Pub Date : 2025-12-25DOI: 10.1016/j.molstruc.2025.145163
Shanting Liu , Kanghui Liu , Kunming Zhang , Yu Xuan Hu , Ya-Ping Ou , Sheng Hua Liu
In this work, we innovatively employs OsC units to react with phenolic derivatives, synthesizing a series of new Osmapentalyne-fused furans (1–4) incorporated into conjugated ring systems, and introduces redox-active substituents (diphenylamino and diarylboron groups). Their structures were confirmed by NMR, high-resolution mass spectrometry, and X-ray crystallography. Single-crystal structures displayed a well-coordinated osmium-fused tetracyclic framework with good coplanarity. Spectroscopy studies feature aggregation-induced emission (AIE) properties in ethanol/water mixtures and near-infrared luminescence in the solid state, with quantum yields up to 14.36%. Electrochemical studies reveal reversible single-electron oxidation for diphenylamino-substituted compounds (3 and 4), along with electronic communication between the metal and organic moieties. Theoretical calculations further clarify their electronic structure characteristics, confirming metal to ligand charge transfer (MLCT) upon oxidation. This study presents a new class of metallacyclic systems and offers insights for applications in near-infrared luminescent materials and molecular electronics.
{"title":"Novel osmapentalene-fused furans bearing redox-active substituents: Synthesis, structural studies, photophysical and electrochemical properties","authors":"Shanting Liu , Kanghui Liu , Kunming Zhang , Yu Xuan Hu , Ya-Ping Ou , Sheng Hua Liu","doi":"10.1016/j.molstruc.2025.145163","DOIUrl":"10.1016/j.molstruc.2025.145163","url":null,"abstract":"<div><div>In this work, we innovatively employs Os<img>C units to react with phenolic derivatives, synthesizing a series of new Osmapentalyne-fused furans <strong>(1–4</strong>) incorporated into conjugated ring systems, and introduces redox-active substituents (diphenylamino and diarylboron groups). Their structures were confirmed by NMR, high-resolution mass spectrometry, and X-ray crystallography. Single-crystal structures displayed a well-coordinated osmium-fused tetracyclic framework with good coplanarity. Spectroscopy studies feature aggregation-induced emission (AIE) properties in ethanol/water mixtures and near-infrared luminescence in the solid state, with quantum yields up to 14.36%. Electrochemical studies reveal reversible single-electron oxidation for diphenylamino-substituted compounds (<strong>3</strong> and <strong>4</strong>), along with electronic communication between the metal and organic moieties. Theoretical calculations further clarify their electronic structure characteristics, confirming metal to ligand charge transfer (MLCT) upon oxidation. This study presents a new class of metallacyclic systems and offers insights for applications in near-infrared luminescent materials and molecular electronics.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145163"},"PeriodicalIF":4.7,"publicationDate":"2025-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881659","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}
Pub Date : 2025-12-25DOI: 10.1016/j.molstruc.2025.145156
El-houssaine Safir , Walid Ettahiri , Othmane Boutaqqa , Jamila Lazrak , Sara Naamane , Zakia Rais , Susanne K. Wiedmer , Mohamed Adardour , Mustapha Taleb
Corrosion of mild steel in acidic environments remains a significant challenge in various industrial processes. In this study, two novel benzimidazole derivatives, SA‑IM and BO‑IM, were synthesized and evaluated as corrosion inhibitors in a 1 M HCl solution. Their molecular structures were confirmed by FT‑IR and NMR analyses. Electrochemical measurements revealed that both inhibitors function as mixed-type agents with very high efficiencies exceeding 98%, surpassing previously reported benzimidazole derivatives indicates an adsorption process predominantly controlled by chemisorption, as supported by thermodynamic parameters and adsorption isotherms, including Langmuir. The originality of this work lies in the combined experimental and theoretical approach. DFT calculations and Monte Carlo simulations demonstrated strong electronic affinity toward the Fe (110) surface and predicted an almost parallel adsorption configuration, optimizing surface coverage. SA‑IM exhibited slightly more negative adsorption energy and higher polarization resistance than BO‑IM, consistent with experimental findings. SEM/EDS analyses confirmed the formation of a dense, homogeneous protective organic film enriched in nitrogen and oxygen on the steel surface.
