Pub Date : 2025-12-17DOI: 10.1016/j.molstruc.2025.145097
Xiao-hui Huang , Lin-fang Nie , Shao-ming Ying , Xiao-jing Hu , Xiaoxing Huang
Two dilacunary γ-Keggin-type germanotungstates compounds namely [Cu(1,2-dap)2][Cu(1,2-dap)2(H2O)]{[Cu(1,2-dap)2]2[GeW10O36]}·2·5H2O (1) and H[H2pip][Cu(1,2-dap)2]0.5[Cu(1,2-dap)2(H2O)]2[GeW10O36]·4H2O(2) have been synthesized. Both compounds demonstrated potent, broad-spectrum cytotoxicity against a panel of human cancer cell lines, with IC₅₀ values below 15 μmol/L. Mechanistic studies in HCT116 colon cancer cells revealed that these compounds inhibit cell proliferation by downregulating key signaling pathways, including AKT and STAT3. Furthermore, they induce caspase-dependent mitochondrial apoptosis, a process regulated by the Bcl-2 family proteins. Cell cycle analysis showed that compound 1 causes S-phase arrest, while compound 2 induces G1-phase arrest. Additionally, both compounds effectively suppress cancer cell migration by inhibiting the epithelial-mesenchymal transition (EMT). The distinct signaling inhibition profiles and efficacies of the two compounds are attributed to their structural differences. These findings highlight the promise of these germanotungstates as anticancer agents and provide valuable insights for the structural design of polyoxometalate-based chemotherapeutics.
{"title":"Two Dilacunary γ-Keggin-Type Germanotungstates: Synthesis, broad-spectrum anticancer activity, and mechanistic insights","authors":"Xiao-hui Huang , Lin-fang Nie , Shao-ming Ying , Xiao-jing Hu , Xiaoxing Huang","doi":"10.1016/j.molstruc.2025.145097","DOIUrl":"10.1016/j.molstruc.2025.145097","url":null,"abstract":"<div><div>Two dilacunary γ-Keggin-type germanotungstates compounds namely [Cu(1,2-dap)<sub>2</sub>][Cu(1,2-dap)<sub>2</sub>(H<sub>2</sub>O)]{[Cu(1,2-dap)<sub>2</sub>]<sub>2</sub>[GeW<sub>10</sub>O<sub>36</sub>]}·2·5H<sub>2</sub>O (<strong>1</strong>) and H[H<sub>2</sub>pip][Cu(1,2-dap)<sub>2</sub>]<sub>0.5</sub>[Cu(1,2-dap)<sub>2</sub>(H<sub>2</sub>O)]<sub>2</sub>[GeW<sub>10</sub>O<sub>36</sub>]·4H<sub>2</sub>O(<strong>2</strong>) have been synthesized. Both compounds demonstrated potent, broad-spectrum cytotoxicity against a panel of human cancer cell lines, with IC₅₀ values below 15 μmol/L. Mechanistic studies in HCT116 colon cancer cells revealed that these compounds inhibit cell proliferation by downregulating key signaling pathways, including AKT and STAT3. Furthermore, they induce caspase-dependent mitochondrial apoptosis, a process regulated by the Bcl-2 family proteins. Cell cycle analysis showed that compound <strong>1</strong> causes S-phase arrest, while compound <strong>2</strong> induces G1-phase arrest. Additionally, both compounds effectively suppress cancer cell migration by inhibiting the epithelial-mesenchymal transition (EMT). The distinct signaling inhibition profiles and efficacies of the two compounds are attributed to their structural differences. These findings highlight the promise of these germanotungstates as anticancer agents and provide valuable insights for the structural design of polyoxometalate-based chemotherapeutics.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145097"},"PeriodicalIF":4.7,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145799812","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 : 2025-12-17DOI: 10.1016/j.molstruc.2025.145064
Zafar Un Nisa , Rabail Javed , Ali Ahmad , Afnan Qabil Alshammari , Murad A. AlDamen , Afkar Qabil Alshammari , Aziz B. Ibragimov , Muhammad Nadeem Akhtar
A cadmium-based complex formulated; [Cd(teaH3)2]SO4·3H2O (1) (where teaH3 = triethanolamine), was prepared by the reaction of CdSO4.8H2O with triethanolamine and 1-methylimidazole in MeOH. In this complex, two teaH₃ ligands adopted distinct tridentate and tetra-dentate coordination modes around the Cd(II) center, along with an anionic sulfate counter ion and three lattice water molecules. These coordination variations resulted in an unusual seven coordination number exhibiting capped octahedral (CShM = 1.497) and capped trigonal prismatic (CShM = 1.229) geometries. The photocatalytic activity of complex 1 was systematically evaluated for the degradation of two organic dyes: methylene blue (MB) and methyl orange (MO). Under optimized conditions (6 mg catalyst, 5 ppm dye concentration, 308 K), complex 1 achieved degradation efficiencies of 86.56 % for MB and 58.25 % for MO within 70 min. Kinetic studies stipulated that the dye degradation followed a pseudo-first-order (PFO) reaction model, with rate constants calculated as 0.02921 min⁻¹ and R² = 0.89675 for MB while 0.01345 min⁻¹ and R² = 0.93236 value for MO. The photocatalytic degradation of dyes was performed through light-induced generation of electron–hole pairs that generate reactive oxygen species (•OH and •O₂⁻), which involves the oxidative degradation of dyes yielded, H₂O and CO₂. Furthermore, recyclability studies demonstrated excellent stability, retained >90 % activity after three cycles. Hirshfeld surface analysis revealed a total surface area of 362.26 Ų and a volume of 469.77 ų, based on normalized contact distances (dnorm), emphasizing the dominant contribution of H···H (57.5 %) and H···O/O···H (42.5 %) interactions in crystal packing. This study highlights the structural versatility and photocatalytic efficacy of Cd(II)-triethanolamine system, underscoring their potential as sustainable photocatalysts for dye-contaminated wastewater remediation.
