Journal of Molecular Structure最新文献

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Reversible phase transition, dielectric and fluorescent properties of chiral 3D double perovskites 手性三维双钙钛矿的可逆相变、介电和荧光性质
IF 4.7 2区 化学
Journal of Molecular Structure Pub Date : 2025-10-09 DOI: 10.1016/j.molstruc.2025.144320
Yuting Li , Xiao Sun , Xin Yin , Hu Cai , Zhenhong Wei
{"title":"Reversible phase transition, dielectric and fluorescent properties of chiral 3D double perovskites","authors":"Yuting Li ,&nbsp;Xiao Sun ,&nbsp;Xin Yin ,&nbsp;Hu Cai ,&nbsp;Zhenhong Wei","doi":"10.1016/j.molstruc.2025.144320","DOIUrl":"10.1016/j.molstruc.2025.144320","url":null,"abstract":"<div><div>Organic-inorganic hybrid rare-earth double perovskite materials, as a novel multifunctional material system, have demonstrated broad application prospects in ferroelectrics, ferroelastics, piezoelectrics, ferromagnetics, superconductivity, and optoelectronic devices due to their unique organic-inorganic synergistic effects and the <em>4f</em> electronic characteristics of rare-earth ions. However, current research predominantly focuses on non-chiral systems, while the integration of chiral organic amines with three-dimensional bimetallic perovskite frameworks remains less explored. In this study, based on a molecular engineering strategy, we successfully synthesized two novel chiral hybrid double perovskite compounds [<em>R</em>-3-HDMP]<sub>2</sub>RbSm(NO<sub>3</sub>)<sub>6</sub> (<strong>1</strong>) and [<em>S</em>-3-HDMP]<sub>2</sub>RbSm(NO<sub>3</sub>)<sub>6</sub> (<strong>2</strong>) (3-HDMP = hydroxy‑<em>N,N</em>-dimethylpyrrolidinium) through precise modification of azacyclic amine skeletons with chiral hydroxyl groups, followed by self-assembly with alkali metal salts and rare-earth metal salts in a 2:1:1 stoichiometric ratio. The enantiomeric configurations of both compounds were demonstrated through vibrational circular dichroism (VCD) spectroscopy. The structures of the compounds were characterized by the variable temperature X-ray single-crystal diffractometer. A differential scanning calorimeter was used to reveal the significant reversible phase transition behavior of <strong>1</strong> and <strong>2</strong> near 251 K/239 K. Meanwhile, the dielectric constant was evaluated to show that stepwise dielectric anomalies occurred near the phase transition temperature. In addition, the fluorescence spectra revealed the characteristic emission behavior of Sm<sup>3</sup>⁺. Obvious peaks were observed at 564 nm (corresponding to the <sup>4</sup><em>G</em><sub>5/2</sub> → <sup>6</sup><em>H</em><sub>5/2</sub> transition), 597 nm (corresponding to the <sup>4</sup><em>G</em><sub>5/2</sub> → <sup>6</sup><em>H</em><sub>7/2</sub> transition) and 646 nm (corresponding to the <sup>4</sup><em>G</em><sub>5/2</sub> → <sup>6</sup><em>H</em><sub>9/2</sub> transition), confirming that the energy level structure of rare earth ions in the hybrid system was well preserved. This study not only expands the material library of chiral hybrid perovskites but also provides new ideas for the collaborative design of multiferroic materials and optoelectronic functional materials.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144320"},"PeriodicalIF":4.7,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145270350","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
A zero-dimensional hybrid manganese bromide with long luminescence lifetime, temperature-dependent emissions, and glass transition behavior 一种零维杂化溴化锰,具有长发光寿命、温度依赖性发射和玻璃化转变行为
IF 4.7 2区 化学
Journal of Molecular Structure Pub Date : 2025-10-09 DOI: 10.1016/j.molstruc.2025.144319
Kai Li, Jia-Qi Du, Cen-Man Wang, Guoli Yang, Jin Kang, Yong-Qiang Chen
