Journal of Molecular Structure最新文献

{"title":"Anti-adipogenic and antioxidant benzophenone dimers from the tea making leaves of cultivated Aquilaria sinensis (Lour.) Spreng","authors":"Wei Luo ,&nbsp;Hui-Zhen Zhou ,&nbsp;Qin-Zhao Kang ,&nbsp;Hu-Lan Chen ,&nbsp;Li-Mei Li","doi":"10.1016/j.molstruc.2025.144219","DOIUrl":"10.1016/j.molstruc.2025.144219","url":null,"abstract":"<div><div><em>Aquilaria sinensis</em> (Lour.) Gilg leaf has been approved as a new food raw material in China and Japan, and used as tea and other health care products. In the chemical study on the water extract of <em>A. sinensis</em> leaf, a pair of benzophenone atropisomers, named aquidibenzophenonsides A and B (<strong>1</strong> and <strong>2</strong>), as well as 10 known compounds, were isolated and identified on the basis of a comprehensive interpretation of the MS, CD, and 1D and 2D NMR spectroscopic data. Compounds <strong>1</strong> and <strong>2</strong> are a class of symmetrical benzophenone dimers, representing an unprecedented 10-membered ring system. In the DPPH and ABTS^•+ assays, compounds <strong>1</strong> and <strong>2</strong> exhibited significant antioxidant activity with IC₅₀ values between 12.24 ± 1.08 <em>µ</em>g/mL and 30.90 ± 0.40 <em>µ</em>g/mL. In the <em>in vivo</em> antioxidant activity assay, compounds <strong>1</strong> and <strong>2</strong> significantly decreased the content of reactive oxygen species (ROS) and improved the survival rate of <em>Caenorhabditis elegans</em>. Furthermore, compounds <strong>1</strong> and <strong>2</strong> could effectively reduce fat deposition in <em>C. elegans</em>. Molecular docking simulations indicated that the anti-adipogenic effects of compounds <strong>1</strong> and <strong>2</strong> may be mediated through their interaction with fatty acid synthase.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144219"},"PeriodicalIF":4.7,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145270514","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}

{"title":"A new fluorinated hydrazone derivative as a multitarget therapeutic agent: Synthesis, crystal structure, spectroscopic characterization, Hirshfeld surface analysis, DFT/TD-DFT studies, NLO properties, in silico molecular docking, ADMET profiling, and biomimetic oxidation activity","authors":"Chaima MAOUCHE ,&nbsp;Salima TABTI ,&nbsp;Douniazed HANNACHI ,&nbsp;Amel DJEDOUANI ,&nbsp;Tinhinane LOUAILECHE ,&nbsp;Abdenour GUERRAOUI ,&nbsp;Sarra GOUDJIL ,&nbsp;Mohamed Larbi MEDJROUBI ,&nbsp;Olivier JEANNIN ,&nbsp;Helen STOECKLI-EVANS","doi":"10.1016/j.molstruc.2025.144227","DOIUrl":"10.1016/j.molstruc.2025.144227","url":null,"abstract":"<div><div>A new hydrazone molecule HL: (E)-2-fluoro-<em>N'</em>-(1-(4-hydroxy-6-methyl-2-oxo-2<em>H</em>-pyran-3-yl)ethylidene)benzohydrazide, was synthesized by condensation of 2-fluorobenzohydrazide with dehydroacetic acid. The structure of HL was confirmed using spectroscopic analysis, including NMR (¹H, ¹³C), UV-visible and infrared, and single crystal <em>X-</em>ray diffraction. This compound adopted a zwitterionic form <strong>HL’</strong> stabilized by intramolecular hydrogen bonding interactions between [N⁺—H…^-O] groups and crystallized in the monoclinic system with space group <em>P2₁/c</em>. Indeed, Hirshfeld surface analysis was performed to visualize and quantify the intermolecular interactions within the crystalline structure, revealing the presence of intermolecular contacts involving H···Ο and H···F hydrogen bonds and non-conventional C–H···H, C–H···π, and π···<em>lp</em> interactions, as well as π–π stacking. DFT calculations were carried out using the ωB97X-D functional with the 6-31+G(d) basis set. Based on DFT conceptual principles, key global molecular reactivity descriptors were obtained, including chemical hardness, electronic chemical potential, electronegativity, and electrophilicity index. Furthermore, the nonlinear optical properties of the compound <strong>HL</strong> and