2-基银配合物的合成。用NMR、FTIR、MS和元素分析等光谱技术对脱质子法得到的配合物进行了结构鉴定。此外，我们还深入研究了合成的Ag(I)-NHC复合物对人类碳酸酐酶I和II （hCAs I和II）以及乙酰胆碱酯酶（AChE）的酶抑制谱。值得注意的是，含有2-氯和4-氟基团的化合物2f对hCA I和AChE具有较好的抑制作用，其Ki值优于对照抑制剂乙酰唑胺（AZA）和他克林（TAC）。这些发现表明，双卤化模式增强了酶活性位点内的静电和疏水相互作用。此外，在SH-SY5Y（神经母细胞瘤），HCT-116（结直肠癌）和MCF-7（乳腺腺癌）细胞系中使用MTT测定了化合物2f的细胞毒活性，IC₅0值分别为35.63±0.84 μM, 49.37±0.97 μM和54.92±1.94 μM。此外，我们检测了三种最有效的化合物（2a， 2e和2f）与三种靶蛋白（hCA I， hCA II和AChE）的硅分子对接的抑制潜力。结合能评分和配体-蛋白相互作用表明所检测化合物具有良好的抑制潜力。总的来说，这些结果突出了2f的多靶点酶阻断能力作为抑制肿瘤生长的有希望的候选物。

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引用次数: 0

Supramolecular assemblies in Zn(II) metal-organic compounds involving 3-aminopyridine and 1,10-phenanthroline: antiproliferative evaluation and theoretical studies 含3-氨基吡啶和1,10-菲罗啉的Zn（II）金属有机化合物中的超分子组装体：抗增殖评价和理论研究

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-12-11 DOI: 10.1016/j.poly.2025.117932

Kamal Krishna Dutta , Mridul Boro , Rosa M. Gomila , Antonio Frontera , Miquel Barcelo-Oliver , Munmi Gogoi , Akalesh Kumar Verma , Manjit K. Bhattacharyya

Two new Zn(II) metal-organic compounds of 3-Aminopyridine and 1,10-phenanthroline ligand viz. [Zn(phen)₂Cl][Zn(3-Ampy)Cl₃] (1) and [Zn(3-Ampy)₂Cl₂] (2) (where, 3-Ampy = 3-Aminopyridine, phen = 1,10-phenanthroline) have been synthesized and characterized using elemental analysis, TGA, spectroscopic (FTIR, electronic) and single crystal X-ray diffraction technique. Crystal structure analysis of the compounds reveal the formation of supramolecular layered architecture in 1 aided by CH⋯Cl, NH⋯Cl, NH⋯N hydrogen bonding interactions along with aromatic π-stacking, CH⋯π and anion(Cl)⋯π interactions. Intriguing anion–π/π–π/anion–π assemblies found in compound 1 have provided further rigidity to the crystal structure. The interesting aspect of compound 2 is the formation of a supramolecular

R_{4}^{4} (8)

synthon via strong directional NH⋯Cl hydrogen bonds and auxiliary CH⋯Cl and π-stacking interactions. These non-covalent interactions helping in the formation of anion–π/π–π/anion–π assemblies in compound 1 and supramolecular

R_{4}^{4} (8)

synthon in compound 2 have been further studied theoretically using density functional theory (DFT) calculations, non-covalent interaction (NCI) plot index, quantum theory of atoms in molecules (QTAIM) and molecular electrostatic potential (MEP) surface analysis. The in vitro cytotoxicity of the compounds through Trypan blue exclusion and apoptosis assays showcase their selective cytotoxic potential toward the Dalton's Lymphoma cancer cell line while sparing healthy PBMC cells. To explore the structure–activity relationship, molecular docking was conducted to understand the binding behavior of the synthesized compounds with target cancer-related receptors.