{"title":"Synthesis, characterization, and mechanistic insight into benzimidazole-based organic inhibitors for mild steel corrosion protection in acidic media","authors":"El-houssaine Safir , Walid Ettahiri , Othmane Boutaqqa , Jamila Lazrak , Sara Naamane , Zakia Rais , Susanne K. Wiedmer , Mohamed Adardour , Mustapha Taleb","doi":"10.1016/j.molstruc.2025.145156","DOIUrl":"10.1016/j.molstruc.2025.145156","url":null,"abstract":"<div><div>Corrosion of mild steel in acidic environments remains a significant challenge in various industrial processes. In this study, two novel benzimidazole derivatives, SA‑IM and BO‑IM, were synthesized and evaluated as corrosion inhibitors in a 1 M HCl solution. Their molecular structures were confirmed by FT‑IR and NMR analyses. Electrochemical measurements revealed that both inhibitors function as mixed-type agents with very high efficiencies exceeding 98%, surpassing previously reported benzimidazole derivatives indicates an adsorption process predominantly controlled by chemisorption, as supported by thermodynamic parameters and adsorption isotherms, including Langmuir. The originality of this work lies in the combined experimental and theoretical approach. DFT calculations and Monte Carlo simulations demonstrated strong electronic affinity toward the Fe (110) surface and predicted an almost parallel adsorption configuration, optimizing surface coverage. SA‑IM exhibited slightly more negative adsorption energy and higher polarization resistance than BO‑IM, consistent with experimental findings. SEM/EDS analyses confirmed the formation of a dense, homogeneous protective organic film enriched in nitrogen and oxygen on the steel surface.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145156"},"PeriodicalIF":4.7,"publicationDate":"2025-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882109","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}
Small molecule inhibitors offer an attractive way to fight cancer. This study highlights the synthesis of 2-(1H-pyrazol-1-yl)pyrimidine derivatives and their anti-cancer activity. The basic molecule design was inspired by identifying a pharmacophore model of EGFR, CDK inhibitors, and combining two pharmacophores, namely pyrazole and pyrimidine, both known for their significant bioactivity against various cancer targets. A total of twenty-seven derivatives were synthesised (P1-P27) and well characterised. A panel of human cancer cell lines was used for the in vitro cell proliferation assay, consisting of oral squamous carcinoma (SCC-25), breast cancer (MCF-7), and lung cancer (U87-MG) cell lines. The human embryonic kidney (HEK293T) cell line was used for the cytotoxicity screening. The results exhibited that several derivatives had antiproliferative activity, with IC₅₀ values in the low micromolar range. Of these, compounds P24 and P25 showed the maximum activity of IC50 1.71±0.03, 5.61±0.38 μM against the SCC-25 cell line and the HEK293T cell line (IC50 58.46±2.80, 55.58±1.96 μM) for cytotoxicity. The SCC-25 cell line was utilised in subsequent investigations, including colony formation assay, apoptotic cell death analysis, and cell cycle arrest studies. Molecular docking and dynamics simulation studies were conducted against the epidermal growth factor receptor (EGFR) kinase (PDB ID: 4ZAU) to support the biological findings. The results showed stable protein-ligand interactions and a strong binding affinity. Pharmacokinetic and drug likeness profiles were predicted by SWISS ADME. The potential of 2-(1H-pyrazol-1-yl) pyrimidine derivatives as promising lead candidates for anticancer therapy is highlighted overall by the integrated synthetic, biological, and computational approach.