{"title":"Triethanolamine-based Cd(II) complex with unusual coordination number: Synthesis, characterization, Hirshfeld surface analysis and photocatalytic degradation of organic dyes","authors":"Zafar Un Nisa , Rabail Javed , Ali Ahmad , Afnan Qabil Alshammari , Murad A. AlDamen , Afkar Qabil Alshammari , Aziz B. Ibragimov , Muhammad Nadeem Akhtar","doi":"10.1016/j.molstruc.2025.145064","DOIUrl":"10.1016/j.molstruc.2025.145064","url":null,"abstract":"<div><div>A cadmium-based complex formulated; [Cd(teaH<sub>3</sub>)<sub>2</sub>]SO<sub>4·</sub>3H<sub>2</sub>O (<strong>1</strong>) (where teaH<sub>3</sub> = triethanolamine), was prepared by the reaction of CdSO<sub>4</sub>.8H<sub>2</sub>O with triethanolamine and 1-methylimidazole in MeOH. In this complex, two teaH₃ ligands adopted distinct tridentate and tetra-dentate coordination modes around the Cd(II) center, along with an anionic sulfate counter ion and three lattice water molecules. These coordination variations resulted in an unusual seven coordination number exhibiting capped octahedral (CShM = 1.497) and capped trigonal prismatic (CShM = 1.229) geometries. The photocatalytic activity of complex <strong>1</strong> was systematically evaluated for the degradation of two organic dyes: methylene blue (MB) and methyl orange (MO). Under optimized conditions (6 mg catalyst, 5 ppm dye concentration, 308 K), complex <strong>1</strong> achieved degradation efficiencies of 86.56 % for MB and 58.25 % for MO within 70 min. Kinetic studies stipulated that the dye degradation followed a pseudo-first-order (PFO) reaction model, with rate constants calculated as 0.02921 min⁻¹ and R² = 0.89675 for MB while 0.01345 min⁻¹ and R² = 0.93236 value for MO. The photocatalytic degradation of dyes was performed through light-induced generation of electron–hole pairs that generate reactive oxygen species (•OH and •O₂⁻), which involves the oxidative degradation of dyes yielded, H₂O and CO₂. Furthermore, recyclability studies demonstrated excellent stability, retained >90 % activity after three cycles. Hirshfeld surface analysis revealed a total surface area of 362.26 Ų and a volume of 469.77 ų, based on normalized contact distances (d<em><sub>norm</sub></em>), emphasizing the dominant contribution of H···H (57.5 %) and H···O/O···H (42.5 %) interactions in crystal packing. This study highlights the structural versatility and photocatalytic efficacy of Cd(II)-triethanolamine system, underscoring their potential as sustainable photocatalysts for dye-contaminated wastewater remediation.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145064"},"PeriodicalIF":4.7,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838612","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 : 2025-12-16DOI: 10.1016/j.molstruc.2025.145095
Di-Ming Chen, Xue-Jing Zhang, Dong-Ying Shi, Lin Han
The separation of C2H6 (ethane) from C2H4 (ethylene) to produce C2H4 with high purity is an important but challenging task in chemical industry due to their similar physical properties including molecular sizes and boiling points. Metal-organic frameworks (MOFs) with modifiable pore surroundings give new avenues for the development of functional materials for the targeted gas selective separation, especially for the design of C2H6-selective ones with simplified separation process and reduced energy consumption compared with those C2H4-selective ones. In the present study, a new Co(II)-based MOF featuring the formula of {[Co2(μ2OH)(CPT)2(HCOO)](DMF)3(MeOH)}n (1) has been successfully prepared by reaction of Co(II) salt with a bifunctional organic ligand 4-(4H-1,2,4-triazol-4-yl)benzoic acid (HCPT). The microporous pore surroundings of 1 feature high density of aromatic benzene ring and triazole groups coupled with uncoordinated O atoms, which collectively generate stronger interactions with C2H6 molecules than with C2H4 as revealed by the following dispersion corrected DFT calculations. As a result, the activated 1 shows a high C2H6 uptake capacity of 109.1 cm3/g with a moderate high C2H6/C2H4 (50:50) selectivity of 1.92 at 298 K and 1 bar, and such a separation ability was further supported by the breakthrough experiment. To further probe the underlying separation mechanism, the molecular dynamic simulation and DFT calculations were carried out, and the results coincide well with the experimental ones, which point out that the multiple synergistic interactions between C2H6 molecules with the pore surface of 1 account for the high C2H6 uptake capacity and C2H6/C2H4 selectivity.