合成了两个新的Zn（II）金属有机化合物- 3-氨基吡啶和1,10-菲罗啉配体[Zn(phen)2Cl][Zn(3-Ampy)Cl3](1)和[Zn(3-Ampy)2Cl2](2)（其中，3-Ampy = 3-氨基吡啶，phen = 1,10-菲罗啉），并利用元素分析、热重分析、光谱（FTIR、电子）和单晶x射线衍射技术对其进行了表征。化合物的晶体结构分析揭示了在1中CH⋯Cl， NH⋯Cl， NH⋯N氢键相互作用以及芳香π堆积，CH⋯π和阴离子(Cl)⋯π相互作用的辅助下形成的超分子层状结构。在化合物1中发现的阴离子-π /π -π /阴离子-π组合为晶体结构提供了进一步的刚性。化合物2有趣的方面是通过强定向NH⋯Cl氢键和辅助CH⋯Cl和π堆积相互作用形成超分子R448合子。利用密度泛函理论（DFT）计算、非共价相互作用（NCI）图指数、分子原子量子理论（QTAIM）和分子静电势（MEP）表面分析，进一步研究了化合物1中阴离子-π /π -π /阴离子-π组合和化合物2中超分子R448合成子的非共价相互作用。通过台盼蓝排斥和细胞凋亡实验，这些化合物的体外细胞毒性显示了它们对道尔顿淋巴瘤细胞系的选择性细胞毒性，同时保留了健康的PBMC细胞。为了探究构效关系，我们进行了分子对接，了解合成的化合物与肿瘤相关靶受体的结合行为。

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引用次数: 0

Synthesis, crystal structure, and multifunctional properties of a tetrabromomercurate(II) hybrid with protonated 4-(dimethylamino)pyridine 与质子化4-（二甲氨基）吡啶的四溴酸盐杂化物的合成、晶体结构和多功能性质

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-12-09 DOI: 10.1016/j.poly.2025.117929

Hafsia Tlili , Ahlem Guesmi , Sandra Walha , Noureddine Mhadhbi , Ali Ben Ahmed , Naoufel Ben Hamadi , Fehmi Boufahja , Houcine Naïli

The newly synthesized organic–inorganic hybrid compound (C₇H₁₁N₂)₂[HgBr₄]·H₂O (1) was obtained via slow evaporation method at room temperature and characterized by single-crystal X-ray diffraction, supported by density functional theory. The crystal structure belongs to the triclinic system and adopts the P-1 space group, comprising two (C₇H₁₁N₂)⁺ cations, one [HgBr₄]²⁻ anion, and a water molecule. These units are connected through N–H···Br, O–H···Br, and O–H···O hydrogen bonds, stabilizing the three-dimensional framework. To gain deeper insight into the crystal packing, Hirshfeld surface analysis was employed, highlighting the significant contributions of H···Br (59.8 %) and H···O (10.5 %) interactions in governing the intermolecular contacts and stabilizing the lattice. In parallel, the optical properties of compound (1) were systematically explored using UV–Vis absorption spectroscopy. The optical band gap, derived from Tauc plot analysis, suggests that the material possesses a semiconducting nature, positioning it as a potential candidate for optoelectronic applications. Furthermore, the biological potential of the compound was assessed through comprehensive antioxidant, antimicrobial, and anti-inflammatory activity assays. The compound exhibited notable free radical scavenging ability, broad-spectrum antimicrobial effects, and significant inhibition of inflammatory markers, indicating its promise as a multifunctional bioactive agent. Additionally, preliminary toxicity evaluations were conducted, showing acceptable biocompatibility levels within the tested concentrations, thus supporting its potential for biomedical applications. The combination of structural, optical, and biological features positions compound (1) as a promising material for optoelectronic and biomedical applications.

新合成的有机-无机杂化化合物（C7H11N2）2[HgBr4]·H₂O(1)在室温下通过慢蒸发法制得，并采用密度泛函理论对其进行了单晶x射线衍射表征。晶体结构属于三斜系，采用P-1空间基团，由两个(C7H11N2)+阳离子、一个[HgBr4]2−阴离子和一个水分子组成。这些单元通过N-H··Br、O - h··Br和O - h··O氢键连接，稳定了三维框架。为了更深入地了解晶体填充，采用Hirshfeld表面分析，突出了H··Br（59.8%）和H··O（10.5%）相互作用在控制分子间接触和稳定晶格方面的重要贡献。同时，利用紫外-可见吸收光谱系统地研究了化合物(1)的光学性质。从Tauc图分析得出的光学带隙表明，该材料具有半导体性质，将其定位为光电应用的潜在候选者。此外，通过全面的抗氧化、抗菌和抗炎活性测定来评估化合物的生物潜力。该化合物具有明显的自由基清除能力、广谱抗菌作用和显著的炎症标志物抑制作用，预示着其作为多功能生物活性剂的前景。此外，进行了初步毒性评估，显示在测试浓度内生物相容性水平可接受，因此支持其生物医学应用的潜力。结构、光学和生物特性的结合使化合物(1)成为光电子和生物医学应用的有前途的材料。

