In this contribution, four Ni(II) complex salts of the type Z2 [Ni(L)2] [Z = (CH3)4N+ (1), (C2H5)4N+(2), (C3H7)4N+(3) and (C5H11)4N+ (4); L = Cyanodithiocarbimate NCNCS22−)] have been synthesized. All four salts were characterized by elemental analysis and spectroscopy; while 1 and 3 were further characterized by single-crystal X-ray diffraction analysis. Their crystal structures exhibit sporadic interionic Ni‧‧‧H anagostic contacts, an uncommon feature in complex salts. The interaction energies of the Ni‧‧‧H contacts were evaluated computationally, revealing stronger interactions in 1 than in 3.
Crystal packing in all complexes is stabilized by C–H‧‧‧Y (YH, N, Csp), S‧‧‧N, C‧‧‧S and S‧‧‧H contacts, in addition to prevailing electrostatic forces. Hirshfeld surface analysis reveals that H‧‧‧H contacts provide the highest contribution among weaker interactions sustaining supramolecular architecture. The antimicrobial activities of complex salts 1–4 were evaluated against Bacillus subtilis (Gram-positive), Shigella boydii (Gram-negative), and the fungi Aspergillus flavus and Fusarium oxysporum. Complexes 1 and 2 have been found to exhibit inhibition efficiencies against B. subtilis comparable to streptomycin, indicating promising potential as alternative antimicrobial agent. Complexes 1 and 2 also inhibited F. oxysporum at 40 μg/disc, whereas 3 and 4 were inactive.
{"title":"Rare intermolecular Ni···H anagostic and non-covalent C–H···X (N, S, H) hydrogen bonding interactions assisted supramolecular structure and antimicrobial activity study of Ni(II) cyanodithiocarbimate salts","authors":"Santosh Kumar Singh , Sudip Mandal , Utkarsh Talukdar , Satish Kumar Verma , Shweta Singh , Michael G.B. Drew , Suman Kushwaha","doi":"10.1016/j.ica.2025.123035","DOIUrl":"10.1016/j.ica.2025.123035","url":null,"abstract":"<div><div>In this contribution, four Ni(II) complex salts of the type Z<sub>2</sub> [Ni(L)<sub>2</sub>] [Z = (CH<sub>3</sub>)<sub>4</sub>N<sup>+</sup> (<strong>1</strong>), (C<sub>2</sub>H<sub>5</sub>)<sub>4</sub>N<sup>+</sup>(<strong>2</strong>), (C<sub>3</sub>H<sub>7</sub>)<sub>4</sub>N<sup>+</sup>(<strong>3</strong>) and (C<sub>5</sub>H<sub>11</sub>)<sub>4</sub>N<sup>+</sup> (<strong>4</strong>); L = Cyanodithiocarbimate NCNCS<sub>2</sub> <sup>2−</sup>)] have been synthesized. All four salts were characterized by elemental analysis and spectroscopy; while <strong>1</strong> and <strong>3</strong> were further characterized by single-crystal X-ray diffraction analysis. Their crystal structures exhibit sporadic interionic Ni‧‧‧H anagostic contacts, an uncommon feature in complex salts. The interaction energies of the Ni‧‧‧H contacts were evaluated computationally, revealing stronger interactions in <strong>1</strong> than in <strong>3</strong>.</div><div>Crystal packing in all complexes is stabilized by C–H‧‧‧Y (Y<img>H, N, C<sub>sp</sub>), S‧‧‧N, C‧‧‧S and S‧‧‧H contacts, in addition to prevailing electrostatic forces. Hirshfeld surface analysis reveals that H‧‧‧H contacts provide the highest contribution among weaker interactions sustaining supramolecular architecture. The antimicrobial activities of complex salts <strong>1–4</strong> were evaluated against <em>Bacillus subtilis</em> (Gram-positive), <em>Shigella boydii</em> (Gram-negative), and the fungi <em>Aspergillus flavus</em> and <em>Fusarium oxysporum</em>. Complexes <strong>1</strong> and <strong>2</strong> have been found to exhibit inhibition efficiencies against <em>B. subtilis</em> comparable to <em>streptomycin</em>, indicating promising potential as alternative antimicrobial agent. Complexes <strong>1</strong> and <strong>2</strong> also inhibited <em>F. oxysporum</em> at 40 μg/disc, whereas <strong>3</strong> and <strong>4</strong> were inactive.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123035"},"PeriodicalIF":3.2,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787878","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-08DOI: 10.1016/j.ica.2025.123036
Jing Li, Yongqiang Tang, Baojuan Jiao, Jiangtao Li, Liuchang Wang
In this study, two new mixed-ligand dysprosium coordination polymers (CPs), [Dy₂(MPIP)₂(1,3-bdc)₃]ₙ·5ₙH₂O (CP1) and [Dy₂(MPIP)(1,3-bdc)₃]ₙ (CP2), were successfully synthesized under hydrothermal and solvothermal conditions. Structural analyses revealed that both CPs possess stable three-dimensional frameworks with distinct coordination environments. Fluorescence investigations demonstrated that CP1 exhibited a strong and selective quenching response toward tryptophan (Trp), following a linear Stern–Volmer relationship (R2 = 0.9933) with a detection limit of 1.85 μM. In contrast, CP2 showed excellent selectivity for chlortetracycline (CTE) with a high Stern–Volmer constant (KSV = 2.53 × 104 M−1) and a low detection limit of 1.2 μM. Mechanistic analyses indicated that the quenching of CP1 originated from competitive energy absorption, while that of CP2 resulted from combined energy transfer and hydrogen bonding interactions. These results highlight the potential of Dy(III)-based CPs as efficient, selective, and reusable fluorescent probes for amino acid and antibiotic detection, contributing to the advancement of lanthanide-based sensing materials for environmental and biomedical applications.