{"title":"A bifunctional ligand-based metal-organic framework with rich aromatic pores and open O donor sites for selective C2H6/C2H4 separation","authors":"Di-Ming Chen, Xue-Jing Zhang, Dong-Ying Shi, Lin Han","doi":"10.1016/j.molstruc.2025.145095","DOIUrl":"10.1016/j.molstruc.2025.145095","url":null,"abstract":"<div><div>The separation of C<sub>2</sub>H<sub>6</sub> (ethane) from C<sub>2</sub>H<sub>4</sub> (ethylene) to produce C<sub>2</sub>H<sub>4</sub> with high purity is an important but challenging task in chemical industry due to their similar physical properties including molecular sizes and boiling points. Metal-organic frameworks (MOFs) with modifiable pore surroundings give new avenues for the development of functional materials for the targeted gas selective separation, especially for the design of C<sub>2</sub>H<sub>6</sub>-selective ones with simplified separation process and reduced energy consumption compared with those C<sub>2</sub>H<sub>4</sub>-selective ones. In the present study, a new Co(II)-based MOF featuring the formula of {[Co<sub>2</sub>(μ<sub>2</sub><sub><img></sub>OH)(CPT)<sub>2</sub>(HCOO)](DMF)<sub>3</sub>(MeOH)}<sub>n</sub> (<strong>1</strong>) has been successfully prepared by reaction of Co(II) salt with a bifunctional organic ligand 4-(4<em>H</em>-1,2,4-triazol-4-yl)benzoic acid (HCPT). The microporous pore surroundings of <strong>1</strong> feature high density of aromatic benzene ring and triazole groups coupled with uncoordinated O atoms, which collectively generate stronger interactions with C<sub>2</sub>H<sub>6</sub> molecules than with C<sub>2</sub>H<sub>4</sub> as revealed by the following dispersion corrected DFT calculations. As a result, the activated <strong>1</strong> shows a high C<sub>2</sub>H<sub>6</sub> uptake capacity of 109.1 cm<sup>3</sup>/g with a moderate high C<sub>2</sub>H<sub>6</sub>/C<sub>2</sub>H<sub>4</sub> (50:50) selectivity of 1.92 at 298 K and 1 bar, and such a separation ability was further supported by the breakthrough experiment. To further probe the underlying separation mechanism, the molecular dynamic simulation and DFT calculations were carried out, and the results coincide well with the experimental ones, which point out that the multiple synergistic interactions between C<sub>2</sub>H<sub>6</sub> molecules with the pore surface of <strong>1</strong> account for the high C<sub>2</sub>H<sub>6</sub> uptake capacity and C<sub>2</sub>H<sub>6</sub>/C<sub>2</sub>H<sub>4</sub> selectivity.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145095"},"PeriodicalIF":4.7,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838815","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 : 2025-12-16DOI: 10.1016/j.molstruc.2025.145081
Hasan Yakan
New 2,6-dimethylphenyl-derived thiosemicarbazones (1–10) were synthesized through the condensation of various aldehydes with N-(o-tolyl)hydrazinecarbothioamide. The key thiosemicarbazide intermediate was obtained from the reaction of 2,6-dimethylphenyl isothiocyanate with hydrazine monohydrate. The chemical structures and purity of all newly synthesized compounds were confirmed by standard spectroscopic techniques, including proton and carbon nuclear magnetic resonance (¹H and ¹³C NMR), Fourier-transform infrared spectroscopy (FT-IR), and elemental analysis. The antioxidant activities of the compounds were evaluated using the 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical scavenging assay. Based on the calculated IC₅₀ values from percent inhibition data, the antioxidant efficacy of the compounds followed the order: Ascorbic acid > 9 > 7 > 5 > 3 > 2 > 6 > 8 > 10 > 4 > 1. The DPPH radical scavenging capacities of compounds 9, 7, and 5 (7.52 ± 0.11, 9.25 ± 0.12, and 9.27 ± 0.12 µM, respectively) were found to be rather close to those of standard ascorbic acid (6.39 ± 0.11 µM). This indicates that these compounds possess free radical scavenging ability similar to that of ascorbic acid, even at low concentrations. Compounds 9, 7, and 5 contain both -OCH₃ and -OH groups, which contribute to their high antioxidant activity by donating electrons to the medium, thereby increasing the stability of the resulting radicals. Additionally, the reducing power of the compounds was assessed using the potassium ferricyanide reduction method, and the absorbance values of all compounds were found to be lower than that of gallic acid. The study examined the influence of structural variations on antioxidant activity, with particular emphasis on the role of different functional groups in modulating radical scavenging efficiency. The structural and electronic characteristics of the compounds were analysed using DFT calculations, which showed a clear correlation with antioxidant activity. The compounds possessing low O–H BDE values and wide spin delocalization stabilized radicals more effectively, leading to enhanced antioxidant behaviour.
