Pub Date : 2025-12-21DOI: 10.1016/j.molstruc.2025.145129
Marjan Mirshahvalad, Ali Morsali
The structural modification of metal-organic frameworks (MOFs) via post-synthetic techniques offers a promising route to tune their physicochemical properties. In this study, we report the incorporation of sulfosuccinic acid into the framework of MOF-801 through a solvent-assisted ligand exchange (SALE) strategy, resulting in the mixed-linker material denoted as MOF-801-Sulf. Detailed spectroscopic and structural characterizations (PXRD, FTIR, BET, XPS, and 1H NMR) confirm successful incorporation of the sulfonic linker without compromising the crystalline framework. MOF-801-Sulf exhibits high Fe3+ adsorption capacity (500 mg/g) and high selectivity at pH 6. XPS analysis revealed distinct sulfur-related S 2p peaks and shifts in binding energy upon Fe3+ adsorption, offering molecular-level insight into the interaction between metal ions and sulfonic sites. BET analysis showed preserved porosity, while FTIR and NMR data supported the chemical integration of the new linker. The material’s structure–function relationship was further explored through adsorption studies, which revealed the enhanced role of sulfonate groups in Fe³⁺ uptake (up to 500 mg/g) at pH 6. The binding interactions were consistent with multilayer adsorption described by the Freundlich isotherm and chemisorption behavior per pseudo-second-order kinetics. These results provide a proof-of-concept for the SALE-based sulfonation of MOFs and highlight how this functionalization strategy tunes molecular adsorption behavior through mechanistic effects.
{"title":"Post-synthetic functionalization of Zr-based MOF with sulfonic linkers for selective adsorption of Fe(III) ion from water","authors":"Marjan Mirshahvalad, Ali Morsali","doi":"10.1016/j.molstruc.2025.145129","DOIUrl":"10.1016/j.molstruc.2025.145129","url":null,"abstract":"<div><div>The structural modification of metal-organic frameworks (MOFs) via post-synthetic techniques offers a promising route to tune their physicochemical properties. In this study, we report the incorporation of sulfosuccinic acid into the framework of MOF-801 through a solvent-assisted ligand exchange (SALE) strategy, resulting in the mixed-linker material denoted as MOF-801-Sulf. Detailed spectroscopic and structural characterizations (PXRD, FTIR, BET, XPS, and <sup>1</sup>H NMR) confirm successful incorporation of the sulfonic linker without compromising the crystalline framework. MOF-801-Sulf exhibits high Fe<sup>3+</sup> adsorption capacity (500 mg/g) and high selectivity at pH 6. XPS analysis revealed distinct sulfur-related S 2p peaks and shifts in binding energy upon Fe<sup>3+</sup> adsorption, offering molecular-level insight into the interaction between metal ions and sulfonic sites. BET analysis showed preserved porosity, while FTIR and NMR data supported the chemical integration of the new linker. The material’s structure–function relationship was further explored through adsorption studies, which revealed the enhanced role of sulfonate groups in Fe³⁺ uptake (up to 500 mg/g) at pH 6. The binding interactions were consistent with multilayer adsorption described by the Freundlich isotherm and chemisorption behavior per pseudo-second-order kinetics. These results provide a proof-of-concept for the SALE-based sulfonation of MOFs and highlight how this functionalization strategy tunes molecular adsorption behavior through mechanistic effects.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145129"},"PeriodicalIF":4.7,"publicationDate":"2025-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881663","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 study, new cyclotriphosphazenes (1a and 2a) were synthesized and their structures were characterized using elemental analysis, spectroscopy and crystallography techniques. Subsequently, a series of quantum chemical calculations based on density functional theory (DFT) were performed to explore the structural, electronic, and nonlinear optical properties of the tetrachloro (1 and 2) and fully substituted (1a and 2a) derivatives. Initially, bond lengths and angles were calculated at the DFT/B3LYP/6-31G(d,p) level to evaluate the consistency between the experimental and optimized geometries. A satisfactory correlation was observed between the theoretically optimized geometry and the corresponding experimental data. The nonlinear optical (NLO) properties of phosphazenes were calculated. The dipole moments range from 1.7380 to 2.7804 Debye, the polarizability values range from 4.01732 to 8.03846 esu, and the hyperpolarizability ranges from 6.7120 to 10.6333 esu. These results are in good agreement with experimental data reported for structurally related systems. Additionally, frontier molecular orbitals (FMOs) were computed. The energy difference between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) (Egap) was calculated to be 1.69–1.77 eV. The results reveal an inverse correlation between Egap and NLO properties. Based on the calculated orbital energies, reactivity descriptors such as chemical hardness (η), chemical potential (µ), electronegativity (χ), electrophilicity index (ω) and chemical softness (S) were determined. These findings highlight the potential applicability of the studied cyclotriphosphazenes in optoelectronic and photonic device technologies. In addition, the intermolecular interactions in the crystal structure of 1a were clarified by Hirshfeld surface (HS) analysis.