{"title":"2-(1H-Pyrazol-1-yl)pyrimidine derivatives as promising anticancer candidates: synthesis, biological studies, and computational insights","authors":"Mahesh Kumar Talamadla , Shreyash Rajendra Moharir , Mihika Katdare , Suryansh Sengar , Swati , Vivek Sharma , Sankaranarayanan Murugesan , Kondapalli Venkata Gowri Chandra Sekhar","doi":"10.1016/j.molstruc.2025.145158","DOIUrl":"10.1016/j.molstruc.2025.145158","url":null,"abstract":"<div><div>Small molecule inhibitors offer an attractive way to fight cancer. This study highlights the synthesis of 2-(<em>1H</em>-pyrazol-1-yl)pyrimidine derivatives and their anti-cancer activity. The basic molecule design was inspired by identifying a pharmacophore model of EGFR, CDK inhibitors, and combining two pharmacophores, namely pyrazole and pyrimidine, both known for their significant bioactivity against various cancer targets. A total of twenty-seven derivatives were synthesised (<strong>P1-P27</strong>) and well characterised. A panel of human cancer cell lines was used for the in vitro cell proliferation assay, consisting of oral squamous carcinoma (SCC-25), breast cancer (MCF-7), and lung cancer (U87-MG) cell lines. The human embryonic kidney (HEK293T) cell line was used for the cytotoxicity screening. The results exhibited that several derivatives had antiproliferative activity, with IC₅₀ values in the low micromolar range. Of these, compounds <strong>P24</strong> and <strong>P25</strong> showed the maximum activity of IC<sub>50</sub> 1.71±0.03, 5.61±0.38 μM against the SCC-25 cell line and the HEK293T cell line (IC<sub>50</sub> 58.46±2.80, 55.58±1.96 μM) for cytotoxicity. The SCC-25 cell line was utilised in subsequent investigations, including colony formation assay, apoptotic cell death analysis, and cell cycle arrest studies. Molecular docking and dynamics simulation studies were conducted against the epidermal growth factor receptor (EGFR) kinase (PDB ID: <span><span>4ZAU</span><svg><path></path></svg></span>) to support the biological findings. The results showed stable protein-ligand interactions and a strong binding affinity. Pharmacokinetic and drug likeness profiles were predicted by SWISS ADME. The potential of 2-(<em>1H</em>-pyrazol-1-yl) pyrimidine derivatives as promising lead candidates for anticancer therapy is highlighted overall by the integrated synthetic, biological, and computational approach.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145158"},"PeriodicalIF":4.7,"publicationDate":"2025-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882024","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}
Pub Date : 2025-12-25DOI: 10.1016/j.molstruc.2025.145164
Shengli Li , Xuyang Du , Shipan Xu , Long Wang , He Yin , Xiaolong Yang , Yousong Ding , Guijiang Zhou , Yuanhui Sun
Three iridium(Ⅲ) complexes (Ir-PVB, Ir-PVO, and Ir-PVSO2) containing C=C double bonds inserted between the pyridine and aryl ring were designed and synthesized. The resultant complexes were characterized by NMR and HRMS. Especially, the single-crystal X-ray diffraction investigation of Ir-PVB revealed that the resultant iridium(Ⅲ) complex adopted a distorted octahedral coordination geometry around the central iridium atom, which was similar to the double bond-free iridium(Ⅲ) complex. The thermal, photophysical, and electrochemical properties of Ir-PVB, Ir-PVO, and Ir-PVSO2 were also investigated. Compared with their corresponding double bond-free analogs, these three complexes exhibited a remarkable redshift exceeding 100 nm, thus enabling their emissions to fall into the deep-red region. Furthermore, the resultant complexes can be used to prepare solution-processed OLEDs, which provides a new approach for the development of deep-red emitters for OLEDs.
{"title":"Synthesis, structural characterization, photophysical properties, and OLED applications of Ir(Ⅲ) complexes","authors":"Shengli Li , Xuyang Du , Shipan Xu , Long Wang , He Yin , Xiaolong Yang , Yousong Ding , Guijiang Zhou , Yuanhui Sun","doi":"10.1016/j.molstruc.2025.145164","DOIUrl":"10.1016/j.molstruc.2025.145164","url":null,"abstract":"<div><div>Three iridium(Ⅲ) complexes (Ir-PVB, Ir-PVO, and Ir-PVSO<sub>2</sub>) containing <em>C</em>=<em>C</em> double bonds inserted between the pyridine and aryl ring were designed and synthesized. The resultant complexes were characterized by NMR and HRMS. Especially, the single-crystal X-ray diffraction investigation of Ir-PVB revealed that the resultant iridium(Ⅲ) complex adopted a distorted octahedral coordination geometry around the central iridium atom, which was similar to the double bond-free iridium(Ⅲ) complex. The thermal, photophysical, and electrochemical properties of Ir-PVB, Ir-PVO, and Ir-PVSO<sub>2</sub> were also investigated. Compared with their corresponding double bond-free analogs, these three complexes exhibited a remarkable redshift exceeding 100 nm, thus enabling their emissions to fall into the deep-red region. Furthermore, the resultant complexes can be used to prepare solution-processed OLEDs, which provides a new approach for the development of deep-red emitters for OLEDs.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145164"},"PeriodicalIF":4.7,"publicationDate":"2025-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881374","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}