{"title":"New 2,6-dimethylphenyl derived thiosemicarbazones: Synthesis, spectroscopic elucidation, antioxidant activities, and theoretical studies","authors":"Hasan Yakan","doi":"10.1016/j.molstruc.2025.145081","DOIUrl":"10.1016/j.molstruc.2025.145081","url":null,"abstract":"<div><div>New 2,6-dimethylphenyl-derived thiosemicarbazones (<strong>1</strong>–<strong>10</strong>) were synthesized through the condensation of various aldehydes with <em>N</em>-(<em>o</em>-tolyl)hydrazinecarbothioamide. The key thiosemicarbazide intermediate was obtained from the reaction of 2,6-dimethylphenyl isothiocyanate with hydrazine monohydrate. The chemical structures and purity of all newly synthesized compounds were confirmed by standard spectroscopic techniques, including proton and carbon nuclear magnetic resonance (¹H and ¹³C NMR), Fourier-transform infrared spectroscopy (FT-IR), and elemental analysis. The antioxidant activities of the compounds were evaluated using the 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical scavenging assay. Based on the calculated IC₅₀ values from percent inhibition data, the antioxidant efficacy of the compounds followed the order: Ascorbic acid > <strong>9</strong> > <strong>7</strong> > <strong>5</strong> > <strong>3</strong> > <strong>2</strong> > <strong>6</strong> > <strong>8</strong> > <strong>10</strong> > <strong>4</strong> > <strong>1</strong>. The DPPH radical scavenging capacities of compounds <strong>9, 7</strong>, and <strong>5</strong> (7.52 ± 0.11, 9.25 ± 0.12, and 9.27 ± 0.12 µM, respectively) were found to be rather close to those of standard ascorbic acid (6.39 ± 0.11 µM). This indicates that these compounds possess free radical scavenging ability similar to that of ascorbic acid, even at low concentrations. Compounds <strong>9, 7</strong>, and <strong>5</strong> contain both -OCH₃ and -OH groups, which contribute to their high antioxidant activity by donating electrons to the medium, thereby increasing the stability of the resulting radicals. Additionally, the reducing power of the compounds was assessed using the potassium ferricyanide reduction method, and the absorbance values of all compounds were found to be lower than that of gallic acid. The study examined the influence of structural variations on antioxidant activity, with particular emphasis on the role of different functional groups in modulating radical scavenging efficiency. The structural and electronic characteristics of the compounds were analysed using DFT calculations, which showed a clear correlation with antioxidant activity. The compounds possessing low O–H BDE values and wide spin delocalization stabilized radicals more effectively, leading to enhanced antioxidant behaviour.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145081"},"PeriodicalIF":4.7,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145799806","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 : 2025-12-16DOI: 10.1016/j.molstruc.2025.145098
Mehdi Abdollahi , Behzad Soltani , Mohammad Janghouri , Daniel Fuhrmann , Farzin Marandi
Three new mononuclear complexes, [Zn(2,2′-bpy)(tfnb)2] (1), [Zn(2,2′-bpy)(tfpb)2] (2), and [Zn(2,2′-bpy)(tfmpb)2] (3), where 2,2′-bpy represents 2,2′-bipyridine, Htfnb is 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione, Htfpb is 4,4,4-trifluoro-1-phenyl-1,3-butanedione, and Htfmpb is 4,4,4-trifluoro-1-(4-methoxyphenyl)-1,3-butanedione, were synthesized. These complexes were comprehensively characterized through elemental analysis, FT-IR, 1H NMR, and single-crystal X-ray diffraction. The geometry around each metal center exhibited a distorted octahedral arrangement. The crystal structures revealed the presence of CH∙∙∙X (X = O, F) interactions and π–π stacking, leading to the formation of supramolecular assemblies. The impact of β-diketone substitutions on the structural and functional properties of these complexes were explored. Devices were fabricated using an (ITO)/PEDOT:PSS (60 nm)/PVK:PBD:Zinc(II) complexes (55 nm)/Al (150 nm) configuration. The resulting devices exhibited peak emissions in the range of 527 nm to 578 nm. It has been shown that incorporating [Zn(2,2′-bpy)] with different fluorinated β-diketonate ligands enables the modification and control of its electrical and optical properties, such as turn-on voltage, operating voltage, luminescence, absorption, Commission Internationale de l'Eclairage (CIE) coordinates, photoluminescence (PL), and electroluminescence (EL), which are critical for applications in the OLED device industry. The results indicated that the device incorporating [Zn(2,2′-bpy)(tfmpb)2] (1) exhibited the most distinct orange emission among all tested devices. This device achieved a maximum power efficiency of 1.3 lm/W and a luminance of approximately 12,874 cd/m² at 12 V.
{"title":"Tunable color emission in Zinc(II)–2,2′-Bipyridine Complexes with fluorinated β-Diketonate ligands: Structural and spectroscopic studies","authors":"Mehdi Abdollahi , Behzad Soltani , Mohammad Janghouri , Daniel Fuhrmann , Farzin Marandi","doi":"10.1016/j.molstruc.2025.145098","DOIUrl":"10.1016/j.molstruc.2025.145098","url":null,"abstract":"<div><div>Three new mononuclear complexes, [Zn(2,2′-bpy)(tfnb)<sub>2</sub>] (<strong>1</strong>), [Zn(2,2′-bpy)(tfpb)<sub>2</sub>] (<strong>2</strong>), and [Zn(2,2′-bpy)(tfmpb)<sub>2</sub>] (<strong>3</strong>), where 2,2′-bpy represents 2,2′-bipyridine, Htfnb is 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione, Htfpb is 4,4,4-trifluoro-1-phenyl-1,3-butanedione, and Htfmpb is 4,4,4-trifluoro-1-(4-methoxyphenyl)-1,3-butanedione, were synthesized. These complexes were comprehensively characterized through elemental analysis, FT-IR, <sup>1</sup>H NMR, and single-crystal X-ray diffraction. The geometry around each metal center exhibited a distorted octahedral arrangement. The crystal structures revealed the presence of C<img>H∙∙∙X (<em>X</em> = <em>O</em>, F) interactions and π–π stacking, leading to the formation of supramolecular assemblies. The impact of <em>β</em>-diketone substitutions