{"title":"A zero-dimensional hybrid manganese bromide with long luminescence lifetime, temperature-dependent emissions, and glass transition behavior","authors":"Kai Li,&nbsp;Jia-Qi Du,&nbsp;Cen-Man Wang,&nbsp;Guoli Yang,&nbsp;Jin Kang,&nbsp;Yong-Qiang Chen","doi":"10.1016/j.molstruc.2025.144319","DOIUrl":"10.1016/j.molstruc.2025.144319","url":null,"abstract":"<div><div>Zero-dimensional (0D) hybrid manganese halides have received substantial attention due to their excellent optoelectronic properties. Herein, a 0D hybrid manganese bromide [DMPBA]<sub>2</sub>[MnBr<sub>4</sub>] (DMPBA<sup>+</sup> = Dimethylphenylbenzylammonium) was successfully synthesized. In the structure, there are not only Coulomb interactions but also strong <em>C</em> − <em>H</em>⋅⋅⋅Br hydrogen-bonding forces between [MnBr<sub>4</sub>]<sup>2−</sup> and DMPBA<sup>+</sup> building units. This compound exhibits a typical green emission with a high photoluminescence (PL) quantum yield value of 62.39 %. Meanwhile, [DMPBA]<sub>2</sub>[MnBr<sub>4</sub>] possesses a long lifetime of 1.3 ms at room temperature, which is far higher than those of reported 0D hybrid manganese bromides. Theoretical calculations show that [DMPBA]<sub>2</sub>[MnBr<sub>4</sub>] has a direct bandgap electronic structure with a band gap value of 2.58 eV where the valence band maximum and conduction band minimum are entirely governed by [MnBr<sub>4</sub>]<sup>2−</sup> units. As the temperature increases from 120 to 400 K, the PL emission of [DMPBA]<sub>2</sub>[MnBr<sub>4</sub>] presents a monotonically blue shift, which is ascribed to the decreased crystal field strength of Mn<sup>2+</sup> owing to the effect of lattice thermal expansion. In addition, [DMPBA]<sub>2</sub>[MnBr<sub>4</sub>] exhibits a crystal-glass transition behavior and the glassy sample shows a near-yellow emission under UV light excitation.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144319"},"PeriodicalIF":4.7,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145270509","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Steroidal arylidene hybrids with phenolic moieties: Integrated in silico, DFT, and electrochemical evaluation for therapeutic targeting 甾体芳基杂化与酚类:集成在硅,DFT,和电化学评价治疗靶向
IF 4.7 2区 化学
Journal of Molecular Structure Pub Date : 2025-10-09 DOI: 10.1016/j.molstruc.2025.144297
Mohammed T. Qaoud , İrfan Çapan , Sinan Saydam , Süleyman Servi
{"title":"Steroidal arylidene hybrids with phenolic moieties: Integrated in silico, DFT, and electrochemical evaluation for therapeutic targeting","authors":"Mohammed T. Qaoud ,&nbsp;İrfan Çapan ,&nbsp;Sinan Saydam ,&nbsp;Süleyman Servi","doi":"10.1016/j.molstruc.2025.144297","DOIUrl":"10.1016/j.molstruc.2025.144297","url":null,"abstract":"<div><div>Targeting dual modulators of androgen biosynthesis enzymes, two phenol-substituted steroidal arylidene analogs—Dehydroepiandrosterone-Fn (DHEA-Fn) and Pregnenolone-Fn (PREG-Fn), where “Fn” denotes a phenolic moiety—were structurally characterized and comprehensively evaluated through a multidisciplinary approach integrating spectroscopic, electrochemical, and in silico analyses. Advanced Nuclear Magnetic Resonance (NMR) techniques, including two-dimensional heteronuclear correlation (2D-HETCOR) NMR, confirmed E/Z isomerism in DHEA-Fn and supported precise assignment of regiochemical and stereoelectronic features. Structure-guided molecular docking and molecular mechanics–generalized Born surface area (MM-GBSA) calculations predicted favorable binding to 5α-reductase type 2 and CYP17A1, positioning the compounds as potential dual inhibitors relevant to prostate cancer therapy. DHEA-Fn exhibited a superior docking profile (–10.53 kcal/mol) compared to the positive control Finasteride. Density functional theory (DFT) calculations indicated narrow HOMO–LUMO energy gaps and high electron affinity values, supporting enhanced redox reactivity and antioxidant potential. Electrochemical characterization using cyclic and square wave voltammetry confirmed quasi-reversible redox behavior consistent with the conjugated arylidene–phenol framework. This conjugated arylidene–phenol is proposed to act as a redox-active structural motif (i.e., a moiety capable of reversible electron transfer), potentially influencing bioactivation, oxidative stability, and interactions with redox-sensitive biological targets. In silico ADMET (absorption, distribution, metabolism, excretion, and