{"title":"Design, synthesis, and photoluminescent sensing properties of two Dy(III) coordination polymers constructed from N-heterocyclic ligands","authors":"Jing Li, Yongqiang Tang, Baojuan Jiao, Jiangtao Li, Liuchang Wang","doi":"10.1016/j.ica.2025.123036","DOIUrl":"10.1016/j.ica.2025.123036","url":null,"abstract":"<div><div>In this study, two new mixed-ligand dysprosium coordination polymers (CPs), [Dy₂(MPIP)₂(1,3-bdc)₃]ₙ·5ₙH₂O (CP1) and [Dy₂(MPIP)(1,3-bdc)₃]ₙ (CP2), were successfully synthesized under hydrothermal and solvothermal conditions. Structural analyses revealed that both CPs possess stable three-dimensional frameworks with distinct coordination environments. Fluorescence investigations demonstrated that CP1 exhibited a strong and selective quenching response toward tryptophan (Trp), following a linear Stern–Volmer relationship (R<sup>2</sup> = 0.9933) with a detection limit of 1.85 μM. In contrast, CP2 showed excellent selectivity for chlortetracycline (CTE) with a high Stern–Volmer constant (KSV = 2.53 × 10<sup>4</sup> M<sup>−1</sup>) and a low detection limit of 1.2 μM. Mechanistic analyses indicated that the quenching of CP1 originated from competitive energy absorption, while that of CP2 resulted from combined energy transfer and hydrogen bonding interactions. These results highlight the potential of Dy(III)-based CPs as efficient, selective, and reusable fluorescent probes for amino acid and antibiotic detection, contributing to the advancement of lanthanide-based sensing materials for environmental and biomedical applications.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123036"},"PeriodicalIF":3.2,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734152","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Reaction of imidazole-2-carbaldehyde thiosemicarbazone (H2L; where H2 depicts the two dissociable protons, the imidazole NH proton and the SH proton) with Ni(ClO4)2·6H2O in presence of triphenylphosphine yielded a complex of type [NiII(HL)(PPh3)]ClO4 (where HL represents mono-anionic ligand via SH proton dissociation). Similar reaction of the thiosemicarbazone with [M(PPh3)2Cl2] (where M = Pd or Pt) afforded complexes with the general formula [MII(L)(PPh3)] (where L depicts fully deprotonated di-anionic ligand). Solid state crystal structures of all the three complexes have been determined by X-ray crystallography. The thiosemicarbazone ligand is found to serve as a N,N,S-donor in all three complexes. These complexes show intense absorptions in the visible and ultraviolet region, the origin of which has been probed through DFT and TDDFT calculations. Redox properties of the complexes have also been studied by cyclic voltammetry. All the three complexes were applied as catalyst for Buchwald-type CN cross-coupling between aryl halides and secondary amines to generate bio-active molecules. Out of the three complexes, the nickel and palladium complexes are found to be very promising for the CN cross-coupling reaction. The observed catalysis was possible in water as solvent, without any additive, and under relatively mild condition. This type of green and cost-effective protocol for the CN bond formation appears to be limited in the literature.