its tautomer <strong>HL</strong> ↔ HL’’ were explored, revealing promising potential for applications in second- and third-order NLO materials. Molecular docking studies were also conducted to evaluate the <em>in silico</em> biological activity of <strong>HL</strong> against cholinesterase enzymes, specifically acetylcholinesterase and butyrylcholinesterase. Furthermore, the physicochemical and pharmacokinetic properties of the molecule were assessed through ADMET analysis, confirming its favorable drug-likeness characteristics. In this study, we aim to evaluate the catalytic activity of <em>in-situ</em> complexes formed using <strong>HL</strong> as a catalyst with Cu^II salts, which are commonly used in the oxidation of catechol to <em>o-</em>quinone.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144227"},"PeriodicalIF":4.7,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145271224","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}

{"title":"Design, synthesis, and insecticidal activities of novel thioether derivatives","authors":"Feng Hao ,&nbsp;Lan Cai ,&nbsp;Huawen Wang ,&nbsp;Li Zhu ,&nbsp;Jiting Li ,&nbsp;Xiao Zhang ,&nbsp;Yinong Wang ,&nbsp;Ju Zhang ,&nbsp;Jingyi Li ,&nbsp;Nali Song ,&nbsp;Xia Zhao ,&nbsp;Le Cai","doi":"10.1016/j.molstruc.2025.144228","DOIUrl":"10.1016/j.molstruc.2025.144228","url":null,"abstract":"<div><div>Mosquitoes are significant vectors of diseases which cause tens of thousands of deaths annually and impose heavy treatment costs on affected regions. Although insecticides have been effective in managing pest damage, their widespread and continuous use has led to the emergence of resistance, presenting a major challenge in pest control. To address this issue, the design of novel insecticides is crucial. A series of novel thioether compounds were synthesized and characterized via a scaffold hopping strategy and their insecticidal activity against both larvae and adult mosquitoes of <em>Armigeres subalbatus</em>, as well as against <em>Brevicoryne brassicae</em> and <em>Pieris rapae</em> Linn were evaluated. All target compounds exhibited excellent insecticidal activity. The insecticidal mechanisms were investigated through Ellman’s method and molecular docking studies. Additionally, DFT calculations were used to analyze why compound <strong>A7</strong> (LC₅₀=0.0155 mg/L) showed less insecticidal activity compared to the positive control, cypermethrin (LC₅₀=0.0145 mg/L) and higher insecticidal activity compared to dichlorvos (LC₅₀=0.0469 mg/L). A 3D-QSAR model was developed to predict the efficacy of this class of compounds and the ADME properties revealed good lipophilicity and well-predicted oral bioavailability. The findings of this study are expected to contribute to the development of more effective and environmentally friendly agricultural chemicals, addressing the issue of pest resistance.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144228"},"PeriodicalIF":4.7,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145270273","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}

{"title":"Research progress on a near-infrared fluorescence probe composed of carbazole skeleton for biological imaging","authors":"Jianqiang Qian ,&nbsp;Yaqin Gu ,&nbsp;Zihao Wang ,&nbsp;Mingshi Pan ,&nbsp;Dingding Li ,&nbsp;Jinfeng Ding","doi":"10.1016/j.molstruc.2025.144222","DOIUrl":"10.1016/j.molstruc.2025.144222","url":null,"abstract":"<div><div>Fluorescence imaging has become an essential, non-invasive tool in biomedical research, enabling the visualization of diseased tissues beyond the capabilities of the human eye and facilitating the distinction between healthy and pathological tissues. Among various imaging approaches, near-infrared (NIR) fluorescence imaging addresses the limitations posed by traditional fluorescence methods, such as strong tissue absorption, scattering, and background autofluorescence. NIR imaging enables deeper tissue penetration and offers higher temporal and spatial resolution <em>in vivo</em>. Therefore, NIR imaging is now widely used across life science research, medical diagnostics, image-guided surgery, and drug development.