toxicity) modeling further predicted excellent oral bioavailability, blood–brain barrier permeability, and no violations of drug-likeness rules. Distinct P-glycoprotein interaction profiles suggest variable CNS efflux, which may influence neuroactivity and systemic distribution. Together, the integration of electrochemical analysis and in silico modeling provides a predictive, mechanism-oriented framework for evaluating the therapeutic viability of steroidal scaffolds. These findings highlight DHEA-Fn and PREG-Fn as rationally designed, multifunctional candidates with favorable physicochemical, electronic, and pharmacological profiles for further development in androgen-related oncology.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144297"},"PeriodicalIF":4.7,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145270259","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Study of the interaction mechanisms of ellagitannins from Phyllanthus emblica L. with acetylcholinesterase using multi-spectroscopy, molecular docking, and molecular dynamic 利用多光谱、分子对接和分子动力学研究余甘子鞣花单宁与乙酰胆碱酯酶的相互作用机制
IF 4.7 2区 化学
Journal of Molecular Structure Pub Date : 2025-10-09 DOI: 10.1016/j.molstruc.2025.144229
Yangzom Dawa , Jin-Wang Wei , Cong-Qing Wang , Juan Chen
{"title":"Study of the interaction mechanisms of ellagitannins from Phyllanthus emblica L. with acetylcholinesterase using multi-spectroscopy, molecular docking, and molecular dynamic","authors":"Yangzom Dawa ,&nbsp;Jin-Wang Wei ,&nbsp;Cong-Qing Wang ,&nbsp;Juan Chen","doi":"10.1016/j.molstruc.2025.144229","DOIUrl":"10.1016/j.molstruc.2025.144229","url":null,"abstract":"<div><div>Ellagitannins, a class of hydrolysable tannins widely present in <em>Phyllanthus emblica</em> L., exhibit inhibitory effects on acetylcholinesterase (AChE) activity; however, their inhibition mechanisms remain poorly characterized to date. In this study, the inhibition mechanism between four ellagitannins and AChE was systematically analyzed by integrating enzyme inhibition kinetics, multi-spectral analysis, molecular docking and molecular dynamics simulation. Enzyme inhibition kinetics indicated that all four ellagitannins were reversible inhibitors of AChE, with corilagin being a mixed inhibitor and ellagic acid, geraniin and chebulagic acid being uncompetitive inhibitors. Fluorescence spectroscopy confirmed that the four ellagitannins formed complexes with AChE and quenched the intrinsic fluorescence of AChE through static quenching, with only one binding site. The binding was mainly driven by hydrogen bonds and van der Waals forces, and the binding process was an enthalpy-driven spontaneous exothermic process. It can also quench the synchronous fluorescence of tyrosine (Tyr) and tryptophan (Trp), and change the microenvironment around the tryptophan residues. Fluorescence resonance energy transfer further verified that the fluorescence quenching was the result of non-radiative energy resonance and static quenching. UV–vis, FT-IR and CD spectroscopy results showed that the formation of enzyme-inhibitor complexes altered the secondary structure of AChE. Molecular docking and molecular dynamics simulation further verified that the four ellagitannins embedded in the hydrophobic pocket of AChE to form stable complexes, and formed hydrogen bonds with surrounding amino acid residues, making the enzyme structure more stable and hindering the entry of substrates, ultimately inhibiting AChE activity. Overall, our study provides novel insights into ellagitannins as natural AChE inhibitors and their potential as therapeutic candidates for Alzheimer’s disease.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144229"},"PeriodicalIF":4.7,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145270347","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
A hydroxyl-extended 1D dysprosium chain with two well-separated magnetic relaxation processes 一个羟基延伸的一维镝链具有两个分离良好的磁弛豫过程
IF 4.7 2区 化学
Journal of Molecular Structure Pub Date : 2025-10-09 DOI: 10.1016/j.molstruc.2025.144303