{"title":"Thiosemicarbazone complexes of nickel, palladium and platinum: catalytic application for CN cross-coupling reaction in water","authors":"Sayanti Datta , Anushri Chandra , Samaresh Bhattacharya","doi":"10.1016/j.ica.2025.123030","DOIUrl":"10.1016/j.ica.2025.123030","url":null,"abstract":"<div><div>Reaction of imidazole-2-carbaldehyde thiosemicarbazone (H<sub>2</sub>L; where H<sub>2</sub> depicts the two dissociable protons, the imidazole N<img>H proton and the S<img>H proton) with Ni(ClO<sub>4</sub>)<sub>2</sub>·6H<sub>2</sub>O in presence of triphenylphosphine yielded a complex of type [Ni<sup>II</sup>(HL)(PPh<sub>3</sub>)]ClO<sub>4</sub> (where HL represents mono-anionic ligand via S<img>H proton dissociation). Similar reaction of the thiosemicarbazone with [M(PPh<sub>3</sub>)<sub>2</sub>Cl<sub>2</sub>] (where M = Pd or Pt) afforded complexes with the general formula [M<sup>II</sup>(L)(PPh<sub>3</sub>)] (where L depicts fully deprotonated di-anionic ligand). Solid state crystal structures of all the three complexes have been determined by X-ray crystallography. The thiosemicarbazone ligand is found to serve as a N,N,S-donor in all three complexes. These complexes show intense absorptions in the visible and ultraviolet region, the origin of which has been probed through DFT and TDDFT calculations. Redox properties of the complexes have also been studied by cyclic voltammetry. All the three complexes were applied as catalyst for Buchwald-type C<img>N cross-coupling between aryl halides and secondary amines to generate bio-active molecules. Out of the three complexes, the nickel and palladium complexes are found to be very promising for the C<img>N cross-coupling reaction. The observed catalysis was possible in water as solvent, without any additive, and under relatively mild condition. This type of green and cost-effective protocol for the C<img>N bond formation appears to be limited in the literature.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123030"},"PeriodicalIF":3.2,"publicationDate":"2025-12-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734158","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-07DOI: 10.1016/j.ica.2025.123016
Amal Yousri , Heba M. Refaat , Atallh A.M. Alotaibi , Ayman El-Faham , Assem Barakat , Matti Haukka , Rajendhraprasad Tatikonda , Saied M. Soliman , Mostafa A. El-Naggar , Raghdaa A. Massoud
The complexes [CoLCl2].H2O, 1 and [CuLCl2].H2O, 2 with the thiazole based s-triazine ligand (L) have been synthesized, and characterized. The structures of L, 1, and 2 are determined utilizing composition analysis, infrared, and UV–vis spectra. Each metal ion is coordinated with one tridentate ligand unit via the N(s-triazine), N(thiazole), and N(hydrazone) atoms showing square pyramidal distortion around the metal centers. Referring to Hirshfeld surface calculations, the most important intermolecular interactions are H⋯H (53.7, 41.2, and 41.2%) and O⋯H (9.3, 10.4, and 11.2%) for L, 1, and 2, respectively. However, Cl⋯H contacts are dominant in 1 and 2 with respective percentages of 18.1 and 17.3%. Energy framework calculations indicated the dominance of dispersion energy for L, 1, and 2. DFT computations revealed the conversion of L in both complexes from the thermodynamically stable Z-isomer to the E-configuration of the thiazole ring and hydrazone group. Furthermore, the investigated complexes have potential anticancer effects (IC50 = 31.62 ± 0.70–197.28 ± 6.04 μM) compared to L (IC50 = 340.00 ± 12.11–521.14 ± 12.47 μM) versus HCT-116 and A-549 carcinoma cells with selectivity index (SI) > 1, confirming their suitable use for anticancer treatments. Additionally, 1 is a more promising antifungal agent with a large diameter of suppression area (30 mm) and minimum inhibitory concentration (MIC) value of 78.1 μg/mL, than the reference drug ketoconazole (DIZ = 20 mm and MIC = 625.0 μg/mL) versus C. albicans.