The synthesis of novel aggregation-induced emission (AIE)-based fluorescent tag Hydrazone N-((1-Methyl-2-oxo-1,2-dihydroquinolin-3-yl)methylene)nicotinohydrazide (INHQ) from 1-Methyl-2-oxo-quinoline-3-carbaldehyde and Isoniazid has been carried out in the present work. Further, the metal complexes are also prepared by refluxing the Ethanolic solution of a ligand with the corresponding metal chloride salts. The synthesized molecule INHQ and its Zn(II) complex have remarkable qualities, including high purity, low cost, environmental friendliness, high photostability, and bright fluorescence in the aggregation state. Vibrant and distinct fluorescence fingerprint ridges are visible on a range of surfaces, exhibiting level 1–3 ridge features, when exposed to UV light with a wavelength of 365 nm. Various analytical techniques are used to confirm the structural characteristics of the synthesized compounds, including FT-IR, UV–Vis, PL-emission, NMR (¹H & ¹³C), HRMS, Molar conductance, Elemental analysis, VSM, ESR, TGA, and Powder XRD. FT-IR spectral data suggest that the ligand behaves as a bidentate N, O donor system. Magnetic susceptibility measurements reveal the paramagnetic behaviour of all the complexes except Zn(II) complex. The potency of the antimycobacterial activity of the compounds was evaluated. The results revealed that compounds [Co(INHQ)Cl2].3H2O and [Ni(INHQ)Cl2].6H2O showed excellent sensitivity at 6.25 μg/mL against the Mycobacterium tuberculosis H37 RV strains.
{"title":"\"Novel fluorescent quinoline-based hydrazone metal complexes: Synthesis, photophysical applications in latent fingerprint detection, anti-counterfeiting, and antitubercular activity\"","authors":"Kumari Pooja T , Yuvaraj TCM , Chethan Krishnamurthy , Pampapathi Shekharagouda","doi":"10.1016/j.molstruc.2025.145146","DOIUrl":"10.1016/j.molstruc.2025.145146","url":null,"abstract":"<div><div>The synthesis of novel aggregation-induced emission (AIE)-based fluorescent tag Hydrazone <strong>N-((1-Methyl-2-oxo-1,2-dihydroquinolin-3-yl)methylene)nicotinohydrazide</strong> (<strong>INHQ</strong>) from 1-Methyl-2-oxo-quinoline-3-carbaldehyde and Isoniazid has been carried out in the present work. Further, the metal complexes are also prepared by refluxing the Ethanolic solution of a ligand with the corresponding metal chloride salts. The synthesized molecule INHQ and its Zn(II) complex have remarkable qualities, including high purity, low cost, environmental friendliness, high photostability, and bright fluorescence in the aggregation state. Vibrant and distinct fluorescence fingerprint ridges are visible on a range of surfaces, exhibiting level 1–3 ridge features, when exposed to UV light with a wavelength of 365 nm. Various analytical techniques are used to confirm the structural characteristics of the synthesized compounds, including FT-IR, UV–Vis, PL-emission, NMR (¹H & ¹³C), HRMS, Molar conductance, Elemental analysis, VSM, ESR, TGA, and Powder XRD. FT-IR spectral data suggest that the ligand behaves as a bidentate N, O donor system. Magnetic susceptibility measurements reveal the paramagnetic behaviour of all the complexes except Zn(II) complex. The potency of the antimycobacterial activity of the compounds was evaluated. The results revealed that compounds [Co(INHQ)Cl<sub>2</sub>].3H<sub>2</sub>O and [Ni(INHQ)Cl<sub>2</sub>].6H<sub>2</sub>O showed excellent sensitivity at 6.25 μg/mL against the <em>Mycobacterium tuberculosis</em> H37 RV strains.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145146"},"PeriodicalIF":4.7,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882022","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}
Pub Date : 2025-12-24DOI: 10.1016/j.molstruc.2025.145114
Ruyi Lu, Shuaijie Jiang, Kejing Zhang, Ming Lu, Pengcheng Wang
Energetic materials with high thermal stability are crucial for applications in extreme environments, such as aerospace vehicles and oil-gas resource development. This study introduces an efficient C–N coupling strategy for the convenient synthesis of bicyclic energetic materials with exceptional thermal stability. Four new heat-resistant energetic compounds, namely ANP-DANP (1), ANP-AT (2), ANP-ANTA (3), and ANP-DAT (4), were successfully created. All these compounds demonstrate remarkable thermal decomposition temperatures (Td > 300°C) and low sensitivity (IS > 50 J). Additionally, quantum chemical methods were utilized to investigate how the molecular structure impacts sensitivity and thermal stability. This research confirms the effectiveness of the C–N coupling strategy in developing heat-resistant energetic materials and offers insights for designing new energetic materials with high thermal stability.