Yan Li , Ya You , Fang-Zhi Li , Qi-Shu Zhong , Yi-Quan Zhang , En-Cui Yang
{"title":"A hydroxyl-extended 1D dysprosium chain with two well-separated magnetic relaxation processes","authors":"Yan Li ,&nbsp;Ya You ,&nbsp;Fang-Zhi Li ,&nbsp;Qi-Shu Zhong ,&nbsp;Yi-Quan Zhang ,&nbsp;En-Cui Yang","doi":"10.1016/j.molstruc.2025.144303","DOIUrl":"10.1016/j.molstruc.2025.144303","url":null,"abstract":"<div><div>A 1D dysprosium chain {[Dy(CH<sub>3</sub>OH)Cl<sub>2</sub>(tpy)]·CH<sub>3</sub>OH}<em><sub>n</sub></em> (Htpy = 4′-(4-hydroxyphenyl)-2,2′:6′,2′'-terpyridine) that behaves as a single-ion magnet (SIM) and displays two well-separated relaxation processes with the zero-field effective energy barriers of 372.5 and 529.8 K, which represents the record thermal relaxation barrier among the reported one-dimensional Dy<sup>III</sup>-based systems containing only one spin center. A magnetic hysteresis loop up to 6.0 K at a sweep rate of 200 Oe s<sup>-1</sup> is also observed. To explore the origin of these distinct relaxations, two crystallographically isostructural analogues including diamagnetic Y<sup>III</sup>- (<strong>2</strong>) and Y<sup>III</sup>-doped Dy<sub>0.2</sub>Y<sub>0.8</sub> (<strong>3</strong>) were prepared and characterized structurally and magnetically. The persistence of bimodal peaks in the out-of-phase magnetic susceptibility (<em>χ″</em>) of diluted sample <strong>3</strong> indicates that the dual-step relaxation behavior primarily originates from the single-ion anisotropy of Dy<sup>III</sup> ions. Structural analyses combined with XRD pattern comparisons pre- and post-magnetic measurements elucidated that the dual-step relaxation in complex <strong>1</strong> is related to partially desolvated samples. This work sheds light on the multiple relaxation mechanism and further provides important information for the development of high-performance SMMs.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144303"},"PeriodicalIF":4.7,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145270337","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Synthesis, structural studies and electrocatalytic water oxidation properties of molecular copper complexes: The influence of N-alkylation of ligand and coordination number 铜分子配合物的合成、结构研究及电催化水氧化性能:配体n -烷基化和配位数的影响
IF 4.7 2区 化学
Journal of Molecular Structure Pub Date : 2025-10-09 DOI: 10.1016/j.molstruc.2025.144339
Lianghui Zhang , Yuan Wang , Haiyan Lan , Tao Xu , Zhijun Ruan , Junqi Lin , Xiangming Liang , Xiaohong Cheng , Jingwen Ran
{"title":"Synthesis, structural studies and electrocatalytic water oxidation properties of molecular copper complexes: The influence of N-alkylation of ligand and coordination number","authors":"Lianghui Zhang ,&nbsp;Yuan Wang ,&nbsp;Haiyan Lan ,&nbsp;Tao Xu ,&nbsp;Zhijun Ruan ,&nbsp;Junqi Lin ,&nbsp;Xiangming Liang ,&nbsp;Xiaohong Cheng ,&nbsp;Jingwen Ran","doi":"10.1016/j.molstruc.2025.144339","DOIUrl":"10.1016/j.molstruc.2025.144339","url":null,"abstract":"<div><div>In this study, we report the synthesis, structural studies, and electrocatalytic water oxidation properties of three novel Cu complexes featuring 2-pyridylmethyl-substituted 1,4,7-triazacyclononane ligands. Structural characterizations reveal the penta-coordination structure of complex [Cu(Py<sub>2</sub>tcan)](ClO<sub>4</sub>)<sub>2</sub> (<strong>1</strong>, Py<sub>2</sub>tcan = 1,4-bis(2-picolyl)-1,4,7-triazacyclononane) and complex [Cu(MePy<sub>2</sub>tcan)](ClO<sub>4</sub>)<sub>2</sub> (<strong>2</strong>, MePy<sub>2</sub>tcan = 1-methyl-4,7-bis(2-picolyl)-1,4,7-triazacyclononane), as well as the six-coordination structure of complex [Cu(Py<sub>3</sub>tcan)](ClO<sub>4</sub>)<sub>2</sub> (<strong>3</strong>, Py<sub>3</sub>tcan = 1,4,7-tris(2-picolyl)-1,4,7-triazacyclononane). Systematic electrochemical analysis reveals that <strong>1</strong> and <strong>2</strong> exhibit high catalytic efficiency for water oxidation. Mechanistic studies suggest that the secondary amine coordination in <strong>1</strong> significantly reduces the catalytic overpotential by