{"title":"Synthesis, X-ray structure, theoretical calculations, cytotoxicity, and antimicrobial studies of new Co2+ and Cu2+ complexes based on s-triazine-Schiff base ligand","authors":"Amal Yousri , Heba M. Refaat , Atallh A.M. Alotaibi , Ayman El-Faham , Assem Barakat , Matti Haukka , Rajendhraprasad Tatikonda , Saied M. Soliman , Mostafa A. El-Naggar , Raghdaa A. Massoud","doi":"10.1016/j.ica.2025.123016","DOIUrl":"10.1016/j.ica.2025.123016","url":null,"abstract":"<div><div>The complexes [CoLCl<sub>2</sub>].H<sub>2</sub>O, <strong>1</strong> and [CuLCl<sub>2</sub>].H<sub>2</sub>O, <strong>2</strong> with the thiazole based <em>s</em>-triazine ligand (<strong>L</strong>) have been synthesized, and characterized. The structures of <strong>L</strong>, <strong>1</strong>, and <strong>2</strong> are determined utilizing composition analysis, infrared, and UV–vis spectra. Each metal ion is coordinated with one tridentate ligand unit via the N<sub>(<em>s</em>-triazine)</sub>, N<sub>(thiazole)</sub>, and N<sub>(hydrazone)</sub> atoms showing square pyramidal distortion around the metal centers. Referring to Hirshfeld surface calculations, the most important intermolecular interactions are H⋯H (53.7, 41.2, and 41.2%) and O⋯H (9.3, 10.4, and 11.2%) for <strong>L</strong>, <strong>1</strong>, and <strong>2</strong>, respectively. However, Cl⋯H contacts are dominant in <strong>1</strong> and <strong>2</strong> with respective percentages of 18.1 and 17.3%. Energy framework calculations indicated the dominance of dispersion energy for <strong>L</strong>, <strong>1</strong>, and <strong>2</strong>. DFT computations revealed the conversion of <strong>L</strong> in both complexes from the thermodynamically stable <em>Z</em>-isomer to the <em>E</em>-configuration of the thiazole ring and hydrazone group. Furthermore, the investigated complexes have potential anticancer effects (IC<sub>50</sub> = 31.62 ± 0.70–197.28 ± 6.04 <em>μ</em>M) compared to <strong>L</strong> (IC<sub>50</sub> = 340.00 ± 12.11–521.14 ± 12.47 <em>μ</em>M) versus HCT-116 and A-549 carcinoma cells with selectivity index (SI) > 1, confirming their suitable use for anticancer treatments. Additionally, <strong>1</strong> is a more promising antifungal agent with a large diameter of suppression area (30 mm) and minimum inhibitory concentration (MIC) value of 78.1 <em>μ</em>g/mL, than the reference drug ketoconazole (DIZ = 20 mm and MIC = 625.0 <em>μ</em>g/mL) versus <em>C. albicans</em>.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123016"},"PeriodicalIF":3.2,"publicationDate":"2025-12-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734157","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-07DOI: 10.1016/j.ica.2025.123031
Craig Goodman , Tyler Williams , Abigail G. McNamee , Julia L. Brumaghim
Oxidative DNA damage in cells causes a variety of pathologies including but not limited to cancers, cardiovascular diseases, and neurodegenerative disorders. Fe3+ reduction by NADH is the rate-limiting step in cellular hydroxyl radical generation and damage, but this aspect of the oxidative stress cycle is little explored. We established a rate law for the NADH-Fe system in vitro that indicates the Fe3+ reduction rate depends primarily on NADH concentration, indicating that NADH may be a critical participant in cellular oxidative stress. Kinetic experiments using ferene established that the overall stoichiometry of this reaction is 1:2 NADH:Fe, supporting an overall scheme in which two Fe3+ ions are separately reduced by NADH in a stepwise fashion. We also observed that sulfur- and selenium-containing antioxidants alter cellular oxidative stress by changing the rate by which NADH reduces Fe3+ into hydroxyl radical-generating Fe2+. Fe3+ reduction rates with and without antioxidants were quantified, demonstrating that the sulfur and selenium compounds that prevent greater Fe2+-mediated DNA damage also enhance the rate of Fe3+ reduction by NADH. Antioxidant rescues in wild-type E. coli and a mutant strain (Δndh) with elevated (∼3 fold higher) NADH levels corroborated this counterintuitive trend: compounds that increased the Fe3+ reduction rate rescued more cells from H2O2-mediated killing. By uncovering this balance involving NADH and iron, we have identified a previously overlooked antioxidant mechanism for these Fe-binding antioxidants, one by which they interact with and modify NADH-Fe redox cycling.