{"title":"Efficient C–N coupling strategy for bicyclic energetic materials with enhanced thermal stability and low sensitivity","authors":"Ruyi Lu, Shuaijie Jiang, Kejing Zhang, Ming Lu, Pengcheng Wang","doi":"10.1016/j.molstruc.2025.145114","DOIUrl":"10.1016/j.molstruc.2025.145114","url":null,"abstract":"<div><div>Energetic materials with high thermal stability are crucial for applications in extreme environments, such as aerospace vehicles and oil-gas resource development. This study introduces an efficient C–N coupling strategy for the convenient synthesis of bicyclic energetic materials with exceptional thermal stability. Four new heat-resistant energetic compounds, namely ANP-DANP (1), ANP-AT (2), ANP-ANTA (3), and ANP-DAT (4), were successfully created. All these compounds demonstrate remarkable thermal decomposition temperatures (Td > 300°C) and low sensitivity (IS > 50 J). Additionally, quantum chemical methods were utilized to investigate how the molecular structure impacts sensitivity and thermal stability. This research confirms the effectiveness of the C–N coupling strategy in developing heat-resistant energetic materials and offers insights for designing new energetic materials with high thermal stability.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145114"},"PeriodicalIF":4.7,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882105","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}
Pub Date : 2025-12-24DOI: 10.1016/j.molstruc.2025.145157
D. Shobana , S. Sudha , Đorđe Kapuran , Dušan Dimić , D. Ramarajan
A new hydrazide derivative, (E)-N′-(2,3-dimethoxybenzylidene)-4-nitrobenzohydrazide (DB4N), was synthesized by condensation of 2,3-dimethoxybenzaldehyde with 4-nitrobenzohydrazide, and its molecular structure was confirmed by single-crystal X-ray diffraction. The compound crystallizes in the monoclinic system, and C − N and N − N bond lengths prove the existence of extended π-electron delocalization. The crystallographic structure is stabilized by intra- and intermolecular hydrogen-bonding interactions, as revealed by Hirshfeld surface and interaction energy analyses of DB4N dimers. Experimental FTIR, FT-Raman, and UV–VIS spectra were recorded and assigned with the aid of density functional theory (DFT) calculations performed using several functionals with the 6–311++G(d,p) basis set. The optimized geometry obtained at the CAM-B3LYP level showed the best agreement with crystallographic bond lengths and angles. Natural Bond Orbital (NBO) and Quantum Theory of Atoms in Molecules (QTAIM) analyses provided detailed insight into intramolecular charge transfer, stabilization interactions, and the role of substituents in electron delocalization. The theoretically predicted vibrational wavenumbers exhibited excellent correlation with experimental values, as supported by potential energy distribution (PED) analysis. Time-dependent DFT (TD-DFT) calculations reproduced the observed absorption maxima and clarified the electronic transitions. The difference of 6 nm between the most intense experimental and theoretical bands was explained by the explicit interactions between DB4N and DMSO solvent molecules. Third-order nonlinear optical (NLO) properties were investigated using the Z-scan technique, yielding a susceptibility of χ3 = 6.554 × 10–4 esu, indicating significant potential for DB4N in photonic and optoelectronic applications. The combined crystallographic, spectroscopic, and computational findings highlight the title molecule's stability, electronic delocalization, and promising NLO activity.