{"title":"Phosphorus-nitrogen compounds: Part 82. Experimental and computational studies of (p-dimethylamino)benzylspiro-(N/N)-cyclotriphosphazene derivatives","authors":"Güler İnci Tanrıkulu , Ayşin Zülfikaroğlu , Gamze Elmas , Aytuğ Okumuş , Zeynel Kılıç , Tuncer Hökelek","doi":"10.1016/j.molstruc.2025.145126","DOIUrl":"10.1016/j.molstruc.2025.145126","url":null,"abstract":"<div><div>Herein study, new cyclotriphosphazenes (<strong>1a</strong> and <strong>2a</strong>) were synthesized and their structures were characterized using elemental analysis, spectroscopy and crystallography techniques. Subsequently, a series of quantum chemical calculations based on density functional theory (<strong>DFT</strong>) were performed to explore the structural, electronic, and nonlinear optical properties of the tetrachloro (<strong>1</strong> and <strong>2</strong>) and fully substituted (<strong>1a</strong> and <strong>2a</strong>) derivatives. Initially, bond lengths and angles were calculated at the DFT/B3LYP/6-31G(d,p) level to evaluate the consistency between the experimental and optimized geometries. A satisfactory correlation was observed between the theoretically optimized geometry and the corresponding experimental data. The nonlinear optical (<strong>NLO</strong>) properties of phosphazenes were calculated. The dipole moments range from 1.7380 to 2.7804 Debye, the polarizability values range from 4.01732 to 8.03846 esu, and the hyperpolarizability ranges from 6.7120 to 10.6333 esu. These results are in good agreement with experimental data reported for structurally related systems. Additionally, frontier molecular orbitals (<strong>FMOs</strong>) were computed. The energy difference between the highest occupied molecular orbital (<strong>HOMO</strong>) and the lowest unoccupied molecular orbital (<strong>LUMO</strong>) (<strong>E<sub>gap</sub></strong>) was calculated to be 1.69–1.77 eV. The results reveal an inverse correlation between <strong>E<sub>gap</sub></strong> and <strong>NLO</strong> properties. Based on the calculated orbital energies, reactivity descriptors such as chemical hardness (η), chemical potential (µ), electronegativity (χ), electrophilicity index (ω) and chemical softness (S) were determined. These findings highlight the potential applicability of the studied cyclotriphosphazenes in optoelectronic and photonic device technologies. In addition, the intermolecular interactions in the crystal structure of <strong>1a</strong> were clarified by Hirshfeld surface (HS) analysis.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145126"},"PeriodicalIF":4.7,"publicationDate":"2025-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838580","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 : 2025-12-21DOI: 10.1016/j.molstruc.2025.145063
Roopa K. N , Y.S. Vidya , H.C. Manjunatha , Rajavaram Ramaraghavulu , R. Munirathnam , S. Manjunatha , Vishwalinga Prasad B , M. Shivanna , Bhanupriya. H , K. Manjunatha , Sheng Yun Wu
<div><div>The effect of Tb<span><math><msup><mrow></mrow><mrow><mn>3</mn><mo>+</mo></mrow></msup></math></span> dopant concentration on photoluminescence and electrochemical properties of Bi<sub>2</sub>Cr<sub>4</sub>O<sub>15</sub> nanoparticles is studied for the first time. Bi<sub>2</sub>Cr<sub>4</sub>O<sub>15</sub>:Tb (1–9 mol%) NPs are synthesized via Aloe vera gel extract mediated green combustion route. Bragg reflections confirmed the formation of the triclinic Bi<sub>2</sub>Cr<sub>4</sub>O<sub>15</sub> structure with no secondary phases up to 5 mol% dopant concentration. At 7 and 9 mol%, minor peak corresponding to <em>α</em> phases of Bi<sub>2</sub>O<sub>3</sub> are observed. The crystallite size was found to decrease from 22 to 10 nm and optical energy band gap decreases from 3.06 to 3.02 eV with increase in dopant concentration. The surface morphology consists aggregated irregular, cubic, rod and plate like structures are observed with variation in dopant concentration. The photoluminescence emission spectrum exhibits multiple peaks at 284, 381, 474, and 712 nm at 242 nm excitation wavelength. The 474 nm peak corresponds to the <sup>5</sup>D<sub>4</sub> → <sup>7</sup>F<sub>6</sub> transition of Tb<span><math><msup><mrow></mrow><mrow><mn>3</mn><mo>+</mo></mrow></msup></math></span>. The red emission at 712 nm band tentatively ascribed to defect-related recombination in the host lattice. Other peaks at 284 nm and 381 nm may arise from additional host emissions or inter-band transitions. The CIE coordinates lies well within the blue region with cooler appearance. Thus, the synthesized sample might finds an application in display