{"title":"Sulfur and selenium compounds alter cellular oxidative stress by the NADH reduction of Fe3+ to Fe2+","authors":"Craig Goodman , Tyler Williams , Abigail G. McNamee , Julia L. Brumaghim","doi":"10.1016/j.ica.2025.123031","DOIUrl":"10.1016/j.ica.2025.123031","url":null,"abstract":"<div><div>Oxidative DNA damage in cells causes a variety of pathologies including but not limited to cancers, cardiovascular diseases, and neurodegenerative disorders. Fe<sup>3+</sup> reduction by NADH is the rate-limiting step in cellular hydroxyl radical generation and damage, but this aspect of the oxidative stress cycle is little explored. We established a rate law for the NADH-Fe system in vitro that indicates the Fe<sup>3+</sup> reduction rate depends primarily on NADH concentration, indicating that NADH may be a critical participant in cellular oxidative stress. Kinetic experiments using ferene established that the overall stoichiometry of this reaction is 1:2 NADH:Fe, supporting an overall scheme in which two Fe<sup>3+</sup> ions are separately reduced by NADH in a stepwise fashion. We also observed that sulfur- and selenium-containing antioxidants alter cellular oxidative stress by changing the rate by which NADH reduces Fe<sup>3+</sup> into hydroxyl radical-generating Fe<sup>2+</sup>. Fe<sup>3+</sup> reduction rates with and without antioxidants were quantified, demonstrating that the sulfur and selenium compounds that prevent greater Fe<sup>2+</sup>-mediated DNA damage also enhance the rate of Fe<sup>3+</sup> reduction by NADH. Antioxidant rescues in wild-type <em>E. coli</em> and a mutant strain (Δ<em>ndh</em>) with elevated (∼3 fold higher) NADH levels corroborated this counterintuitive trend: compounds that increased the Fe<sup>3+</sup> reduction rate rescued more cells from H<sub>2</sub>O<sub>2</sub>-mediated killing. By uncovering this balance involving NADH and iron, we have identified a previously overlooked antioxidant mechanism for these Fe-binding antioxidants, one by which they interact with and modify NADH-Fe redox cycling.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123031"},"PeriodicalIF":3.2,"publicationDate":"2025-12-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145839360","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-06DOI: 10.1016/j.ica.2025.123011
Debu Jana, Kalipada Paul, Samar K. Das
In this study, we successfully synthesized a water-soluble single-crystalline cobalt-aqua-complex containing decavanadate compound Cs2[Co(H2O)6]2[V10O28]∙2H2O (1), isolated with cesium cations. We utilized single-crystal X-ray crystallography along with various spectroscopic and microscopic analyses to characterize compound 1. Notably, compound 1 serves as a stable homogeneous electrocatalyst for the hydrogen evolution reaction (HER) in an acidic aqueous environment. The electrocatalytic stability of compound 1, which includes the absence of electrodeposition, has been investigated through multiple electrochemical, spectroscopic, and microscopic studies. In the present homogeneous HER electrocatalysis (catalyzed by compound 1), we have attained an overpotential value (Ecat/2) of 572 mV and a Faradaic efficiency of 76 %. We determined the rate constant (kobs) value (0.61 s−1) for this homogeneous HER, employing the foot-of-the-wave analysis concept. The synergy of [V10O28]6− with [Co(H2O)6]2+ within the crystal matrix of compound 1, due to hydrogen bonding interaction between [V10O28]6− and [Co(H2O)6]2+, significantly enhances the homogeneous electrocatalytic HER activity of compound 1. Notably, individual homogeneous solutions of Na6[V10O28] and CoCl2‧6H2O do not exhibit HER activity, despite [V10O28]6− and [Co(H2O)6]2+ being the major sub-units of compound 1.
{"title":"A cesium‑cobalt-decavanadate polyoxometalate as a homogeneous electrocatalyst for hydrogen evolution in water","authors":"Debu Jana, Kalipada Paul, Samar K. Das","doi":"10.1016/j.ica.2025.123011","DOIUrl":"10.1016/j.ica.2025.123011","url":null,"abstract":"<div><div>In this study, we successfully synthesized a water-soluble single-crystalline cobalt-aqua-complex containing decavanadate compound Cs<sub>2</sub>[Co(H<sub>2</sub>O)<sub>6</sub>]<sub>2</sub>[V<sub>10</sub>O<sub>28</sub>]∙2H<sub>2</sub>O (<strong>1</strong>), isolated with cesium cations. We utilized single-crystal X-ray crystallography along with various spectroscopic and microscopic analyses to characterize compound <strong>1</strong>. Notably, compound <strong>1</strong> serves as a stable homogeneous electrocatalyst for the hydrogen evolution reaction (HER) in an acidic aqueous environment. The electrocatalytic stability of compound <strong>1</strong>, which includes the absence of electrodeposition, has been investigated through multiple electrochemical, spectroscopic, and microscopic studies. In the present homogeneous HER electrocatalysis (catalyzed by compound <strong>1</strong>), we have attained an overpotential value (E<sub>cat/2</sub>) of 572 mV and a Faradaic efficiency of 76 %. We determined the rate constant (k<sub>obs</sub>) value (0.61 s<sup>−1</sup>) for this homogeneous HER, employing the foot-of-the-wave analysis concept. The synergy of [V<sub>10</sub>O<sub>28</sub>]<sup>6−</sup> with [Co(H<sub>2</sub>O)<sub>6</sub>]<sup>2+</sup> within the crystal matrix of compound <strong>1</strong>, due to hydrogen bonding interaction between [V<sub>10</sub>O<sub>28</sub>]<sup>6−</sup> and [Co(H<sub>2</sub>O)<sub>6</sub>]<sup>2+</sup>, significantly enhances the homogeneous electrocatalytic HER activity of compound <strong>1</strong>. Notably, individual homogeneous solutions of Na<sub>6</sub>[V<sub>10</sub>O<sub>28</sub>] and CoCl<sub>2</sub>‧6H<sub>2</sub>O do not exhibit HER activity, despite [V<sub>10</sub>O<sub>28</sub>]<sup>6−</sup> and [Co(H<sub>2</sub>O)<sub>6</sub>]<sup>2+</sup> being the major sub-units of compound <strong>1</strong>.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123011"},"PeriodicalIF":3.2,"publicationDate":"2025-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734155","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-06DOI: 10.1016/j.ica.2025.123034