{"title":"Synthesis, crystal structure, and multifunctional properties of a tetrabromomercurate(II) hybrid with protonated 4-(dimethylamino)pyridine","authors":"Hafsia Tlili , Ahlem Guesmi , Sandra Walha , Noureddine Mhadhbi , Ali Ben Ahmed , Naoufel Ben Hamadi , Fehmi Boufahja , Houcine Naïli","doi":"10.1016/j.poly.2025.117929","DOIUrl":"10.1016/j.poly.2025.117929","url":null,"abstract":"<div><div>The newly synthesized organic–inorganic hybrid compound (C7H11N2)2[HgBr4]·H₂O (1) was obtained via slow evaporation method at room temperature and characterized by single-crystal X-ray diffraction, supported by density functional theory. The crystal structure belongs to the triclinic system and adopts the P-1 space group, comprising two (C7H11N2)+ cations, one [HgBr4]2− anion, and a water molecule. These units are connected through N–H···Br, O–H···Br, and O–H···O hydrogen bonds, stabilizing the three-dimensional framework. To gain deeper insight into the crystal packing, Hirshfeld surface analysis was employed, highlighting the significant contributions of H···Br (59.8 %) and H···O (10.5 %) interactions in governing the intermolecular contacts and stabilizing the lattice. In parallel, the optical properties of compound (1) were systematically explored using UV–Vis absorption spectroscopy. The optical band gap, derived from Tauc plot analysis, suggests that the material possesses a semiconducting nature, positioning it as a potential candidate for optoelectronic applications. Furthermore, the biological potential of the compound was assessed through comprehensive antioxidant, antimicrobial, and anti-inflammatory activity assays. The compound exhibited notable free radical scavenging ability, broad-spectrum antimicrobial effects, and significant inhibition of inflammatory markers, indicating its promise as a multifunctional bioactive agent. Additionally, preliminary toxicity evaluations were conducted, showing acceptable biocompatibility levels within the tested concentrations, thus supporting its potential for biomedical applications. The combination of structural, optical, and biological features positions compound (1) as a promising material for optoelectronic and biomedical applications.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"285 ","pages":"Article 117929"},"PeriodicalIF":2.6,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145748528","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Efficient photocatalytic degradation of rhodamine B by amorphous MOF-coated hydrogenated titanium dioxide core-shell photocatalyst coupled with peroxymonosulfate activation 非晶态mof包覆氢化二氧化钛核壳光催化剂耦合过氧单硫酸盐活化对罗丹明B的高效光催化降解

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-12-08 DOI: 10.1016/j.poly.2025.117919

Tiantian Luo , Junyi Wang , Ruiyan Wang , Jiale Wang , Hao Yan , Bei Zhang , Qi Zhou

In this study, a one-dimensional core–shell photocatalyst composed of hydrogenated TiO₂ (H-TiO₂) coated with an amorphous metal–organic framework (MOF) was synthesized via a simple hydrothermal method and applied as an efficient peroxymonosulfate (PMS) activator for Rhodamine B (RhB) degradation. Under simulated sunlight irradiation for 20 min, the optimized H-TiO₂/BPDC*2 catalyst achieved 99.40 % RhB removal at an initial concentration of 100 mg/L. Its apparent kinetic rate constant was 4.28 and 1.06 times higher than those of H-TiO₂ and H-TiO₂/BPDC, respectively. The enhanced performance is attributed to the core–shell heterojunction structure, which improves light absorption and charge separation, as evidenced by increased photocurrent, reduced photoluminescence intensity, and shorter time-resolved photoluminescence (TRPL) decay. Furthermore, the catalyst exhibited excellent stability over multiple cycles, demonstrating strong potential for practical wastewater treatment applications. Mechanistic studies revealed that ·O₂^- and ¹O₂ were the dominant reactive species involved in the degradation process.