technology as a blue nanophosphor material. The supercapacitive behavior of Tb<span><math><msup><mrow></mrow><mrow><mn>3</mn><mo>+</mo></mrow></msup></math></span>-doped Bi<sub>2</sub>Cr<sub>4</sub>O<sub>15</sub> nanoparticles was investigated across doping concentrations ranging from 1 to 9 mol%. A significant enhancement in specific capacitance was observed, increasing from 30.03 F/g at 1 mol% to 69.3 F/g at 9 mol%, with near-linear improvement up to 7 mol% and marginal saturation thereafter. The improvement is attributed to increased oxygen vacancy concentration, enhanced electron transport, and the substitution of Tb<span><math><msup><mrow></mrow><mrow><mn>3</mn><mo>+</mo></mrow></msup></math></span> at Bi<span><math><msup><mrow></mrow><mrow><mn>3</mn><mo>+</mo></mrow></msup></math></span> lattice sites, facilitating efficient redox activity. The 9 mol% doped sample demonstrated superior electrochemical performance, with the largest CV area, longest GCD discharge time, and highest specific capacitance. Electrochemical impedance spectroscopy and Warburg analysis confirmed reduced charge transfer resistance and enhanced ionic diffusion, with a high Warburg coefficient (<em>σ</em> = 1184.0 Ω·s<sup>1/2</sup>). These findings establish 9 mol% Tb<span><math><msup><mrow></mrow><mrow><mn>3</mn><mo>+</mo></mrow></msup>
{"title":"Exploring the dual functionalities: Photoluminescence and electrochemical studies of Bi2Cr4O15: Tb3+ nanoparticles","authors":"Roopa K. N , Y.S. Vidya , H.C. Manjunatha , Rajavaram Ramaraghavulu , R. Munirathnam , S. Manjunatha , Vishwalinga Prasad B , M. Shivanna , Bhanupriya. H , K. Manjunatha , Sheng Yun Wu","doi":"10.1016/j.molstruc.2025.145063","DOIUrl":"10.1016/j.molstruc.2025.145063","url":null,"abstract":"<div><div>The effect of Tb<span><math><msup><mrow></mrow><mrow><mn>3</mn><mo>+</mo></mrow></msup></math></span> dopant concentration on photoluminescence and electrochemical properties of Bi<sub>2</sub>Cr<sub>4</sub>O<sub>15</sub> nanoparticles is studied for the first time. Bi<sub>2</sub>Cr<sub>4</sub>O<sub>15</sub>:Tb (1–9 mol%) NPs are synthesized via Aloe vera gel extract mediated green combustion route. Bragg reflections confirmed the formation of the triclinic Bi<sub>2</sub>Cr<sub>4</sub>O<sub>15</sub> structure with no secondary phases up to 5 mol% dopant concentration. At 7 and 9 mol%, minor peak corresponding to <em>α</em> phases of Bi<sub>2</sub>O<sub>3</sub> are observed. The crystallite size was found to decrease from 22 to 10 nm and optical energy band gap decreases from 3.06 to 3.02 eV with increase in dopant concentration. The surface morphology consists aggregated irregular, cubic, rod and plate like structures are observed with variation in dopant concentration. The photoluminescence emission spectrum exhibits multiple peaks at 284, 381, 474, and 712 nm at 242 nm excitation wavelength. The 474 nm peak corresponds to the <sup>5</sup>D<sub>4</sub> → <sup>7</sup>F<sub>6</sub> transition of Tb<span><math><msup><mrow></mrow><mrow><mn>3</mn><mo>+</mo></mrow></msup></math></span>. The red emission at 712 nm band tentatively ascribed to defect-related recombination in the host lattice. Other peaks at 284 nm and 381 nm may arise from additional host emissions or inter-band transitions. The CIE coordinates lies well within the blue region with cooler appearance. Thus, the synthesized sample might finds an application in display technology as a blue nanophosphor material. The supercapacitive behavior of Tb<span><math><msup><mrow></mrow><mrow><mn>3</mn><mo>+</mo></mrow></msup></math></span>-doped Bi<sub>2</sub>Cr<sub>4</sub>O<sub>15</sub> nanoparticles was investigated across doping concentrations ranging from 1 to 9 mol%. A significant enhancement in specific capacitance was observed, increasing from 30.03 F/g at 1 mol% to 69.3 F/g at 9 mol%, with near-linear improvement up to 7 mol% and marginal saturation thereafter. The improvement is attributed to increased oxygen vacancy concentration, enhanced electron transport, and the substitution of Tb<span><math><msup><mrow></mrow><mrow><mn>3</mn><mo>+</mo></mrow></msup></math></span> at Bi<span><math><msup><mrow></mrow><mrow><mn>3</mn><mo>+</mo></mrow></msup></math></span> lattice sites, facilitating efficient redox activity. The 9 mol% doped sample demonstrated superior electrochemical performance, with the largest CV area, longest GCD discharge time, and highest specific capacitance. Electrochemical impedance spectroscopy and Warburg analysis confirmed reduced charge transfer resistance and enhanced ionic diffusion, with a high Warburg coefficient (<em>σ</em> = 1184.0 Ω·s<sup>1/2</sup>). These findings establish 9 mol% Tb<span><math><msup><mrow></mrow><mrow><mn>3</mn><mo>+</mo></mrow></msup>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145063"},"PeriodicalIF":4.7,"publicationDate":"2025-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881253","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 : 2025-12-20DOI: 10.1016/j.molstruc.2025.145118