Yanni Shan , Xudong Fan , Jie Zhang , Xiaoqian Tang , Xinjun Cai , Chongyang Wu
A series of mixed-ligand ruthenium (II) complexes [RuCl(ecz)(PP)(NN)]PF6 (3a–3f) were synthesized with econazole (ecz) as bioactive ligand, alongside phosphine (PPh3, dppb, dppf) and nitrogen (bipy, phen) donors. Characterized by elemental analysis, FTIR, NMR, UV–vis, HRMS, TGA, and X-ray diffraction, they showed stable distorted octahedral geometry. Biological evaluations demonstrated that most complexes (particularly 3c) exhibited potent and selective cytotoxicity against A549, U251, and LLC cancer cells, with superior anticancer activity to cisplatin while showing lower toxicity toward normal cells. Mechanistically, complex 3c induces cell death via dual pathways of cell membrane disruption and intracellular ROS accumulation. In antimicrobial assays, most complexes enhanced econazole's activity, with 3f showing notable improvements that include efficacy against econazole-resistant S. aureus and heightened antifungal activity against C. albicans. In silico ADME studies revealed favorable bioavailability and CYP3A4 non-inhibition in 3b, 3c, 3e, 3f, supporting their potential as multi-functional metallodrug candidates.
{"title":"Synthesis, structure and multi-therapeutic activities of econazole-containing ruthenium (II) mixed-ligand complexes: Anticancer, antimicrobial and in silico ADME profiles","authors":"Yanni Shan , Xudong Fan , Jie Zhang , Xiaoqian Tang , Xinjun Cai , Chongyang Wu","doi":"10.1016/j.ica.2025.123034","DOIUrl":"10.1016/j.ica.2025.123034","url":null,"abstract":"<div><div>A series of mixed-ligand ruthenium (II) complexes [RuCl(ecz)(P<img>P)(N<img>N)]PF<sub>6</sub> (<strong>3a–3f</strong>) were synthesized with econazole (ecz) as bioactive ligand, alongside phosphine (PPh<sub>3</sub>, dppb, dppf) and nitrogen (bipy, phen) donors. Characterized by elemental analysis, FTIR, NMR, UV–vis, HRMS, TGA, and X-ray diffraction, they showed stable distorted octahedral geometry. Biological evaluations demonstrated that most complexes (particularly <strong>3c</strong>) exhibited potent and selective cytotoxicity against A549, U251, and LLC cancer cells, with superior anticancer activity to cisplatin while showing lower toxicity toward normal cells. Mechanistically, complex <strong>3c</strong> induces cell death via dual pathways of cell membrane disruption and intracellular ROS accumulation. In antimicrobial assays, most complexes enhanced econazole's activity, with <strong>3f</strong> showing notable improvements that include efficacy against econazole-resistant <em>S. aureus</em> and heightened antifungal activity against <em>C. albicans</em>. In silico ADME studies revealed favorable bioavailability and CYP3A4 non-inhibition in <strong>3b, 3c, 3e, 3f,</strong> supporting their potential as multi-functional metallodrug candidates.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123034"},"PeriodicalIF":3.2,"publicationDate":"2025-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734153","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-06DOI: 10.1016/j.ica.2025.123015
Saili Vikram Lokhande , Ashis Kumar Satpati , Afsar Ali Siddiki , Rohit Singh Chauhan , Raymond J. Butcher
The study presents a comprehensive investigation into the synthesis, characterization, and evaluation of nickel thiolate complexes as potential molecular catalysts for the hydrogen evolution reaction (HER). The growing need for efficient, sustainable hydrogen production methods has led to the exploration of various catalysts, with nickel-based complexes being promising candidates due to their abundance, low cost, and favourable catalytic properties. With this impetus, two categories of nickel complexes viz mono and binuclear were synthesized. Reaction of [NiCl2(N∩N)] (N∩N = 1,10-phenanthroline, 2,2′-bipyridine) with sodium salt of 4,6-dimethylpyrimidine−2-thiolate in the presence of NaPF6 resulted in a mononuclear neutral complex of composition [Ni{L1}2(N∩N)] (L1 = SC4H(4,6-Me)2N2; N∩N = 1,10-phenanthroline 1a, 2,2′-bipyridine 1b). However, a similar reaction with dibenzyl disulfide ligand system in the presence of tBuOK base yielded a cationic binuclear moiety [Ni{L2}(N∩N)2]22+ (L2 = {O2(SC7H7)}; N∩N = 1,10-phenanthroline 2a, 2,2′-bipyridine 2b). An insertion of nascent oxygen between Ni−S bonds is quite interesting, probably a reason to stabilize an eight-membered ring having chair confirmation which is comprised of asymmetric fragments “[Ni(O2SCH2Ph)(N∩N)2]”. A mononuclear complex [Ni{L1}2(Phen)] (1a) and a dinuclear [Ni{L2}(Phen)2]2[PF6]2 (2a) have been structurally characterized by Single crystal X-ray diffraction. All the synthesized complexes have been employed as proton-reducing catalysts through electrocatalytic activity using cyclic voltammetry (CV) and chronoamperometry in an acidic medium where sulfuric acid act as proton source. In order to have better insights about the electrocatalytic behavior of the synthesized complexes, electrochemical impedance measurements (EIS) were also conducted.