本研究采用简单的水热法合成了一种由氢化TiO2 （H-TiO2）包覆无定形金属有机骨架（MOF）组成的一维核壳光催化剂，并将其作为一种高效的过氧单硫酸盐（PMS）活化剂用于罗丹明B （RhB）的降解。在模拟阳光照射20 min的条件下，优化后的H-TiO2/BPDC*2催化剂在初始浓度为100 mg/L时，对RhB的去除率达到99.40%。其表观动力学速率常数分别是H-TiO2和H-TiO2/BPDC的4.28倍和1.06倍。增强的性能归因于核壳异质结结构，该结构改善了光吸收和电荷分离，表现为光电流增加，光致发光强度降低，时间分辨光致发光（TRPL）衰减缩短。此外，该催化剂在多次循环中表现出优异的稳定性，显示出在实际废水处理应用中的强大潜力。机制研究表明，·O2-和1O2是参与降解过程的主要反应物质。

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引用次数: 0

Corrigendum to “Synthesis of zirconia and HPA based catalyst system with high acidity for n-hexane isomerization” [Polyhedron 282 (2025) 117810] “合成高酸性氧化锆和HPA基正己烷异构化催化剂体系”的勘误表[多面体282 (2025)117810]

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-12-04 DOI: 10.1016/j.poly.2025.117916

Amit Kumar , Priyanka , Mayora Varshney , Bhavtosh Sharma

引用次数: 0

Two electrochemical sensors based on different skeleton silver(I) complex modified glassy carbon electrodes for determination of H2O2 两种基于不同骨架银(I)配合物修饰玻碳电极的电化学传感器测定H2O2

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-12-01 DOI: 10.1016/j.poly.2025.117918

Rongrong Gao, Yuanyue Ma, Quanlong Cai, Junjie Teng, Huilu Wu

Two new silver(I) complexes, {[Ag₂(S-3Py)₂(fumarate)]·2C₂H₅OH·2H₂O}_n (1) and [Ag₂(S-4Py)₂(fumarate)]·3C₂H₅OH (2), (S-3Py = bis[1-(pyridin-3-ylmethyl)-benzimidazol-2-ylmethyl]sulfane, S-4Py = bis[1-(pyridin-4-ylmethyl)-benzimidazol-2-ylmethyl]sulfane), were synthesized. Single-crystal structural analysis revealed that Complex 1 adopts a one-dimensional chain structure, while Complex 2 exhibits a discrete binuclear configuration. The difference of skeleton structure of silver(I) complexes is due to the steric hindrance of main ligands S-3Py and S-4Py. The electrochemical sensing performance of two silver(I) complexes modified glassy carbon electrodes (Ag-1@GCE and Ag-2@GCE) for hydrogen peroxide detection in 0.2 M PBS was studied by constant voltage chronoamperometry. The Ag-1@GCE and Ag-2@GCE sensors for H₂O₂ was realized with a good linear response over the concentration range from 0.5 μM to 4 mM, a detection limit of 0.136 μM and 0.214 μM (S/N = 3), high selectivity and short response time (< 3 s). Relative to Ag-2@GCE, Ag-1@GCE has better H₂O₂ recognition activity, which is attributed to the extensible one-dimensional structure and more electrocatalytic active sites of complex 1. Moreover, the two electrodes demonstrate high accuracy, with a recovery rate of 96.5 % -103.3 % for H₂O₂ detection. This paper provides a new method for the development of metal complex electrochemical sensors.

合成了两个新的银(I)配合物{[Ag2(S-3Py)2（富马酸酯）]·2C2H5OH·2H2O}n(1)和[Ag2(S-4Py)2（富马酸酯）]·3C2H5OH (2), (S-3Py =双[1-（吡啶-3-甲基）-苯并咪唑-2-基甲基]磺胺，S-4Py =双[1-（吡啶-4-甲基）-苯并咪唑-2-基甲基]磺胺。单晶结构分析表明，配合物1为一维链结构，配合物2为离散双核构型。银(I)配合物骨架结构的差异是由于主配体S-3Py和S-4Py的位阻作用所致。采用恒压计时电流法研究了两种银(I)配合物修饰的玻碳电极（Ag-1@GCE和Ag-2@GCE）在0.2 M PBS中检测过氧化氢的电化学传感性能。该传感器在0.5 μM ~ 4 mM范围内具有良好的线性响应，检测限分别为0.136 μM和0.214 μM (S/N = 3)，选择性高，响应时间短（< 3 S）。相对于Ag-2@GCE， Ag-1@GCE具有更好的H2O2识别活性，这归功于配合物1具有可扩展的一维结构和更多的电催化活性位点。此外，两电极对H2O2的检测精度较高，回收率为96.5% ~ 103.3%。本文为金属络合电化学传感器的研制提供了一种新的途径。