Baiyang Fan, He Zhao, Quanhao Wei, Guiyan Liu, Pengchong Xue
A phenothiazine derivative, PTTCN, was synthesized and crystallized from different solvents (benzene, toluene, and ethanol) to yield three distinct polymorphs: PTTCN-Bz, PTTCN-Tol, and PTTCN-EtOH. These polymorphs exhibit blue-purple, cyan, and yellowish-green fluorescence, respectively, under UV light, which is attributed to their distinct molecular conformations (quasi-equatorial or quasi-axial) and packing modes. The crystals display reversible mechanofluorochromic (MFC) behavior upon grinding, with fluorescence reversibility achieved through solvent vapor fuming. Powder X-ray diffraction confirmed that the MFC behavior involves a phase transition between crystalline and amorphous states. Furthermore, the three polymorphs can be interconverted through selective solvent vapor fuming. This controllable fluorescence switching and polymorphic transformation were leveraged to demonstrate a multi-level anti-counterfeiting application with time-dependent information disclosure. This work highlights the potential of PTTCN polymorphs as smart, stimulus-responsive materials for optical encryption and security labeling.
{"title":"Three color fluorescent switching and stimulus-response of a phenothiazine derivative for anti-counterfeiting","authors":"Baiyang Fan, He Zhao, Quanhao Wei, Guiyan Liu, Pengchong Xue","doi":"10.1016/j.molstruc.2025.145118","DOIUrl":"10.1016/j.molstruc.2025.145118","url":null,"abstract":"<div><div>A phenothiazine derivative, PTTCN, was synthesized and crystallized from different solvents (benzene, toluene, and ethanol) to yield three distinct polymorphs: PTTCN-Bz, PTTCN-Tol, and PTTCN-EtOH. These polymorphs exhibit blue-purple, cyan, and yellowish-green fluorescence, respectively, under UV light, which is attributed to their distinct molecular conformations (quasi-equatorial or quasi-axial) and packing modes. The crystals display reversible mechanofluorochromic (MFC) behavior upon grinding, with fluorescence reversibility achieved through solvent vapor fuming. Powder X-ray diffraction confirmed that the MFC behavior involves a phase transition between crystalline and amorphous states. Furthermore, the three polymorphs can be interconverted through selective solvent vapor fuming. This controllable fluorescence switching and polymorphic transformation were leveraged to demonstrate a multi-level anti-counterfeiting application with time-dependent information disclosure. This work highlights the potential of PTTCN polymorphs as smart, stimulus-responsive materials for optical encryption and security labeling.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145118"},"PeriodicalIF":4.7,"publicationDate":"2025-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838577","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}
In this study, we developed a novel strategy to fabricate multiple mode and multiple stimuli-responsive metal organic crystalline smart materials (MOCSMs) based on 4,4′-azodibenzoic acid (4,4′-ADB) and manganese dichloride. The 4,4′-ADB as organic linker and divalent manganese ion as metal node were used to facilely synthesize MOCSMs by a green solvothermal synthesis method. The structure of MOCSMs was confirmed by X-Ray diffraction (XRD) analysis, Fourier transform infrared (FTIR) spectroscopy, and ultraviolet-visible (UV–vis) spectroscopy. The experimental results showed the MOCSMs include isomorphic crystalline forms with the reported crystal structures (CCDC: No.745678) and have excellent stimulus response performance to different external light or acidic-alkaline stimulation. Furthermore, the morphological transformation, structural changes, and electrochemical and photoelectrochemical performances of the MOCSMs under different acidic-alkaline stimulation and cis-trans photoisomerization of the MOCSMs with external different wavelength light stimulation have been thoroughly investigated. These investigations showed that the MOCSMs could be used as multiple mode and multiple environmentally stimuli-responsive smart crystalline materials. The study will prompt us to develop promising strategy for the development of SRCMs with the structures and functions similar to MOCSMs based on azobenzene derivatives.