{"title":"Engineering novel nickel(II) complexes: Unlocking electrocatalytic performance for efficient hydrogen evolution","authors":"Saili Vikram Lokhande , Ashis Kumar Satpati , Afsar Ali Siddiki , Rohit Singh Chauhan , Raymond J. Butcher","doi":"10.1016/j.ica.2025.123015","DOIUrl":"10.1016/j.ica.2025.123015","url":null,"abstract":"<div><div>The study presents a comprehensive investigation into the synthesis, characterization, and evaluation of nickel thiolate complexes as potential molecular catalysts for the hydrogen evolution reaction (HER). The growing need for efficient, sustainable hydrogen production methods has led to the exploration of various catalysts, with nickel-based complexes being promising candidates due to their abundance, low cost, and favourable catalytic properties. With this impetus, two categories of nickel complexes <em>viz</em> mono and binuclear were synthesized. Reaction of [NiCl<sub>2</sub>(N∩N)] (N∩<em>N</em> = 1,10-phenanthroline, 2,2′-bipyridine) with sodium salt of 4,6-dimethylpyrimidine−2-thiolate in the presence of NaPF<sub>6</sub> resulted in a mononuclear neutral complex of composition [Ni{L1}<sub>2</sub>(N∩N)] (L1 = SC<sub>4</sub>H(4,6-Me)<sub>2</sub>N<sub>2</sub>; N∩N = 1,10-phenanthroline <strong>1a</strong>, 2,2′-bipyridine <strong>1b</strong>). However, a similar reaction with dibenzyl disulfide ligand system in the presence of <sup>t</sup>BuOK base yielded a cationic binuclear moiety [Ni{L2}(N∩N)<sub>2</sub>]<sub>2</sub><sup>2+</sup> (L<sub>2</sub> = {O<sub>2</sub>(SC<sub>7</sub>H<sub>7</sub>)}; N∩N = 1,10-phenanthroline <strong>2a</strong>, 2,2′-bipyridine <strong>2b</strong>). An insertion of nascent oxygen between Ni−S bonds is quite interesting, probably a reason to stabilize an eight-membered ring having chair confirmation which is comprised of asymmetric fragments “[Ni(O<sub>2</sub>SCH<sub>2</sub>Ph)(N∩N)<sub>2</sub>]”. A mononuclear complex [Ni{L1}<sub>2</sub>(Phen)] (<strong>1a</strong>) and a dinuclear [Ni{L2}(Phen)<sub>2</sub>]<sub>2</sub>[PF<sub>6</sub>]<sub>2</sub> (<strong>2a</strong>) have been structurally characterized by Single crystal X-ray diffraction. All the synthesized complexes have been employed as proton-reducing catalysts through electrocatalytic activity using cyclic voltammetry (CV) and chronoamperometry in an acidic medium where sulfuric acid act as proton source. In order to have better insights about the electrocatalytic behavior of the synthesized complexes, electrochemical impedance measurements (EIS) were also conducted.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123015"},"PeriodicalIF":3.2,"publicationDate":"2025-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734221","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-04DOI: 10.1016/j.ica.2025.123023
Yingjie Zhang , Timothy A. Ablott , Tao Wei , Sophie Fletcher , Mohamed R. Rafiuddin
Uranium oxide hydrate frameworks (UOHFs) with lanthanide ions are fundamentally important to uranium crystal chemistry. Earlier works revealed a possible phase transition from high symmetry space groups (monoclinic or orthorhombic) for UOHF-Ln (Ln = Pr → Dy) to a low symmetry space group (triclinic) for UOHF-Ln (Ln = Er → Lu). However, given holmium lies close to this apparent transition boundary, whether these frameworks with holmium adopt a high or low symmetry structure is unknown. Herein, we report the synthesis of Ho2(H2O)4(OH)2[(UO2)10UO13(OH)4]·H2O (UOHF-Ho) and subsequent structural and spectroscopic investigations. Synchrotron single crystal X-ray diffraction confirmed that UOHF-Ho crystallises in the orthorhombic C2221 space group, further validated by electron diffraction with transmission electron microscopy. The framework structure is constructed with β-U3O8 type layers linked by double uranyl units in pentagonal bipyramids, with disordered Ho3+ ions lying inside the channels. While Raman spectroscopy revealed the U6+ dominant vibrational modes, diffuse reflectance spectroscopy unearthed characteristic absorption bands for both U6+ and Ho3+ ions. This work uncovers the exact phase transition for UOHF-Ln series and has implications to the uranium structural chemistry and possible spent nuclear fuel alterations.