</div><div>Carbazole derivatives have emerged as promising materials for use in fluorescence imaging due to their excellent photophysical properties, chemical stability, and synthetic versatility. Although extensively explored in optoelectronics, particularly in organic light-emitting diodes, their application in the life sciences remains limited, primarily due to short emission wavelengths (around 368 nm) and insufficient biocompatibility. This review summarizes recent advances in the development and use of carbazole-based fluorophores with extended NIR emission for use in biosensing, bioimaging, and theranostics. Rational design strategies for developing NIR-emitting carbazole probes tailored for biological imaging are also discussed.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144222"},"PeriodicalIF":4.7,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145270633","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}

{"title":"Unraveling the direct effect of cationic methylation on molecular structure, electronic structure, and stability of pentazolate salts in an external electric field","authors":"Liu Song ,&nbsp;Zhenyu Yuan ,&nbsp;Chen Yang ,&nbsp;Guo Chen ,&nbsp;Junqi Wang ,&nbsp;Changlin Zhou ,&nbsp;Bingcheng Hu","doi":"10.1016/j.molstruc.2025.144186","DOIUrl":"10.1016/j.molstruc.2025.144186","url":null,"abstract":"<div><div>Polynitrogen compounds, particularly cyclo-pentazolate (<em>c</em>-N₅ˉ) salts, hold significant potential as high-energy-density materials but are hindered by sensitivity issues. Here, we report the synthesis and characterization of two novel methyl-functionalized pentazolate salts: methoxyammonium pentazolate (MOA⁺N₅ˉ) and dimethylbiguanidinium pentazolate (DMBG⁺N₅ˉ). Both salts exhibit onset decomposition temperatures ≥ 82 °C and low mechanical sensitivities (<em>IS</em> ≥ 30 J, <em>FS</em> ≥ 300 N). In addition to material synthesis, this study integrates cation methylation with external electric field (EEF) modulation to explore structural and electronic responses. First-principles and quantum chemical calculations demonstrate that methylation mitigates field-induced polarization across varying EEF intensities. The N–N trigger bonds within the <em>c</em>-N₅ˉ rings show remarkable structural resilience. Frontier orbital analysis reveals that the HOMO–LUMO gap responds controllably to field polarity: the gap widens under moderate positive EEF (0.002–0.006 Ry a.u.) and narrows under equivalent negative fields (-0.006 to -0.002 Ry a.u.). Electrostatic potential analysis further indicates that methylation maintains stable, large positive regions (49% for MOA⁺N₅ˉ and 61% for DMBG⁺N₅ˉ) even under field perturbations. Simulated impact sensitivities under EEF confirm enhanced mechanical stability. This work highlights the coupling effect of methylation and EEF regulation, offering new insights into the design of structurally resilient, field-tolerant energetic materials and advancing the understanding of pentazolate chemistry.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144186"},"PeriodicalIF":4.7,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145223392","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}