{"title":"Design and preparation of multiple mode and multiple stimuli-responsive crystalline material based on Mn (II) and 4,4′-azodibenzoic acid and its acidic-alkaline and light stimulus response characteristics","authors":"Guo Yu, Yuan Feng, Yuxiu Liu, Xin Xu, Xiaocheng Bi, Ximing Guo","doi":"10.1016/j.molstruc.2025.145119","DOIUrl":"10.1016/j.molstruc.2025.145119","url":null,"abstract":"<div><div>In this study, we developed a novel strategy to fabricate multiple mode and multiple stimuli-responsive metal organic crystalline smart materials (MOCSMs) based on 4,4′-azodibenzoic acid (4,4′-ADB) and manganese dichloride. The 4,4′-ADB as organic linker and divalent manganese ion as metal node were used to facilely synthesize MOCSMs by a green solvothermal synthesis method. The structure of MOCSMs was confirmed by X-Ray diffraction (XRD) analysis, Fourier transform infrared (FTIR) spectroscopy, and ultraviolet-visible (UV–vis) spectroscopy. The experimental results showed the MOCSMs include isomorphic crystalline forms with the reported crystal structures (CCDC: No.745678) and have excellent stimulus response performance to different external light or acidic-alkaline stimulation. Furthermore, the morphological transformation, structural changes, and electrochemical and photoelectrochemical performances of the MOCSMs under different acidic-alkaline stimulation and cis-trans photoisomerization of the MOCSMs with external different wavelength light stimulation have been thoroughly investigated. These investigations showed that the MOCSMs could be used as multiple mode and multiple environmentally stimuli-responsive smart crystalline materials. The study will prompt us to develop promising strategy for the development of SRCMs with the structures and functions similar to MOCSMs based on azobenzene derivatives.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145119"},"PeriodicalIF":4.7,"publicationDate":"2025-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838687","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 : 2025-12-20DOI: 10.1016/j.molstruc.2025.145116
Ali Barazzouq , Mouna Azogagh , Ghizlane Lahlalate , Abouelhaoul El Alami , Anouar El Magri , Youssef Edder , Mohammed Daoudi , Layachi Khamliche , Driss Ouzebla , Rachid Hsissou
Our group is dedicated to creating innovative, eco-friendly methods for synthesis of novel sulfonamide derivatives. Utilizing the ecologically safe catalyst calcined red algae doped with magnesium chloride (MgCl₂@CRA), we have effectively alkylated a range of heterocyclic compounds with 4-toluenesulfonyl chloride. The exceptional catalytic effectiveness of MgCl₂@CRA was thoroughly assessed using sophisticated characterization methods including, Brunauer, Emmett, and Teller (BET), Barrett–Joyner–Halenda (BJH), energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD). Besides, the BET surface area of MgCl₂@CRA reaches a maximum of 6.669 m²/g. Furthermore, the structural integrity and purity of the produced sulfonamide derivatives were comprehensively confirmed by FTIR, mass spectrometry, and nuclear magnetic resonance spectroscopy (¹H NMR and ¹³C NMR). Moreover, to ensuring higher product yields and following green chemistry guidelines, our approach provides a very effective and environmentally friendly alternative to the manufacturing of sulfonamide derivatives.
我们的团队致力于创造创新的，环保的方法来合成新的磺胺衍生物。利用掺杂氯化镁（MgCl₂@CRA）的生态安全催化剂煅烧红藻，我们有效地将一系列杂环化合物与4-甲苯磺酰氯烷基化。采用复杂的表征方法，包括Brunauer， Emmett, and Teller (BET), Barrett-Joyner-Halenda (BJH)，能量色散x射线能谱（EDS），扫描电子显微镜（SEM），傅里叶变换红外光谱（FTIR）和x射线衍射（XRD），对MgCl₂@CRA的卓越催化效果进行了全面评估。MgCl₂@CRA的BET比表面积最大，达到6.669 m²/g。此外，通过FTIR、质谱和核磁共振谱（¹H NMR和¹³C NMR）综合证实了所制磺胺衍生物的结构完整性和纯度。此外，为了确保更高的产品产量和遵循绿色化学准则，我们的方法为磺胺衍生物的生产提供了一种非常有效和环保的替代方案。
{"title":"Synthesis and investigation of novel sulfonamide derivatives via two routes catalyzed by MgCl2@CRA as a green heterogeneous catalyst","authors":"Ali Barazzouq , Mouna Azogagh , Ghizlane Lahlalate , Abouelhaoul El Alami , Anouar El Magri , Youssef Edder , Mohammed Daoudi , Layachi Khamliche , Driss Ouzebla , Rachid Hsissou","doi":"10.1016/j.molstruc.2025.145116","DOIUrl":"10.1016/j.molstruc.2025.145116","url":null,"abstract":"<div><div>Our group is dedicated to creating innovative, eco-friendly methods for synthesis of novel sulfonamide derivatives. Utilizing the ecologically safe catalyst calcined red algae doped with magnesium chloride (MgCl₂@CRA), we have effectively alkylated a range of heterocyclic compounds with 4-toluenesulfonyl chloride. The exceptional catalytic effectiveness of MgCl₂@CRA was thoroughly assessed using sophisticated characterization methods including, Brunauer, Emmett, and Teller (BET), Barrett–Joyner–Halenda (BJH), energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD). Besides, the BET surface area of MgCl₂@CRA reaches a maximum of 6.669 m²/g. Furthermore, the structural integrity and purity of the produced sulfonamide derivatives were comprehensively confirmed by FTIR, mass spectrometry, and nuclear magnetic resonance spectroscopy (¹H NMR and ¹³C NMR). Moreover, to ensuring higher product yields and following green chemistry guidelines, our approach provides a very effective and environmentally friendly alternative to the manufacturing of sulfonamide derivatives.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145116"},"PeriodicalIF":4.7,"publicationDate":"2025-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838816","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}