on the structural and functional properties of these complexes were explored. Devices were fabricated using an (ITO)/PEDOT:PSS (60 nm)/PVK:PBD:Zinc(II) complexes (55 nm)/Al (150 nm) configuration. The resulting devices exhibited peak emissions in the range of 527 nm to 578 nm. It has been shown that incorporating [Zn(2,2′-bpy)] with different fluorinated β-diketonate ligands enables the modification and control of its electrical and optical properties, such as turn-on voltage, operating voltage, luminescence, absorption, Commission Internationale de l'Eclairage (CIE) coordinates, photoluminescence (PL), and electroluminescence (EL), which are critical for applications in the OLED device industry. The results indicated that the device incorporating [Zn(2,2′-bpy)(tfmpb)<sub>2</sub>] (<strong>1</strong>) exhibited the most distinct orange emission among all tested devices. This device achieved a maximum power efficiency of 1.3 lm/W and a luminance of approximately 12,874 cd/m² at 12 V.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145098"},"PeriodicalIF":4.7,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838734","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 : 2025-12-15DOI: 10.1016/j.molstruc.2025.145084
Hongtian Yang , Jiayu Wang , Haohao Guo , Lan Miao , Yuchen Song , Xia Zhang , Fang Lu , Yufeng Liu , Ying Zhang
Human serum albumin (HSA) serves as a critical carrier for systemic drug delivery.This study elucidates the competitive binding dynamics of the main active component of saffron, crocin-1, and its aglycone metabolite crocetin to HSA through integrated multispectral and computational analyses. Ultracentrifugation revealed high plasma protein binding (PPB) rates for both compounds (crocin-1: 90 %; crocetin: >99 %), indicating susceptibility to displacement by high-affinity drugs like warfarin. Static quenching dominated HSA interactions, confirmed by temperature-dependent KSV decay, Kq exceeding diffusion limits, and UV–Vis spectral shifts. Crocetin exhibited 43 % higher affinity (Ka = 3.49×105 M-1) than crocin-1 (Ka = 2.44 × 105 M-1) at 310 K, driven by bidentate hydrogen bonding (LYS199/HIS242) and deeper hydrophobic pocket penetration, as evidenced by molecular docking. Thermodynamically, crocin-1 binding was enthalpy-driven (ΔH = −38.55 kJ/mol) but hindered by glycosyl conformational entropy loss, whereas crocetin leveraged strong exothermicity (ΔH = − 65.15 kJ/mol) to overcome entropy penalties. Structurally, crocin-1 reduced HSA α-helix content by 5.2 %, while crocetin preserved integrity. Critically, co-incubation with crocin-1/crocetin doubled free warfarin concentrations (P < 0.001), highlighting clinical risks for anticoagulant co-therapy. These findings provide a foundation for developing albumin-based delivery systems for saffron-derived neuroprotectants while highlighting clinical risks in co-therapy.
{"title":"Albumin-mediated binding mechanisms of crocin-1 and crocetin: thermodynamics, molecular dynamics, and implications for warfarin displacement","authors":"Hongtian Yang , Jiayu Wang , Haohao Guo , Lan Miao , Yuchen Song , Xia Zhang , Fang Lu , Yufeng Liu , Ying Zhang","doi":"10.1016/j.molstruc.2025.145084","DOIUrl":"10.1016/j.molstruc.2025.145084","url":null,"abstract":"<div><div>Human serum albumin (HSA) serves as a critical carrier for systemic drug delivery.This study elucidates the competitive binding dynamics of the main active component of saffron, crocin-1, and its aglycone metabolite crocetin to HSA through integrated multispectral and computational analyses. Ultracentrifugation revealed high plasma protein binding (PPB) rates for both compounds (crocin-1: 90 %; crocetin: >99 %), indicating susceptibility to displacement by high-affinity drugs like warfarin. Static quenching dominated HSA interactions, confirmed by temperature-dependent <em>K</em><sub>SV</sub> decay, <em>K</em><sub>q</sub> exceeding diffusion limits, and UV–Vis spectral shifts. Crocetin exhibited 43 % higher affinity (<em>K</em><sub>a</sub> = 3.49×10<sup>5</sup> M<sup>-1</sup>) than crocin-1 (<em>K</em><sub>a</sub> = 2.44 × 10<sup>5</sup> M<sup>-1</sup>) at 310 K, driven by bidentate hydrogen bonding (LYS199/HIS242) and deeper hydrophobic pocket penetration, as evidenced by molecular docking. Thermodynamically, crocin-1 binding was enthalpy-driven (Δ<em>H</em> = −38.55 kJ/mol) but hindered by glycosyl conformational entropy loss, whereas crocetin leveraged strong exothermicity (Δ<em>H</em> = − 65.15 kJ/mol) to overcome entropy penalties. Structurally, crocin-1 reduced HSA α-helix content by 5.2 %, while crocetin preserved integrity. Critically, co-incubation with crocin-1/crocetin doubled free warfarin concentrations (<em>P</em> < 0.001), highlighting clinical risks for anticoagulant co-therapy. These findings provide a foundation for developing albumin-based delivery systems for saffron-derived neuroprotectants while highlighting clinical risks in co-therapy.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145084"},"PeriodicalIF":4.7,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145882103","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 : 2025-12-15DOI: 10.1016/j.molstruc.2025.145090
A.L. Ruiz-Castillo , Brenda Acosta Ruelas , Eduardo Arenas Sánchez , Elena Smolentseva , C.E. Niño González , M.A. Urbano-Peña , F. Ruiz