{"title":"Arylformylhydrazone triphenylphosphine Ni(II) complexes: synthesis, crystal structure, and efficient catalysis access to selenophenes","authors":"Penghui Ni ,&nbsp;Jing Tan ,&nbsp;Jiazhao Duan,&nbsp;Yuxing Tan,&nbsp;Wujiu Jiang","doi":"10.1016/j.molstruc.2025.144220","DOIUrl":"10.1016/j.molstruc.2025.144220","url":null,"abstract":"<div><div>Three arylformylhydrazone triphenylphosphine Ni(II) complexes [X-C₆H₄-(O)C=N-N=C(Me)-CH=C(O)-Ph]Ni(PPh₃) (<strong>Ni-1</strong>: X = H; <strong>Ni-2</strong>: X = 4-NO₂; <strong>Ni-3</strong>: X = 4-CH₃) were synthesized by microwave “one-pot” reaction with arylformylhydrazine, benzoylacetone, triphenylphosphine and Ni(II) chloride hexahydrate. These Ni(II) complexes were systematically characterized using IR, NMR, X-ray single-crystal diffraction, and TGA analysis. Structural determination confirmed that the fully deprotonated arylformylhydrazone acts as a dianionic tridentate (ONO) pincer ligand, coordinating to the center Ni(II) through its oxygen and nitrogen donor atoms. The Ni(II) adopts a distorted square planar coordination geometry, with the triphenylphosphine occupying the fourth coordination site. Importantly, these complexes demonstrated significant catalytic potential in the synthesis of selenophene derivatives from readily available terminal alkynes and elemental selenium. Exceptional catalytic efficiency was achieved at a low loading of 5 mol %.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144220"},"PeriodicalIF":4.7,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145269852","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}

{"title":"Microwave-assisted synthesis of poly aromatic pyrimido[4,5-b]quinoline derivatives: Design, in silico pharmacokinetics, molecular dynamics simulation, molecular docking, POM analysis, and in vitro antimicrobial screening","authors":"Anand W. Mehta ,&nbsp;Ragini C. Patil ,&nbsp;Ajmal R. Bhat ,&nbsp;Mohammad Murwih Alidmat ,&nbsp;Shadid Alotaibi ,&nbsp;Taibi Ben Hadda ,&nbsp;Pranali Vijaykumar Kuthe ,&nbsp;Murugesan Sankaranarayanan ,&nbsp;Sujata Kundan ,&nbsp;Sumeer Ahmed ,&nbsp;Gabriela Tataringa","doi":"10.1016/j.molstruc.2025.144201","DOIUrl":"10.1016/j.molstruc.2025.144201","url":null,"abstract":"<div><div>A series of polyaromatic Pyrimido[4,5-b]quinoline derivatives <strong>4</strong>(<strong>a</strong>–<strong>j</strong>) were synthesized using a rapid and efficient microwave-assisted method. The targeted Compounds <strong>4</strong>(<strong>a</strong>–<strong>j</strong>) showed significant antibacterial and antifungal activity. Structural design was guided by rational drug design principles to enhance antimicrobial potential. The synthesized compounds were subjected to comprehensive in silico pharmacokinetic profiling (ADMET) to predict drug-likeness and bioavailability. Molecular docking studies were performed to assess binding interactions with key microbial targets, followed by molecular dynamics (MD) simulations to evaluate the stability of ligand–target complexes. POM (Petra/Osiris/Molinspiration) analysis further supported the biological relevance of the compounds. In vitro antimicrobial screening against selected bacterial and fungal strains revealed promising activity, with some derivatives demonstrating superior potency compared to standard drugs. The integration of green synthesis, computational modeling, and biological validation highlights these compounds as potential scaffolds for future antimicrobial drug development. Docking studies with S. aureus NDK (PDB ID: 3Q89) revealed strong molecular interactions. ADME, Lipinski, and Veber analyses predicted good bioavailability and safety. Molecular dynamics confirmed stability, highlighting this method's promise in green medicinal chemistry.Structural elucidation of the synthesized compounds was confirmed through FT-IR, ¹H NMR, ¹³C NMR, and ESI mass spectrometry</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144201"},"PeriodicalIF":4.7,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145270276","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}