enhancing the σ-donor effect, thereby facilitating Cu center oxidation and enhancing the catalytic cycle. While <strong>2</strong> featuring two pyridine groups and three tertiary amine groups in its coordination environment performs higher catalytic overpotential than <strong>1</strong> because of the poor σ-donor properties of its <em>N</em>–CH<sub>3</sub> structure. Besides, <strong>3</strong> shows much lower catalytic activity, underscoring the necessity of an unsaturated coordination geometry for efficient water oxidation. Compared to its analogous Ni complex [Ni(Py<sub>3</sub>tcan)]<sup>2+</sup> (<strong>4</strong>) and Fe complex [Fe(Py<sub>3</sub>tcan)]<sup>2+</sup>, <strong>3</strong> shows higher onset overpotential and lower catalytic activity, indicating that even when stabilized by the same Py<sub>3</sub>tacn ligand, the Cu center possesses inferior intrinsic catalytic activity for water oxidation relative to Ni and Fe centers. Nevertheless, the catalytic performance of such Cu complex can be enhanced through rational modulation of the ligand structure and coordination number.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144339"},"PeriodicalIF":4.7,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145270905","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Novel thiazoline derivatives: Synthesis, characterisation, and molecular docking investigations as potential anticancer agents 新型噻唑啉衍生物:合成、表征和潜在抗癌药物的分子对接研究
IF 4.7 2区 化学
Journal of Molecular Structure Pub Date : 2025-10-09 DOI: 10.1016/j.molstruc.2025.144321
Zena M. Mostaf , Mukhlif Mohsin Slaihim
{"title":"Novel thiazoline derivatives: Synthesis, characterisation, and molecular docking investigations as potential anticancer agents","authors":"Zena M. Mostaf ,&nbsp;Mukhlif Mohsin Slaihim","doi":"10.1016/j.molstruc.2025.144321","DOIUrl":"10.1016/j.molstruc.2025.144321","url":null,"abstract":"<div><div>To synthesise new thiazoline derivative compounds and evaluate their structural characteristics and molecular binding affinities in comparison to the standard drug 5-fluorouracil.</div><div>New thiazoline derivatives were synthesised by reacting equimolar amounts of carbon disulfide and 3-chloroacetyl-2,4‑dione with aromatic amine derivatives in absolute ethanol. The melting points of the synthesised compounds were determined using an Electro Melting Point Apparatus. Structural characterisation was carried out utilizing Fourier-transform infrared spectroscopy (FTIR-8400), proton nuclear magnetic resonance (<sup>1</sup>HNMR ),carbon-13 nuclear magnetic resonance (<sup>13</sup>CNMR ), and gas chromatography-mass spectrometry GC–MS, model MASS-ll. Molecular docking studies were performed using AutoDock Vina to assess the binding interactions between the synthesised compounds and selected protein targets, with comparisons made to the binding affinity of 5-fluorouracil. The synthesised thiazoline derivatives exhibited distinct melting points and were successfully characterised by the applied spectroscopic techniques. Molecular docking results revealed that the free binding energies of the synthesised compounds with the target proteins were higher than those of 5-fluorouracil, suggesting potentially stronger protein-ligand interactions. The newly synthesised thiazoline derivatives demonstrate promising binding affinities towards target proteins, surpassing those of the conventional drug 5-fluorouracil, and thus may serve as potential candidates for further pharmaceutical development.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144321"},"PeriodicalIF":4.7,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145270892","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Structural design of polyoxometalate-based coordination polymers for near-infrared-responsive photothermal catalytic degradation of organic pollutants 近红外响应光热催化降解有机污染物的多金属酸氧基配位聚合物结构设计
IF 4.7 2区 化学
Journal of Molecular Structure Pub Date : 2025-10-09 DOI: 10.1016/j.molstruc.2025.144302
Wenxu Ma, Yunqiong Yang