Water pollution by persistent organic contaminants requires multifunctional materials capable of removing diverse pollutants by multiple processes. This study provides a systematic comparison of Bi2O3/BiOX (where X is F, Cl, Br, or I) heterojunctions across the entire halide series, which is scarcely reported. The role of the halogen identity on the structure-function relationship is highlighted. Bi2O3/BiOX heterojunctions were synthesized via a solvothermal method through in-situ modification of bismuth oxide (Bi2O3), with corresponding halide salts. The resulting materials were characterized using scanning and transmission electron microscopy (SEM and TEM), X-ray diffraction (XRD), nitrogen physisorption, Fourier-transformed infrared (FTIR), Raman and UV-Vis diffuse reflectance spectroscopies (DRS). Their multifunctionality was evaluated through methylene blue (MB) adsorption, caffeine photodegradation in aqueous solutions and catalytic 4-nitrophenol (4-NP) reduction. Clear differences in photocatalytic oxidation rates were observed across the series, with Bi₂O₃/BiOBr exhibiting the best performance, achieving 98% MB removal within 50 minutes, and caffeine degradation efficiencies of 81% under UV and 53% under visible light. Scavenger experiments identified photogenerated holes (h+) and superoxide radical (·O₂⁻) as the primary reactive species involved in the degradation process. Incorporation of silver nanoparticles (Ag, 0.25wt%) onto Bi2O3/BiOBr further improved the photodegradation of caffeine to 92% under UV and 68% under visible light and enabled efficient catalytic reduction of 4-NP with an apparent reaction rate constant (kapp) of 0.049 min−1. Reusability tests showed a significant decrease in catalytic activity (TOF drop >70% after two cycles), attributed to active site blocking by 4-AP, partial Ag leaching, and nanoparticle agglomeration.
This study establishes Bi2O3/BiOBr as the most efficient heterojunction within the BiOX series and demonstrates that Ag modification not only enhances photocatalysis but also enables catalytic reduction reactions. These findings demonstrate the heterojunctions' multifunctionality and highlight their strong potential for wastewater treatment applications, offering new insights for the rational design of multifunctional photocatalysts for wastewater treatment.
{"title":"Bi2O3/BiOX (X=F, Cl, Br or I) multifunctional heterojunctions type for efficient polluted water remediation","authors":"A.L. Ruiz-Castillo , Brenda Acosta Ruelas , Eduardo Arenas Sánchez , Elena Smolentseva , C.E. Niño González , M.A. Urbano-Peña , F. Ruiz","doi":"10.1016/j.molstruc.2025.145090","DOIUrl":"10.1016/j.molstruc.2025.145090","url":null,"abstract":"<div><div>Water pollution by persistent organic contaminants requires multifunctional materials capable of removing diverse pollutants by multiple processes. This study provides a systematic comparison of Bi<sub>2</sub>O<sub>3</sub>/BiOX (where X is F, Cl, Br, or I) heterojunctions across the entire halide series, which is scarcely reported. The role of the halogen identity on the structure-function relationship is highlighted. Bi<sub>2</sub>O<sub>3</sub>/BiOX heterojunctions were synthesized via a solvothermal method through in-situ modification of bismuth oxide (Bi<sub>2</sub>O<sub>3</sub>), with corresponding halide salts. The resulting materials were characterized using scanning and transmission electron microscopy (SEM and TEM), X-ray diffraction (XRD), nitrogen physisorption, Fourier-transformed infrared (FTIR), Raman and UV-Vis diffuse reflectance spectroscopies (DRS). Their multifunctionality was evaluated through methylene blue (MB) adsorption, caffeine photodegradation in aqueous solutions and catalytic 4-nitrophenol (4-NP) reduction. Clear differences in photocatalytic oxidation rates were observed across the series, with Bi₂O₃/BiOBr exhibiting the best performance, achieving 98% MB removal within 50 minutes, and caffeine degradation efficiencies of 81% under UV and 53% under visible light. Scavenger experiments identified photogenerated holes (h<sup>+</sup>) and superoxide radical (·O₂⁻) as the primary reactive species involved in the degradation process. Incorporation of silver nanoparticles (Ag, 0.25wt%) onto Bi<sub>2</sub>O<sub>3</sub>/BiOBr further improved the photodegradation of caffeine to 92% under UV and 68% under visible light and enabled efficient catalytic reduction of 4-NP with an apparent reaction rate constant (<em>k<sub>app</sub></em>) of 0.049 min<sup>−1</sup>. Reusability tests showed a significant decrease in catalytic activity (TOF drop >70% after two cycles), attributed to active site blocking by 4-AP, partial Ag leaching, and nanoparticle agglomeration.</div><div>This study establishes Bi<sub>2</sub>O<sub>3</sub>/BiOBr as the most efficient heterojunction within the BiOX series and demonstrates that Ag modification not only enhances photocatalysis but also enables catalytic reduction reactions. These findings demonstrate the heterojunctions' multifunctionality and highlight their strong potential for wastewater treatment applications, offering new insights for the rational design of multifunctional photocatalysts for wastewater treatment.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145090"},"PeriodicalIF":4.7,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771868","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 : 2025-12-15DOI: 10.1016/j.molstruc.2025.145093
Hamed Vosoughi Motlagh , Mina Emami , Mohammad Hosein Sayahi , Manica Negahdaripour , Navid Dastyafteh , Younes Ghasemi , Mohammad Reza Gohari , Mehdi Asadi , Bagher Larijani , Mohammad Reza Mohajeri-Tehrani , Mehdi Abedi , Zahra Pakrouh Jahromi , Sayed Mahmoud Sajjadi-Jazi , Mohammad Mahdavi , Massoud Amanlou , Sara Ranjbar
This study presents the synthesis of new 2-amino-1,4-naphthoquinone-N-alkyl/arylbenzamide derivatives (5a-n) and evaluates their cytotoxicity against two human cancer cells (A549 and MCF-7), as well as against normal human cells (MRC-5), using the MTT assay. Compound 5a demonstrated superior cytotoxicity compared to other derivatives against the A549 and MCF-7 cells, with IC50 values of 11.4 ± 2.7 and 13.9 ± 1.1 μM, respectively. Its anti-tumor activity was comparable to that of cisplatin. Additionally, 5a exhibited selectivity toward cancer cell lines over MRC-5 (IC50 = 72.7 ± 3.2 μM). Further investigations revealed that 5a could effectively cause cell cycle arrest at the G0/G1 phase and induce apoptosis in A549 cells. Molecular docking studies were also conducted to assess the potential interactions of 5a with the binding sites of phosphatidylinositol 3-kinase and caspase-8. These findings provide new insights for further development of naphthoquinone derivatives as anti-cancer agents.