{"title":"Supramolecular assemblies in fumarato and succinato based Mn(II) and Ni(II) coordination solids involving pyridine and phenanthroline: Anticancer activities and theoretical studies","authors":"Trishnajyoti Baishya ,&nbsp;Mridul Boro ,&nbsp;Rosa M. Gomila ,&nbsp;Antonio Frontera ,&nbsp;Miquel Barcelo-Oliver ,&nbsp;Akalesh Kumar Verma ,&nbsp;Aminur Rahman ,&nbsp;Manjit K. Bhattacharyya","doi":"10.1016/j.molstruc.2025.144191","DOIUrl":"10.1016/j.molstruc.2025.144191","url":null,"abstract":"<div><div>Two new coordination compounds [Mn(3-Mepy)₂(µ-fum)(H₂O)₂]_n (<strong>1</strong>) and [Ni(phen)(succH_0.5)(H₂O)₃](NO₃)_0.5·2H₂O (<strong>2</strong>) (3-Mepy = 3-Methylpyridine, phen = 1,10-phenanthroline, fum = fumarate, succH = monoanion of succinic acid) were synthesized and characterized by SCXRD technique, electronic, FT-IR spectroscopy and thermogravimetric analysis (TGA). Polymer compound <strong>1</strong> exhibits two distinct polymeric chains with identical coordination environment, slightly differing in bond distances and bond angles surrounding the Mn(II) metal centres. The polymeric chains are interconnected via various hydrogen-bonding and π-stacking interactions forming the 2D supramolecular layered architecture. Crystal structure analysis of <strong>2</strong>, a Ni(II) monomer, reveals the enclathration of dual guest water molecules and nitrate anions in Ni(II) supramolecular host cavities. DFT (Density Functional Theory) was used to analyze the important non-covalent interactions present in the crystal structures of the compounds. Moreover, MEP (Molecular Electrostatic Potential) surface calculations, QTAIM (Quantum Theory of Atoms In Molecules), and NCI (Non-Covalent Interaction) plot analyses were also employed to rationalize and characterize these interactions. Computational studies confirm the strong stabilizing role of the network of H-bonds and π-stacking interactions in extending the polymeric chains into 2D supramolecular architectures in compound <strong>1</strong>. Similarly, for compound <strong>2</strong>, the QTAIM/NCI plot analysis of the H-bonded self-assembled dimer, reveals the contribution of O–H···O and C–H···O H-bonds. The <em>in vitro</em> cytotoxicity of compounds <strong>1</strong> and <strong>2</strong> were evaluated against Dalton’s lymphoma (DL) cancer cell line supported by Trypan blue assay and LDH (Lactate Dehydrogenase) leakage parameters. Apoptosis was investigated through dual fluorochrome staining and mitochondrial membrane potential (MMP) studies. Results demonstrated that both the compounds induced cytotoxicity and apoptosis in DL cells, highlighting their potential as therapeutic agents for further study.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144191"},"PeriodicalIF":4.7,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145270510","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}

{"title":"Impact of substituents on bromination sites of (E)-1-[5-methyl-1-aryl-1H-1,2,3-triazol-4-yl]-3-arylprop-2-en-1-ones using N-bromosuccinimide: Synthesis and crystal structure elucidation","authors":"Bakr F. Abdel-Wahab ,&nbsp;Hanan A. Mohamed ,&nbsp;Mohamed S. Bekheit ,&nbsp;Benson M. Kariuki ,&nbsp;Gamal A. El-Hiti","doi":"10.1016/j.molstruc.2025.144172","DOIUrl":"10.1016/j.molstruc.2025.144172","url":null,"abstract":"<div><div>The bromination of (<em>E</em>)-1-[1-aryl-5-methyl-1<em>H</em>-1,2,3-triazol-4-yl]-3-arylprop-2-en-1-ones using <em>N</em>-bromosuccinimide (NBS) in polar protic solvents, such as methanol and ethanol, under acidic conditions was investigated. The bromination site was found to depend on the substituents in chalcones and the reaction conditions. Bromination of phenyl, 4-chlorophenyl, and 4-fluorophenyl-1<em>H</em>-1,2,3-triazolyl chalcones using NBS in methanol occurred at the aliphatic carbon-carbon double bond, producing the corresponding α‑methoxy bromide derivatives with a 90–95 % yield. In contrast, bromination of chalcones with a 4-methoxyphenyl group attached to the unsaturated center under similar conditions resulted in bromination on both the aliphatic double bond and <em>ortho</em> to the methoxy group on the aryl ring, producing the corresponding dibrominated triazoles in 85–90 % yields. When chalcones with a phenyl group on the triazole ring and a phenyl or 4-methoxyphenyl group on the unsaturated center were treated with NBS in ethanol, bromination occurred at the aliphatic double bond, yielding α-ethoxy bromide derivatives in 90–92 % yield. The crystal structures of the synthesized compounds have been determined to confirm their molecular structures, and Hirshfeld surfaces have been utilized to analyze intermolecular interactions within the crystals.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1350 ","pages":"Article 144172"},"PeriodicalIF":4.7,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145222503","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}