{"title":"Structural design of polyoxometalate-based coordination polymers for near-infrared-responsive photothermal catalytic degradation of organic pollutants","authors":"Wenxu Ma,&nbsp;Yunqiong Yang","doi":"10.1016/j.molstruc.2025.144302","DOIUrl":"10.1016/j.molstruc.2025.144302","url":null,"abstract":"<div><div>Two new polyoxometalate-based coordination polymers (POM@CPs), namely [Cu<sub>3</sub>(biim)<sub>6</sub>(PMo<sub>12</sub>O<sub>40</sub>)]·5H<sub>2</sub>O (JOU-46) and [Cu<sub>2</sub>(Cl)(impy)<sub>4</sub>][PMo<sub>12</sub>O<sub>40</sub>]·H<sub>2</sub>O (JOU-47), were synthesized via a hydrothermal method (biim = 2,2’-biimidazole, impy = 2-(imidazol-2-yl) pyridine). Single-crystal X-ray diffraction revealed that JOU-46 forms a three-dimensional (3D) supramolecular framework constructed from ladder-type chains linked by hydrogen bonds, whereas JOU-47 exhibits a 3D supramolecular architecture assembled from Cu-impy fragments and [PMo<sub>12</sub>O<sub>40</sub>]<sup>3−</sup> clusters. Benefiting from their broad absorption range and excellent photothermal conversion efficiency, these materials significantly enhance photocatalytic performance and solar energy utilization. Under the irradiation of simulated sunlight, surface temperature of JOU-47 increased from 32 °C to 166 °C within 120 s. Compared with JOU-46, JOU-47 exhibited a broader light absorption range and a higher photothermal conversion efficiency (44.4% vs. 29.1%). In JOU-47/H<sub>2</sub>O<sub>2</sub> system, 95.2% of tetracycline hydrochloride was degraded within 50 min, giving a rate constant of 0.06 min<sup>−1</sup>. Moreover, this system can also efficiently remove various organic pollutants. This work provides insights for designing efficient POM@CP-based photothermal catalysts for water purification.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144302"},"PeriodicalIF":4.7,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145270893","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
The dicyanoisophorone Scaffold: A versatile platform for near-infrared, large stokes shift fluorescent probes in sensing and bioimaging 二氰异佛龙支架:近红外,大斯托克斯位移荧光探针传感和生物成像的多功能平台
IF 4.7 2区 化学
Journal of Molecular Structure Pub Date : 2025-10-09 DOI: 10.1016/j.molstruc.2025.144298
Bin Lin, Shuting Li, Yifeng Han
{"title":"The dicyanoisophorone Scaffold: A versatile platform for near-infrared, large stokes shift fluorescent probes in sensing and bioimaging","authors":"Bin Lin,&nbsp;Shuting Li,&nbsp;Yifeng Han","doi":"10.1016/j.molstruc.2025.144298","DOIUrl":"10.1016/j.molstruc.2025.144298","url":null,"abstract":"<div><div>Dicyanoisophorone (DCI) derivatives are an emerging platform for NIR, large‑Stokes‑shift fluorescent probes. We synthesize recent advances in DCI probe design, photophysics, and applications, with emphasis on structure–property rules and translational use. These characteristics make DCI-based probes highly suitable for demanding applications in complex biological systems and in vivo imaging, overcoming limitations associated with traditional fluorophores such as autofluorescence interference and limited tissue penetration. This review summarizes the significant advancements in the design and application of functional fluorescent probes based on the DCI scaffold reported in recent literature. Compared with BODIPY and rhodamine (often narrow Stokes shifts) and cyanines/hemicyanines (photostability and quantum‑yield limitations), DCI derivatives offer NIR emission with large Stokes shifts driven by robust ICT, supporting deep imaging with reduced crosstalk. We systematically categorize these probes based on their target analytes, encompassing reactive oxygen species (ROS), reactive nitrogen species (RNS), reactive sulfur species (RSS), reactive carbonyl species (RCS) including carbon monoxide (CO), cellular microenvironment parameters (viscosity, pH, polarity), environmental pollutants (metal ions, organic contaminants), enzyme activities (hydrolases, oxidoreductases), and specific subcellular organelles (lipid droplets, lysosomes) or biomolecules (amino acids, proteins, amyloid aggregates). Key