{"title":"Synthesis, spectroscopic and computational examination of an optically active E-N'-2,3-dimethoxybenzylidene-4-nitrobenzohydrazide crystal","authors":"D. Shobana , S. Sudha , Đorđe Kapuran , Dušan Dimić , D. Ramarajan","doi":"10.1016/j.molstruc.2025.145157","DOIUrl":"10.1016/j.molstruc.2025.145157","url":null,"abstract":"<div><div>A new hydrazide derivative, (E)-N′-(2,3-dimethoxybenzylidene)-4-nitrobenzohydrazide (<strong>DB4N</strong>), was synthesized by condensation of 2,3-dimethoxybenzaldehyde with 4-nitrobenzohydrazide, and its molecular structure was confirmed by single-crystal X-ray diffraction. The compound crystallizes in the monoclinic system, and <em>C</em> − <em>N</em> and <em>N</em> − <em>N</em> bond lengths prove the existence of extended π-electron delocalization. The crystallographic structure is stabilized by intra- and intermolecular hydrogen-bonding interactions, as revealed by Hirshfeld surface and interaction energy analyses of <strong>DB4N</strong> dimers. Experimental FTIR, FT-Raman, and UV–VIS spectra were recorded and assigned with the aid of density functional theory (DFT) calculations performed using several functionals with the 6–311++<em>G</em>(d,p) basis set. The optimized geometry obtained at the CAM-B3LYP level showed the best agreement with crystallographic bond lengths and angles. Natural Bond Orbital (NBO) and Quantum Theory of Atoms in Molecules (QTAIM) analyses provided detailed insight into intramolecular charge transfer, stabilization interactions, and the role of substituents in electron delocalization. The theoretically predicted vibrational wavenumbers exhibited excellent correlation with experimental values, as supported by potential energy distribution (PED) analysis. Time-dependent DFT (TD-DFT) calculations reproduced the observed absorption maxima and clarified the electronic transitions. The difference of 6 nm between the most intense experimental and theoretical bands was explained by the explicit interactions between <strong>DB4N</strong> and DMSO solvent molecules. Third-order nonlinear optical (NLO) properties were investigated using the Z-scan technique, yielding a susceptibility of χ<sup>3</sup> = 6.554 × 10<sup>–4</sup> esu, indicating significant potential for <strong>DB4N</strong> in photonic and optoelectronic applications. The combined crystallographic, spectroscopic, and computational findings highlight the title molecule's stability, electronic delocalization, and promising NLO activity.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145157"},"PeriodicalIF":4.7,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881528","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}
Pub Date : 2025-12-24DOI: 10.1016/j.molstruc.2025.145123
Ebtehal M. Husseiny , Ramadan M. Ramadan , Eman S. Nossier , Asmaa Saleh , Najla A. Altwaijry , Kurls E. Anwer
Applying drug design approaches such as molecular hybridization and substituent variation, two series of tetrahydrobenzo[b]thiophene carbohydrazides were synthesized, using eco-friendly procedures, as CDK-2 inhibitors. The synthesis of the target hybrids was carried out by two methods, conventional and microwave-assisted procedures. Such congeners were estimated for their cytotoxicity against liver HepG2 and breast MCF-7 and MDA-MB-231 cells, where benzoyl- and phenylacetyl-containing compounds (7 and 11) exhibited potent cytotoxicity and selectivity toward the tested carcinomas, especially breast cancer cells. Therefore, they were chosen for more biological assays to detect their mode of action. The outcomes suggest that these candidates may exhibit anticancer activity through interaction with CDK-2 receptors. Specifically, phenylacetyl derivative 11 exerted the greatest CDK-2 inhibition, which is higher than Roscovitine. Additionally, it stimulated MDA-MB-231 cycle arrest at G0/G1 phase by apoptotic induction. The in silico molecular docking study of the synthesized compound showed strong interaction with the binding site of CDK-2 receptor, inspiring such hybrids’ potential lead inhibitors.