{"title":"Exploring density functional theory to gain insight into the enolimine-ketoenamine tautomerism of dihydroxyl Schiff bases derived from 4-(diethylamino)salicylaldehyde and investigating their use as antidiabetes and antioxidant agents","authors":"Segun D. Oladipo ,&nbsp;Robert C. Luckay ,&nbsp;Abosede A. Badeji ,&nbsp;Kolawole A. Olofinsan","doi":"10.1016/j.molstruc.2025.144188","DOIUrl":"10.1016/j.molstruc.2025.144188","url":null,"abstract":"<div><div>Three dihydroxyl Schiff bases namely, 5-chloro-2-((4-(diethylamino)-2-hydroxybenzylidene)amino)phenol (<strong>DAC</strong>), 2-((4-(diethylamino)-2-hydroxybenzylidene)amino)-4-methylphenol (<strong>DAM</strong>) and 5-(diethylamino)-2-(((2-hydroxy-4-nitrophenyl)imino)methyl)phenol (<strong>DAN</strong>) were prepared by the condensation reaction between 4-(diethylamino)salicylaldehyde and amino-phenol derivatives. The compounds were elucidated using spectroscopic and elemental analysis techniques. Attempts to grow the crystal structure of <strong>DAC</strong> and <strong>DAM</strong> (enolimine form) at 60 –70 °C in methanol resulted in the formation of their ketoenamine form and are denoted as <strong>DAC′</strong> and <strong>DAM′</strong>. The molecular conformation of <strong>DAC′</strong> and <strong>DAM′</strong> revealed that the 4-diethylamino and the aminophenol phenyl rings are coplanar with the azomethine functional group as evident by C13—C8—C7—N1 dihedral angles of -178.78º (<strong>DAC′</strong>) and -174.99º (<strong>DAM′</strong>) as well as C1/C3—C6/C4—N1—C7 dihedral angles of 179.16º (<strong>DAC′</strong>) and 174.08º (<strong>DAM′</strong>). The longer bond length observed in C7—N1 as well as slightly shorter bond length observed in C9—O1 of <strong>DAC′</strong> and <strong>DAM′</strong> affirms their tautomeric properties related to <strong>DAC</strong> and <strong>DAM</strong>. We used Density functional theory (DFT) to investigate the structural, electronic, and tautomeric properties of <strong>DAM, DAC</strong>, and <strong>DAN</strong>. Notably, all the compounds exhibit single intramolecular hydrogen bonding that stabilizes its structure and facilitates proton transfer to yield its ketoenamine tautomer. However, the enamine tautomer is more stabilized due to the presence of dual intermolecular hydrogen bonding, hence supporting the crystallization of <strong>DAC′</strong> and <strong>DAM′</strong> over <strong>DAC</strong> and <strong>DAM</strong>. Compound <strong>DAN</strong> with the lowest energy bandgap of 6.158 eV is suggested to be the most reactive and polarizable molecule among the three compounds. Ferric reducing ability power (FRAP), 2,2-diphenyl-1-picrylhydrazyl (DPPH) as well as nitric oxide assays were explored to evaluate the antioxidant potential of the compounds. They exhibited good to moderate antioxidant activities i.e., <strong>DAN</strong> with IC₅₀ value of 0.51 μΜ scavenge nitric oxide radical better than quercetin with an IC₅₀ value of 149.96 μΜ. The evaluation of the antidiabetic potential was carried out using α-glucosidase and α-amylase inhibition assays. For the α-amylase assay, <strong>DAC</strong> with an IC₅₀ value of 0.13 μΜ exhibited almost equivalent capacity as acarbose with IC₅₀ value of 0.11 μΜ.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1351 ","pages":"Article 144188"},"PeriodicalIF":4.7,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145222871","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}