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引用次数: 0

Antioxidant, anti-acetylcholinesterase, antimicrobial, and anticancer activities of Morin–Cu(II) hybrid Nanoflowers Morin-Cu （II）杂交纳米花的抗氧化、抗乙酰胆碱酯酶、抗菌和抗癌活性

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-12-01 DOI: 10.1016/j.poly.2025.117917

Metin Yıldırım , Burcu Somtürk Yilmaz , Mehmet Çimentepe , Adem Necip , Özden Dellal

In recent years, various nanostructures, including nanoflowers, have attracted attention due to their effective biomedical properties. In this study, M@hNFs were synthesized using morin as the organic component and Cu²⁺ ions as the inorganic component. The prepared nanoflowers were characterized by SEM, EDX, FTIR, and XRD analyses, and their biological activities were subsequently investigated, including anticancer effects against MCF-7 breast cancer cells, acetylcholinesterase (AChE) inhibitory activity, antioxidant capacity, antibacterial activity against Staphylococcus aureus, Enterococcus faecalis (E. faecalis), Pseudomonas aeruginosa, Escherichia coli, methicillin-resistant Staphylococcus aureus (MRSA), and multidrug-resistant Escherichia coli (MDR E. coli) using the broth microdilution method, as well as antibiofilm activity against MRSA and MDR E. coli. SEM analysis revealed that the synthesized M@hNFs exhibited a diameter of 24.69 μm. Antioxidant assays demonstrated IC₅₀ values of 131.3 μg/mL (DPPH) and 51.3 μg/mL (ABTS). The AChE inhibitory activity was confirmed with an IC₅₀ value of 72.2 ± 2.1 μg/mL. Furthermore, M@hNFs reduced the viability of MCF-7 cells to 56 % at 500 μg/mL. In antibacterial assays, the synthesized hNFs exhibited stronger activity compared with morin alone, showing the most potent effect against E. faecalis with a MIC value of 32 μg/mL. Importantly, the hNFs also demonstrated activity against resistant strains, inhibiting MRSA and MDR E. coli at 256 μg/mL. At 1024 μg/mL, M@Cu-hNFs inhibited biofilm formation by MRSA and MDR E. coli by 69.7 % and 66.3 %, respectively. Taken together, these findings indicate that the prepared M@hNFs possess multiple biomedical properties and hold significant potential for further studies and future biomedical applications.

近年来，包括纳米花在内的各种纳米结构因其有效的生物医学特性而备受关注。本研究以桑里素为有机组分，Cu2+离子为无机组分合成了M@hNFs。采用SEM、EDX、FTIR和XRD对制备的纳米花进行了表征，并对其生物活性进行了研究，包括对MCF-7乳腺癌细胞的抗癌作用、对乙酰胆碱酯酶（AChE）的抑制活性、抗氧化能力、对金黄色葡萄球菌、粪肠球菌（E. faecalis）、铜绿假单胞菌、大肠杆菌、耐甲氧西林金黄色葡萄球菌（MRSA）的抑菌活性。利用肉汤微量稀释法检测耐多药大肠杆菌（MDR E. coli），以及抗MRSA和MDR E. coli的抗菌膜活性。SEM分析表明，合成的M@hNFs的直径为24.69 μm。抗氧化试验显示IC₅₀值为131.3 μg/mL （DPPH）和51.3 μg/mL （ABTS）。证实了AChE的抑制活性，IC₅₀值为72.2±2.1 μg/mL。此外，M@hNFs在500 μg/mL时将MCF-7细胞的存活率降低至56%。在抗菌实验中，合成的hNFs比单独的桑苷具有更强的抑菌活性，对粪肠杆菌的抑制作用最强，MIC值为32 μg/mL。重要的是，hnf也显示出对耐药菌株的活性，在256 μg/mL的浓度下抑制MRSA和MDR大肠杆菌。在1024 μg/mL浓度下，M@Cu-hNFs对MRSA和MDR大肠杆菌形成生物膜的抑制作用分别为69.7%和66.3%。综上所述，这些发现表明制备的M@hNFs具有多种生物医学特性，具有进一步研究和未来生物医学应用的巨大潜力。

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引用次数: 0

A Keplerate type polyoxometalate-based ionic liquids as heterogeneous hybrid catalysts for efficient oxidation desulfurization using hydrogen peroxide under mild reaction conditions 以Keplerate型多金属氧酸盐为基础的离子液体作为多相杂化催化剂，在温和反应条件下对过氧化氢进行高效氧化脱硫