In the present study, a series of novel and known thiazole derivatives were synthesized via a three-component one-pot reaction involving aromatic aldehydes, thiosemicarbazide, and phenacyl bromides. The reaction was carried out at room temperature using choline chloride: l-proline as a low transition temperature mixture (LTTM), serving as a green solvent system. The developed protocol delivered the target compounds in excellent yields (87–94%) within short reaction times (8–23 min.), highlighting its efficiency under environmentally benign conditions. This approach emphasizes the implementation of an eco-friendly and economical catalytic system for the synthesis of thiazoles. All the novel thiazole derivatives were fully characterized by using IR, HRMS, 1H, and 13C NMR analytical techniques. Then, molecular docking studies were conducted on the synthesized compounds against breast cancer, liver cancer, and CDK2 target proteins to understand their structural relationships. Furthermore, the synthesized thiazole derivatives were evaluated in an in vivo histotoxicological study against the muscle and liver tissues of freshwater fish (catla) to assess their acute toxicity. From docking and in vivo studies, the derivative 4f was observed as the safest and the most effective thiazole derivative for further applications.
{"title":"LTTM mediated environmentally benign synthesis of novel thiazole derivatives: Computational & biological investigations","authors":"Prasad Swami , Dnyaneshwar Kshirsagar , Sneha Rochlani , Nagesh Birajdar , Lalit Bhosale , Sandip Deshmukh , Sandeep Sankpal , Shankar Hangirgekar","doi":"10.1016/j.molstruc.2025.145094","DOIUrl":"10.1016/j.molstruc.2025.145094","url":null,"abstract":"<div><div>In the present study, a series of novel and known thiazole derivatives were synthesized via a three-component one-pot reaction involving aromatic aldehydes, thiosemicarbazide, and phenacyl bromides. The reaction was carried out at room temperature using choline chloride: <em><span>l</span></em>-proline as a low transition temperature mixture (LTTM), serving as a green solvent system. The developed protocol delivered the target compounds in excellent yields (87–94%) within short reaction times (8–23 min.), highlighting its efficiency under environmentally benign conditions. This approach emphasizes the implementation of an eco-friendly and economical catalytic system for the synthesis of thiazoles. All the novel thiazole derivatives were fully characterized by using IR, HRMS, <sup>1</sup>H, and <sup>13</sup>C NMR analytical techniques. Then, molecular docking studies were conducted on the synthesized compounds against breast cancer, liver cancer, and CDK2 target proteins to understand their structural relationships. Furthermore, the synthesized thiazole derivatives were evaluated in an <em>in vivo</em> histotoxicological study against the muscle and liver tissues of freshwater fish (catla) to assess their acute toxicity. From docking and <em>in vivo</em> studies, the derivative <strong>4f</strong> was observed as the safest and the most effective thiazole derivative for further applications.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145094"},"PeriodicalIF":4.7,"publicationDate":"2025-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838685","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 : 2025-12-20DOI: 10.1016/j.molstruc.2025.145127
Ömer Kayır , Sevil Özkinali Sarı
This study, aimed at developing sustainable and high performance textile coloration approaches, focuses on the development of new molecules by synthesizing naturally sourced vanillic acid-derived azo dyes and their metal complexes, targeting a significant gap in the literature for industrial dyeing applications. Novel azo dyes were synthesized from vanillic acid and further complexed with transition metals, including Mn(II), Fe(II), Ni(II), Cu(II), and Zn(II). The structures of the ligands and their corresponding metal complexes were thoroughly characterized using FT-IR, 1H- and 13C-NMR, UV-Vis, mass spectrometry, elemental analysis, and thermal (TGA/DTG) techniques. Thermal analysis indicated that all complexes possessed good stability, with L1Mn and L2Zn being the most thermally stable.