{"title":"Synthesis, biological evaluation, and molecular docking analysis of novel 1,4-naphthoquinone-benzamides as anti-cancer agents","authors":"Hamed Vosoughi Motlagh , Mina Emami , Mohammad Hosein Sayahi , Manica Negahdaripour , Navid Dastyafteh , Younes Ghasemi , Mohammad Reza Gohari , Mehdi Asadi , Bagher Larijani , Mohammad Reza Mohajeri-Tehrani , Mehdi Abedi , Zahra Pakrouh Jahromi , Sayed Mahmoud Sajjadi-Jazi , Mohammad Mahdavi , Massoud Amanlou , Sara Ranjbar","doi":"10.1016/j.molstruc.2025.145093","DOIUrl":"10.1016/j.molstruc.2025.145093","url":null,"abstract":"<div><div>This study presents the synthesis of new 2-amino-1,4-naphthoquinone-<em>N-</em>alkyl/arylbenzamide derivatives (<strong>5a-n</strong>) and evaluates their cytotoxicity against two human cancer cells (A549 and MCF-7), as well as against normal human cells (MRC-5), using the MTT assay. Compound <strong>5a</strong> demonstrated superior cytotoxicity compared to other derivatives against the A549 and MCF-7 cells, with IC<sub>50</sub> values of 11.4 ± 2.7 and 13.9 ± 1.1 μM, respectively. Its anti-tumor activity was comparable to that of cisplatin. Additionally, <strong>5a</strong> exhibited selectivity toward cancer cell lines over MRC-5 (IC<sub>50</sub> = 72.7 ± 3.2 μM). Further investigations revealed that <strong>5a</strong> could effectively cause cell cycle arrest at the G<sub>0</sub>/G<sub>1</sub> phase and induce apoptosis in A549 cells. Molecular docking studies were also conducted to assess the potential interactions of <strong>5a</strong> with the binding sites of phosphatidylinositol 3-kinase and caspase-8. These findings provide new insights for further development of naphthoquinone derivatives as anti-cancer agents.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145093"},"PeriodicalIF":4.7,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145839087","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 : 2025-12-15DOI: 10.1016/j.molstruc.2025.145083
Jing Liu , Jianhua Wang , Xiaolu Hou , Zhenming Dong , Yu Wang , Shaomin Shuang
Based on the hemicyanine fluorescent dye scaffold, a novel hydrazine-sensitive luminescent probe, CY-Br, was developed by introducing a 4-bromobutyric acid functional moiety as the responsive group. The nucleophilic attack of hydrazine triggers the elimination of the 4-bromobutyrate group from CY-Br to yield the corresponding phenol product (CY-OH), thereby promoting the intramolecular charge transfer (ICT) process and consequently giving rise to pronounced optical signal alterations (red-shifted UV absorption spectrum and amplified fluorescence emission). CY-Br demonstrates several notable advantages, comprising near-infrared luminescence at 730 nm, a fast response time of 40 s, superior selectivity and sensitivity (detection limit of 16.2 nM), as well as precise mitochondria targeting capability. The response mechanism was investigated employing nuclear magnetic titration and mass spectrometry techniques, with subsequent validation through theoretical computational analysis. CY-Br-coated paper strips were developed as a portable and efficient sensing platform for hydrazine detection. Furthermore, CY-Br exhibited remarkable efficacy in fluorescence imaging of both exogenous and endogenous hydrazine in live cellular and zebrafish models. By employing CY-Br, the in situ visualization of drug-induced hydrazine release within live cells and zebrafish has been achieved.