{"title":"Investigating the cytotoxicity, CDK-2 inhibition, mechanistic insights, in silico DFT and molecular docking studies of eco-friendly synthesized benzo[b]thiophene carbohydrazides","authors":"Ebtehal M. Husseiny , Ramadan M. Ramadan , Eman S. Nossier , Asmaa Saleh , Najla A. Altwaijry , Kurls E. Anwer","doi":"10.1016/j.molstruc.2025.145123","DOIUrl":"10.1016/j.molstruc.2025.145123","url":null,"abstract":"<div><div>Applying drug design approaches such as molecular hybridization and substituent variation, two series of tetrahydrobenzo[<em>b</em>]thiophene carbohydrazides were synthesized, using eco-friendly procedures, as CDK-2 inhibitors. The synthesis of the target hybrids was carried out by two methods, conventional and microwave-assisted procedures. Such congeners were estimated for their cytotoxicity against liver HepG2 and breast MCF-7 and MDA-MB-231 cells, where benzoyl- and phenylacetyl-containing compounds (<strong>7</strong> and <strong>11</strong>) exhibited potent cytotoxicity and selectivity toward the tested carcinomas, especially breast cancer cells. Therefore, they were chosen for more biological assays to detect their mode of action. The outcomes suggest that these candidates may exhibit anticancer activity through interaction with CDK-2 receptors. Specifically, phenylacetyl derivative <strong>11</strong> exerted the greatest CDK-2 inhibition, which is higher than Roscovitine. Additionally, it stimulated MDA-MB-231 cycle arrest at G0/G1 phase by apoptotic induction. The <em>in silico</em> molecular docking study of the synthesized compound showed strong interaction with the binding site of CDK-2 receptor, inspiring such hybrids’ potential lead inhibitors.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145123"},"PeriodicalIF":4.7,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881658","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}
Pub Date : 2025-12-24DOI: 10.1016/j.molstruc.2025.145151
Najla E. AlShaikh , Abdesslem Jedidi , Dalal Alezi , Ehab M.M. Ali , Mohammad A. Basabrain , Bandar A. Babgi
This study investigates the synthesis, biomolecular interactions, and anticancer potential of two copper(I) complexes with the general formula CuBr(PPh₃)(L): Cu-dppz and Cu-dpaz, derived from dipyridophenazine (dppz) and dipyridoalloxazine (dpaz) ligands. DNA-binding studies confirmed intercalation as the primary binding mode for all compounds. BSA-binding assays revealed that the free ligands (dppz, dpaz) exhibit high affinity (Kb ≈ 10⁹ M⁻¹) and static quenching via two binding sites, whereas the Cu complexes showed distinct behaviors: Cu-dppz displayed high quenching efficiency (KSV = 6.37 × 10⁴ M⁻¹) but lower binding affinity (Kb = 1.33 × 10⁸ M⁻¹) due to steric hindrance from the PPh₃ group, while Cu-dpaz retained strong binding (Kb = 2.01 × 10⁹ M⁻¹). In vitro cytotoxicity assays revealed that Cu-dppz is significantly more potent than cisplatin, showing ∼4-fold higher activity in MCF-7 and HCT-116 and over 16-fold higher potency in MDA-MB-231 cells. Cu-dpaz showed moderate activity, with potencies ∼2-fold higher than cisplatin in MCF-7 but slightly lower in HCT-116. Selectivity indices (SI) demonstrated that Cu-dppz possesses a markedly broader therapeutic window (SI = 2.95 – 12.35) compared with cisplatin (SI = 1.00 – 1.93). Mechanistic assays established that both copper complexes induce S-phase arrest, in contrast with the G2/M arrest typical of cisplatin. JC-1 and Annexin V/PI assays demonstrated mitochondrial membrane depolarization and apoptosis induction, consistent with ROS-assisted Cu(I)/Cu(II) redox cycling and mitochondrial pathway activation. Cu-dppz favored late apoptosis, associated with strong DNA interaction and pronounced ΔΨm collapse. Collectively, the results demonstrate that subtle ligand modifications substantially alter biological behavior and identify Cu-dppz as a promising candidate for non-cisplatin-like, mitochondria-targeted anticancer therapy.
{"title":"Copper(I) complexes with extended aromatic ligands: biomolecular interactions and anticancer activity","authors":"Najla E. AlShaikh , Abdesslem Jedidi , Dalal Alezi , Ehab M.M. Ali , Mohammad A. Basabrain , Bandar A. Babgi","doi":"10.1016/j.molstruc.2025.145151","DOIUrl":"10.1016/j.molstruc.2025.145151","url":null,"abstract":"<div><div>This study investigates the synthesis, biomolecular interactions, and anticancer potential of two copper(I) complexes with the general formula CuBr(PPh₃)(L): Cu-dppz and Cu-dpaz, derived from dipyridophenazine (dppz) and dipyridoalloxazine (dpaz) ligands. DNA-binding studies confirmed intercalation as the primary binding mode for all compounds. BSA-binding assays revealed that the free ligands (dppz, dpaz) exhibit high affinity (<em>K</em><sub>b</sub> ≈ 10⁹ M⁻¹) and static quenching via two binding sites, whereas the Cu complexes