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-12-01 DOI: 10.1016/j.poly.2025.117913

Mostafa Riahi Farsani

A novel heterogeneous catalyst based on a Keplerate-type polyoxometalate and ionic liquid, W₇₂Fe₃₀-IL, was synthesized via anion exchange between the giant {W₇₂Fe₃₀} cluster and [3-aminoethyl-1-methylimidazolium]Br. The structure of this catalyst was confirmed by FT-IR, Raman, XRD, CHNS, XRF, ICP and thermogravimetric analyses. The resulting hybrid exhibited excellent catalytic performance in the oxidative desulfurization (ODS) of model sulfur-containing compounds, including dibenzothiophene (DBT), benzothiophene (BT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT), using hydrogen peroxide as a green oxidant under mild conditions. Various reaction parameters—oxidant-to-substrate ratio, catalyst loading, temperature, acid promoter, and substrate type—were systematically studied. W₇₂Fe₃₀-IL achieved 99.5 % sulfur removal from DBT at 40 °C within 90 min with an optimal H₂O₂/DBT molar ratio of 4:1. The catalytic activity followed the order DBT > 4,6-DMDBT > BT, correlating with electronic density and steric hindrance around the sulfur atom. Moreover, the catalyst showed excellent reusability over five cycles with minimal activity loss. High structural stability was confirmed by XRD and FTIR, with the hot filtration test and ICP analyse indicating no leaching. This study highlights the potential of Keplerate-type POM-ILs as efficient, recyclable, and environmentally friendly catalysts for deep fuel desulfurization, offering a promising alternative to conventional hydrodesulfurization, which operates under harsher conditions.

以keplerate型多金属氧酸盐和离子液体W₇₂Fe₃₀-IL为原料，通过巨大的{W₇₂Fe₃₀}簇与[3-氨基乙基-1-甲基咪唑]Br之间的阴离子交换，合成了一种新型非均相催化剂W₇₂Fe₃₀-IL。通过FT-IR、Raman、XRD、CHNS、XRF、ICP和热重分析证实了催化剂的结构。该杂化物在温和条件下以过氧化氢为绿色氧化剂，对二苯并噻吩（DBT）、苯并噻吩（BT）和4,6-二甲基二苯并噻吩（4,6- dmdbt）等模型含硫化合物的氧化脱硫（ODS）表现出优异的催化性能。系统地研究了各种反应参数——氧化剂与底物比、催化剂负载、温度、酸促进剂和底物类型。W₇₂Fe₃₀-IL在40°C下90分钟内从DBT中脱除99.5%的硫，最佳H₂O₂/DBT摩尔比为4:1。催化活性为DBT >； 4,6- dmdbt >； BT，与硫原子周围的电子密度和位阻有关。此外，该催化剂在5次循环中表现出优异的可重复使用性，且活性损失最小。XRD和FTIR分析证实了该材料具有较高的结构稳定性，热过滤试验和ICP分析表明其无浸出。该研究强调了keplerate型pom - il作为高效、可回收、环保的深层燃料脱硫催化剂的潜力，为在恶劣条件下运行的传统加氢脱硫提供了一种有希望的替代方案。

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引用次数: 0

Catalytic oxidation pathways for biomass-derived aromatics from lignin 木质素生物质衍生芳烃的催化氧化途径

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron

Pub Date : 2025-11-29 DOI: 10.1016/j.poly.2025.117911

Xinquan Li , Hao Zhang , Mahdi M. Abu-Omar

The selective oxidation of lignin into value-added aromatic compounds represents a promising strategy for biomass valorization and the advancement of sustainable chemical feedstocks. This review highlights recent developments in aerobic lignin oxidation methods over the past decade. A mechanistic understanding of bond activation, including CC and CO cleavage pathways, is examined through studies of both model lignin compounds and complex lignin polymers. The role of transition-metal catalysts is discussed in the context of maximizing activity and selectivity.

木质素选择性氧化为高附加值芳香族化合物是生物质增值和可持续化工原料发展的一个有前途的策略。本文综述了近十年来好氧木质素氧化方法的最新进展。通过模型木质素化合物和复杂木质素聚合物的研究，对键激活的机制理解，包括CC和CO裂解途径进行了研究。从活性和选择性最大化的角度讨论了过渡金属催化剂的作用。

引用次数: 0