{"title":"A novel mitochondria targeting near-infrared fluorescent probe for specific visualization of toxic hydrazine in aqueous environments, live cells and zebrafish","authors":"Jing Liu , Jianhua Wang , Xiaolu Hou , Zhenming Dong , Yu Wang , Shaomin Shuang","doi":"10.1016/j.molstruc.2025.145083","DOIUrl":"10.1016/j.molstruc.2025.145083","url":null,"abstract":"<div><div>Based on the hemicyanine fluorescent dye scaffold, a novel hydrazine-sensitive luminescent probe, CY-Br, was developed by introducing a 4-bromobutyric acid functional moiety as the responsive group. The nucleophilic attack of hydrazine triggers the elimination of the 4-bromobutyrate group from CY-Br to yield the corresponding phenol product (CY-OH), thereby promoting the intramolecular charge transfer (ICT) process and consequently giving rise to pronounced optical signal alterations (red-shifted UV absorption spectrum and amplified fluorescence emission). CY-Br demonstrates several notable advantages, comprising near-infrared luminescence at 730 nm, a fast response time of 40 s, superior selectivity and sensitivity (detection limit of 16.2 nM), as well as precise mitochondria targeting capability. The response mechanism was investigated employing nuclear magnetic titration and mass spectrometry techniques, with subsequent validation through theoretical computational analysis. CY-Br-coated paper strips were developed as a portable and efficient sensing platform for hydrazine detection. Furthermore, CY-Br exhibited remarkable efficacy in fluorescence imaging of both exogenous and endogenous hydrazine in live cellular and zebrafish models. By employing CY-Br, the in situ visualization of drug-induced hydrazine release within live cells and zebrafish has been achieved.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145083"},"PeriodicalIF":4.7,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771896","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 : 2025-12-15DOI: 10.1016/j.molstruc.2025.145088
Nageswara Reddy Gosu , Ramakrishna Reddy K , Venkatesh Sadhana , Prabakaran Arunachalam , Mohanraj P , Gnana Sekar Gopu
The Cu2+ and La3+ complexes of a novel Schiff base (HL) were synthesized by condensing 4-methylbenzohydrazide with 2-Formylphenol. Spectroscopic studies, including electronic spectra, proton NMR, FT-IR, magnetic measurement, molar conductance, thermogravimetric analysis, and melting point, were used to characterised the Schiff base and it’s Cu, La metal complexes. Elemental analysis for confirmed the formation of 1:2 [M:L] complexes. Molar conductivity measurements indicated that the complexes are non-electrolytic in nature. Both coordinated and hydrated water molecules have been detected in the complexes, as demonstrated by thermogravimetric analysis. The Schiff base coordinated with Cu2+ and La3+ metal ions via N2O2 atoms, functioning as a tetra dentate molecule. Cu2+ and La3+ complexes, represented by the initials I and II, respectively, exhibited octahedral geometries, according to the data reported. DFT calculations were utilized to investigate the quantum chemical parameters and confirm the molecular structures of HL and its corresponding metal complexes. The prepared HL, and its I, II metal complexes showcased significant antimicrobial and tested for their antibacterial properties against Escherichia coli and Enterococcus faecalis bacteria, as well as Bacillus subtilis. The findings reveal that these complexes possess significant antimicrobial activity, underscoring their potential as effective therapeutic agents. Furthermore, molecular docking analysis the binding affinity and residue interactions between the Schiff base ligand and its complexes with the E. coli DNA Gyrase subunit B (1QFG) protein. DFT calculations confirmed the optimized structures and provided insights into their energy levels, including HOMO, LUMO, MESP, MESP bar, and global reactivity parameters.
{"title":"Synthesis, spectroscopic analysis, molecular docking, biological evaluation, and DFT optimization of 4-methylbenzohydrazide Schiff base metal complexes","authors":"Nageswara Reddy Gosu , Ramakrishna Reddy K , Venkatesh Sadhana , Prabakaran Arunachalam , Mohanraj P , Gnana Sekar Gopu","doi":"10.1016/j.molstruc.2025.145088","DOIUrl":"10.1016/j.molstruc.2025.145088","url":null,"abstract":"<div><div>The Cu<sup>2+</sup> and La<sup>3+</sup> complexes of a novel Schiff base (HL) were synthesized by condensing 4-methylbenzohydrazide with 2-Formylphenol. Spectroscopic studies, including electronic spectra, proton NMR, FT-IR, magnetic measurement, molar conductance, thermogravimetric analysis, and melting point, were used to characterised the Schiff base and it’s Cu, La metal complexes. Elemental analysis for confirmed the formation of 1:2 [M:L] complexes. Molar conductivity measurements indicated that the complexes are non-electrolytic in nature. Both coordinated and hydrated water molecules have been detected in the complexes, as demonstrated by thermogravimetric analysis. The Schiff base coordinated with Cu<sup>2+</sup> and La<sup>3+</sup> metal ions via N<sub>2</sub>O<sub>2</sub> atoms, functioning as a tetra dentate molecule. Cu<sup>2+</sup> and La<sup>3+</sup> complexes, represented by the initials <strong>I</strong> and <strong>II</strong>, respectively, exhibited octahedral geometries, according to the data reported. DFT calculations were utilized to investigate the quantum chemical parameters and confirm the molecular structures of HL and its corresponding metal complexes. The prepared HL, and its <strong>I, II</strong> metal complexes showcased significant antimicrobial and tested for their antibacterial properties against <em>Escherichia coli</em> and <em>Enterococcus faecalis</em> bacteria, as well as <em>Bacillus subtilis</em>. The findings reveal that these complexes possess significant antimicrobial activity, underscoring their potential as effective therapeutic agents. Furthermore, molecular docking analysis the binding affinity and residue interactions between the Schiff base ligand and its complexes with the <em>E. coli</em> DNA <em>Gyrase subunit B</em> (1QFG) protein. DFT calculations confirmed the optimized structures and provided insights into their energy levels, including HOMO, LUMO, MESP, MESP bar, and global reactivity parameters.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1356 ","pages":"Article 145088"},"PeriodicalIF":4.7,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145799808","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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