The synthesized dyes and their complexes were applied to wool and polyester fabrics, producing a wide range of reproducible color shades evaluated using the Farbenatlas scale. Fastness assessments revealed that the metal complexes generally exhibited improved performance compared to the free ligands.
Overall, the results highlight vanillic acid as a valuable precursor for the development of eco-friendly azo dyes with strong dye–fiber interactions and enhanced fastness properties. The study demonstrates that vanillic acid-based azo dyes and their transition metal complexes can serve as promising candidates for sustainable textile dyeing applications, bridging a noticeable gap in the literature regarding their industrial potential.
{"title":"Vanillic Acid Azo Dyes: Synthesis, Complexes, Spectroscopic and Dyeing Properties","authors":"Ömer Kayır , Sevil Özkinali Sarı","doi":"10.1016/j.molstruc.2025.145127","DOIUrl":"10.1016/j.molstruc.2025.145127","url":null,"abstract":"<div><div>This study, aimed at developing sustainable and high performance textile coloration approaches, focuses on the development of new molecules by synthesizing naturally sourced vanillic acid-derived azo dyes and their metal complexes, targeting a significant gap in the literature for industrial dyeing applications. Novel azo dyes were synthesized from vanillic acid and further complexed with transition metals, including Mn(II), Fe(II), Ni(II), Cu(II), and Zn(II). The structures of the ligands and their corresponding metal complexes were thoroughly characterized using FT-IR, <sup>1</sup>H- and <sup>13</sup>C-NMR, UV-Vis, mass spectrometry, elemental analysis, and thermal (TGA/DTG) techniques. Thermal analysis indicated that all complexes possessed good stability, with L<sub>1</sub>Mn and L<sub>2</sub>Zn being the most thermally stable.</div><div>The synthesized dyes and their complexes were applied to wool and polyester fabrics, producing a wide range of reproducible color shades evaluated using the Farbenatlas scale. Fastness assessments revealed that the metal complexes generally exhibited improved performance compared to the free ligands.</div><div>Overall, the results highlight vanillic acid as a valuable precursor for the development of eco-friendly azo dyes with strong dye–fiber interactions and enhanced fastness properties. The study demonstrates that vanillic acid-based azo dyes and their transition metal complexes can serve as promising candidates for sustainable textile dyeing applications, bridging a noticeable gap in the literature regarding their industrial potential.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145127"},"PeriodicalIF":4.7,"publicationDate":"2025-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838668","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 : 2025-12-20DOI: 10.1016/j.molstruc.2025.145130
Shilendra K. Pathak , Zohra Siddiqui , Anushree Maurya , Mamta Pal , Raj Shukla , Ruchi Srivastava , Vikas K. Shukla , Onkar Prasad , Leena Sinha
Epidermal Growth Factor Receptor (EGFR) plays a crucial role in cancer progression, especially in non-small cell lung cancer (NSCLC), where its overexpression renders it a prime therapeutic target. In this study, we investigate a novel EGFR-targeting hybrid compound-Pyridine-2-carboxylic acid (2-oxo-1,2-dihydro-indol-3-ylidene) hydrazide (P1)-which integrates isatin and pyridine moieties via a hydrazone linkage. Furthermore, we explore the impact of five different substitutions at the C-5 position of the isatin ring to evaluate their effect on binding affinity.
Molecular docking studies with EGFR proteins (2J6M and 4I23) revealed that P1 exhibits promising binding affinities of -8.1 and -8.0 kcal/mol, respectively. To further investigate the effect of substitution, five groups-CH₃, OCH₃, F, NO₂, and CF₃-were introduced at the C-5 position of P1, resulting in derivatives C1–C5. Docking into the EGFR (2J6M) binding site showed that the C5 derivative demonstrated the highest binding affinity (-8.4 kcal/mol). For EGFR (4I23), the derivatives except C2 outperformed P1 (-8.0 kcal/mol), with C5 achieving a binding affinity of -8.5 kcal/mol, surpassing even the native ligand dacomitinib (-8.4 kcal/mol).
The geometries of P1 and its analogs were optimized using DFT, and their electronic and reactivity descriptors were subsequently evaluated. Additionally, ADMET analysis supported the drug-likeness and pharmacokinetic potential of these compounds. MD simulations and MM-GBSA binding free-energy calculations further confirmed the structural stability of P1 and C5 toward EGFR. In vitro MTT assay additionally demonstrated dose-dependent cytotoxicity of P1 against A549 lung cancer cells.