design strategies, including analyte-triggered modulation of ICT, PET, FRET, ESIPT, and TICT mechanisms, as well as aggregation-induced emission (AIE) and specific binding interactions, are discussed. The diverse applications highlighted herein, ranging from fundamental cell biology studies, in vivo imaging in various disease models (e.g., cancer, neurodegeneration, diabetes, inflammation, liver injury), environmental monitoring, and food safety analysis to potential diagnostics and theranostics, underscore the remarkable versatility and growing impact of DCI-based probes. This comprehensive overview aims to provide valuable insights and guide future research in the rational design and application of advanced NIR fluorescent probes with large Stokes shifts for biomedical and analytical sciences.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144298"},"PeriodicalIF":4.7,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145270348","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Azo-based-functionalized rice husk silica nanocomposites for dual-mode sensing of Hg(II) and Ag(I): Experimental insights and DFT-elucidated mechanism 偶氮基功能化稻壳二氧化硅纳米复合材料对汞(II)和银(I)的双模传感:实验见解和dft解析机制
IF 4.7 2区 化学
Journal of Molecular Structure Pub Date : 2025-10-06 DOI: 10.1016/j.molstruc.2025.144294
Wafa Mazi , Omaymah Alaysuy , Kholood M. Alkhamis , Marwah A. Alsharif , Amnah S. Al Zbedy , Renad Almughathawi , Bandar A. Babgi , Nashwa M. El-Metwaly
{"title":"Azo-based-functionalized rice husk silica nanocomposites for dual-mode sensing of Hg(II) and Ag(I): Experimental insights and DFT-elucidated mechanism","authors":"Wafa Mazi ,&nbsp;Omaymah Alaysuy ,&nbsp;Kholood M. Alkhamis ,&nbsp;Marwah A. Alsharif ,&nbsp;Amnah S. Al Zbedy ,&nbsp;Renad Almughathawi ,&nbsp;Bandar A. Babgi ,&nbsp;Nashwa M. El-Metwaly","doi":"10.1016/j.molstruc.2025.144294","DOIUrl":"10.1016/j.molstruc.2025.144294","url":null,"abstract":"<div><div>A cost-effective dual-mode sensor was fabricated by covalently immobilizing para red 1-((4-nitrophenyl)diazenyl)naphthalen-2-ol on rice-husk-derived mesoporous silica to yield PR@RHS, a nanocomposite that couples agricultural-waste valorization with high-performance metal-ion detection. Thorough physicochemical characterization confirmed retention of the amorphous silica framework (broad XRD halo at 2θ≈21.35°) and preservation of well-defined mesoporosity (BET surface area 285 m<sup>2</sup>/g), while FTIR analysis revealed the emergence of <em>C</em> = <em>N</em> and <em>N</em> = <em>N</em> stretching bands, evidencing successful azo-based grafting. Density Functional Theory calculations clarified that Hg(II) coordinates through bidentate ON-chelation, inducing a bathochromic shift, whereas Ag(I) binds linearly to the azo nitrogens, producing a hypsochromic shift and distinct spectral fingerprints. Under optimized conditions (20 mg material in 10 mL solution, pH 4.0 for Hg(II) and pH 3.5 for Ag(I), 25 °C), PR@RHS achieved limits of detection of 13.67 ± 0.45 ppb (RSD = 3.3 %) ppb for Hg(II) and 10.25 ppb ± 0.38 ppb (RSD = 3.1 %) for Ag(I) with rapid response times of 140 s and 90 s, respectively, and negligible interference from 13 common metal ions even at 100 ppm. The probe retained ≥80 % of its initial signal after five EDTA/thiourea regeneration cycles and ≥81 % activity after 12-month room-temperature storage, highlighting outstanding durability. Practical utility was demonstrated by quantitative mercury screening in commercial skin-lightening creams (recoveries 95.8–101.2 %, RSD ≤ 3.8 %) and high-efficiency silver recovery from electronic-waste leachates (overall yield 93.85 % for e-waste). These results establish PR@RHS as a sustainable, reusable platform that bridges environmental monitoring and resource reclamation through green nanotechnology.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144294"},"PeriodicalIF":4.7,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145270346","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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