showed distinct behaviors: Cu-dppz displayed high quenching efficiency (<em>K</em><sub>SV</sub> = 6.37 × 10⁴ M⁻¹) but lower binding affinity (<em>K</em><sub>b</sub> = 1.33 × 10⁸ M⁻¹) due to steric hindrance from the PPh₃ group, while Cu-dpaz retained strong binding (<em>K</em><sub>b</sub> = 2.01 × 10⁹ M⁻¹). In vitro cytotoxicity assays revealed that Cu-dppz is significantly more potent than cisplatin, showing ∼4-fold higher activity in MCF-7 and HCT-116 and over 16-fold higher potency in MDA-MB-231 cells. Cu-dpaz showed moderate activity, with potencies ∼2-fold higher than cisplatin in MCF-7 but slightly lower in HCT-116. Selectivity indices (SI) demonstrated that Cu-dppz possesses a markedly broader therapeutic window (SI = 2.95 – 12.35) compared with cisplatin (SI = 1.00 – 1.93). Mechanistic assays established that both copper complexes induce S-phase arrest, in contrast with the G2/M arrest typical of cisplatin. JC-1 and Annexin V/PI assays demonstrated mitochondrial membrane depolarization and apoptosis induction, consistent with ROS-assisted Cu(I)/Cu(II) redox cycling and mitochondrial pathway activation. Cu-dppz favored late apoptosis, associated with strong DNA interaction and pronounced ΔΨm collapse. Collectively, the results demonstrate that subtle ligand modifications substantially alter biological behavior and identify Cu-dppz as a promising candidate for non-cisplatin-like, mitochondria-targeted anticancer therapy.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145151"},"PeriodicalIF":4.7,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882102","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}
Herein, a diacetyl dihydrazone-derived nitrobenzaldehyde bis-Schiff Base L has been reported. FTIR, NMR, ESI-MS, chemical analyses, and DFT studies have been used to characterise L. L can efficiently identify Al3+ with good sensitivity and high selectivity when other metal ions are present. By using colorimetry and fluorometry, the LOD of L towards Al3+ were determined to be 6.60 × 10-6 M and 1.20 × 10-6 M, respectively. The fluorescent emission peak emerged at 313 and 358 nm upon stimulation at 245 nm when L was exploited with Al3+ and the colour of the 1:1 methanol-water solution changed from colourless to yellow, as could be seen with the bared eye. Job's plot, ESI-MS spectrometry, FT-IR and DFT calculations were used to analyse the interaction between L and Al3+. L uses "off−on−off" type fluorescence signalling to detect Al3+. Moreover, L can function in a broad pH range and be effectively used for Al3+ detection and quantification in environmental samples and the construction of INHIBIT type logic gate. L shows anti-oxidant activity and antimicrobial activity towards S. aureus and E. coli.
{"title":"A diacetyl dihydrazone-derived nitrobenzaldehyde bis-Schiff base as fluorescent and colorimetric dual-mode optical sensor for selective and sensitive detection of Al³⁺: Environmental and biological assessments","authors":"Abhilash Pandey , Devanand Sahu , Srishti Dutta , Dishen Kumar , Annpurna Sahu , Dharmendra Kumar Parihar , Goutam Kumar Patra","doi":"10.1016/j.molstruc.2025.145153","DOIUrl":"10.1016/j.molstruc.2025.145153","url":null,"abstract":"<div><div>Herein, a diacetyl dihydrazone-derived nitrobenzaldehyde bis-Schiff Base <strong>L</strong> has been reported. FTIR, NMR, ESI-MS, chemical analyses, and DFT studies have been used to characterise <strong>L. L</strong> can efficiently identify Al<sup>3+</sup> with good sensitivity and high selectivity when other metal ions are present. By using colorimetry and fluorometry, the LOD of <strong>L</strong> towards Al<sup>3+</sup> were determined to be 6.60 × 10<sup>-6</sup> M and 1.20 × 10<sup>-6</sup> M, respectively. The fluorescent emission peak emerged at 313 and 358 nm upon stimulation at 245 nm when <strong>L</strong> was exploited with Al<sup>3+</sup> and the colour of the 1:1 methanol-water solution changed from colourless to yellow, as could be seen with the bared eye. Job's plot, ESI-MS spectrometry, FT-IR and DFT calculations were used to analyse the interaction between <strong>L</strong> and Al<sup>3+</sup>. <strong>L</strong> uses \"off−on−off\" type fluorescence signalling to detect Al<sup>3+</sup>. Moreover, <strong>L</strong> can function in a broad pH range and be effectively used for Al<sup>3+</sup> detection and quantification in environmental samples and the construction of INHIBIT type logic gate. <strong>L</strong> shows anti-oxidant activity and antimicrobial activity towards <em>S. aureus</em> and <em>E. coli</em>.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1357 ","pages":"Article 145153"},"PeriodicalIF":4.7,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145883779","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}
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