{"title":"Hydrazone-linked isatin-pyridine hybrids for EGFR inhibition: Insights from density functional and molecular docking analyses","authors":"Shilendra K. Pathak , Zohra Siddiqui , Anushree Maurya , Mamta Pal , Raj Shukla , Ruchi Srivastava , Vikas K. Shukla , Onkar Prasad , Leena Sinha","doi":"10.1016/j.molstruc.2025.145130","DOIUrl":"10.1016/j.molstruc.2025.145130","url":null,"abstract":"<div><div>Epidermal Growth Factor Receptor (EGFR) plays a crucial role in cancer progression, especially in non-small cell lung cancer (NSCLC), where its overexpression renders it a prime therapeutic target. In this study, we investigate a novel EGFR-targeting hybrid compound-Pyridine-2-carboxylic acid (2-oxo-1,2-dihydro-indol-3-ylidene) hydrazide (P1)-which integrates isatin and pyridine moieties via a hydrazone linkage. Furthermore, we explore the impact of five different substitutions at the C-5 position of the isatin ring to evaluate their effect on binding affinity.</div><div>Molecular docking studies with EGFR proteins (2J6M and 4I23) revealed that P1 exhibits promising binding affinities of -8.1 and -8.0 kcal/mol, respectively. To further investigate the effect of substitution, five groups-CH₃, OCH₃, F, NO₂, and CF₃-were introduced at the C-5 position of P1, resulting in derivatives C1–C5. Docking into the EGFR (2J6M) binding site showed that the C5 derivative demonstrated the highest binding affinity (-8.4 kcal/mol). For EGFR (4I23), the derivatives except C2 outperformed P1 (-8.0 kcal/mol), with C5 achieving a binding affinity of -8.5 kcal/mol, surpassing even the native ligand dacomitinib (-8.4 kcal/mol).</div><div>The geometries of P1 and its analogs were optimized using DFT, and their electronic and reactivity descriptors were subsequently evaluated. Additionally, ADMET analysis supported the drug-likeness and pharmacokinetic potential of these compounds. MD simulations and MM-GBSA binding free-energy calculations further confirmed the structural stability of P1 and C5 toward EGFR. In vitro MTT assay additionally demonstrated dose-dependent cytotoxicity of P1 against A549 lung cancer cells.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145130"},"PeriodicalIF":4.7,"publicationDate":"2025-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838686","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 : 2025-12-20DOI: 10.1016/j.molstruc.2025.145117
Jiafeng Lin , Shuwen Wang , Jiaqi Su , Changle Fang , Xiao Han , Guoqiang Li , Yuanyuan Feng , Xianguo Li , Dahai Zhang
Nine previously undescribed polyphenols and their derivatives, named penipolyphenols A-I (1-9), were isolated from a deep-sea sediment-derived fungus Penicillium brefeldianum XT05. Their structures and absolute configurations were elucidated through a combined approach employing spectroscopic techniques, single-crystal X-ray diffraction analysis, and calculated ECD spectra. DPPH and ABTS radical scavenging assays, as well as an in vivo zebrafish skin oxidative damage model were evaluated. These demonstrated that compound 6 exhibited significant antioxidant activity. These findings provided a scientific foundation for developing previously undescribed antioxidants derived from deep-sea fungal polyphenols.
从深海沉积物衍生真菌青霉菌XT05中分离出9种先前未被描述的多酚及其衍生物，命名为penipolyphenols a - i（1-9）。通过光谱技术、单晶x射线衍射分析和计算ECD谱相结合的方法阐明了它们的结构和绝对构型。对DPPH和ABTS自由基清除实验以及斑马鱼体内皮肤氧化损伤模型进行了评估。结果表明，化合物6具有明显的抗氧化活性。这些发现为开发从深海真菌多酚中提取的抗氧化剂提供了科学基础。
{"title":"Penipolyphenols A-I from the deep-sea sediment-derived fungus penicillium brefeldianum XT05: Isolation, Structure elucidation and antioxidant bioassay","authors":"Jiafeng Lin , Shuwen Wang , Jiaqi Su , Changle Fang , Xiao Han , Guoqiang Li , Yuanyuan Feng , Xianguo Li , Dahai Zhang","doi":"10.1016/j.molstruc.2025.145117","DOIUrl":"10.1016/j.molstruc.2025.145117","url":null,"abstract":"<div><div>Nine previously undescribed polyphenols and their derivatives, named penipolyphenols A-I (<strong>1</strong>-<strong>9</strong>), were isolated from a deep-sea sediment-derived fungus <em>Penicillium brefeldianum</em> XT05. Their structures and absolute configurations were elucidated through a combined approach employing spectroscopic techniques, single-crystal X-ray diffraction analysis, and calculated ECD spectra. DPPH and ABTS radical scavenging assays, as well as an in <em>vivo</em> zebrafish skin oxidative damage model were evaluated. These demonstrated that compound <strong>6</strong> exhibited significant antioxidant activity. These findings provided a scientific foundation for developing previously undescribed antioxidants derived from deep-sea fungal polyphenols.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145117"},"PeriodicalIF":4.7,"publicationDate":"2025-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145839088","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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