{"title":"Towards uranium oxide hydrate framework with holmium(III) ions: High or low symmetry structure?","authors":"Yingjie Zhang , Timothy A. Ablott , Tao Wei , Sophie Fletcher , Mohamed R. Rafiuddin","doi":"10.1016/j.ica.2025.123023","DOIUrl":"10.1016/j.ica.2025.123023","url":null,"abstract":"<div><div>Uranium oxide hydrate frameworks (UOHFs) with lanthanide ions are fundamentally important to uranium crystal chemistry. Earlier works revealed a possible phase transition from high symmetry space groups (monoclinic or orthorhombic) for UOHF-Ln (Ln = Pr → Dy) to a low symmetry space group (triclinic) for UOHF-Ln (Ln = Er → Lu). However, given holmium lies close to this apparent transition boundary, whether these frameworks with holmium adopt a high or low symmetry structure is unknown. Herein, we report the synthesis of Ho<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>(OH)<sub>2</sub>[(UO<sub>2</sub>)<sub>10</sub>UO<sub>13</sub>(OH)<sub>4</sub>]·H<sub>2</sub>O (<strong>UOHF-Ho</strong>) and subsequent structural and spectroscopic investigations. Synchrotron single crystal X-ray diffraction confirmed that <strong>UOHF-Ho</strong> crystallises in the orthorhombic <em>C</em>222<sub>1</sub> space group, further validated by electron diffraction with transmission electron microscopy. The framework structure is constructed with β-U<sub>3</sub>O<sub>8</sub> type layers linked by double uranyl units in pentagonal bipyramids, with disordered Ho<sup>3+</sup> ions lying inside the channels. While Raman spectroscopy revealed the U<sup>6+</sup> dominant vibrational modes, diffuse reflectance spectroscopy unearthed characteristic absorption bands for both U<sup>6+</sup> and Ho<sup>3+</sup> ions. This work uncovers the exact phase transition for UOHF-Ln series and has implications to the uranium structural chemistry and possible spent nuclear fuel alterations.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123023"},"PeriodicalIF":3.2,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145683085","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The demand for metal ion sensors is growing at a rapid pace owing to the metal ions toxic effect on the environment, aquatic life and human health. Among these, Sn(II) detection holds particular importance due to its wide industrial use and potential bioaccumulation leading to neurological, hepatic and immunological disorders, making its sensitive and selective monitoring highly advantageous. This work presents the synthesis of a fluorometric turn-off sensor, a benzyloxy-derived triazole-based organosilane (5) for the selective detection of Sn(II). Probe 5 exhibited minimal interference from competing metal ions and achieved detection limits of 13.3 × 10−9 M (fluorometric spectroscopy) and 13.5 × 10−8 M (UV–Visible spectroscopy), both well below the WHO's permissible level for Sn(II) in drinking water. Its effectiveness was further validated in real water samples, showing recovery rates above 97%, thereby confirming its practical applicability. Moreover, molecular docking and molecular dynamics simulations revealed effective inhibition of the Matrix metalloproteinase-2 (MMP-2) enzyme with a binding energy of −9.41 kcal mol−1, and confirmed the interaction stability of probe 5 with the protein, supporting its potential as an anticancer drug candidate in the pharmaceutical domain.
{"title":"Benzyloxy triazole-functionalized organosilane: Dual application in Sn(II) detection and MMP-2 enzyme inhibition through in silico insights","authors":"Gurjaspreet Singh , Devina Sharma , Tsering Diskit , Anu Radha , Komal , Parul , Jandeep Singh , Nancy George","doi":"10.1016/j.ica.2025.123008","DOIUrl":"10.1016/j.ica.2025.123008","url":null,"abstract":"<div><div>The demand for metal ion sensors is growing at a rapid pace owing to the metal ions toxic effect on the environment, aquatic life and human health. Among these, Sn(II) detection holds particular importance due to its wide industrial use and potential bioaccumulation leading to neurological, hepatic and immunological disorders, making its sensitive and selective monitoring highly advantageous. This work presents the synthesis of a fluorometric turn-off sensor, a benzyloxy-derived triazole-based organosilane (<strong>5</strong>) for the selective detection of Sn(II). Probe <strong>5</strong> exhibited minimal interference from competing metal ions and achieved detection limits of 13.3 × 10<sup>−9</sup> M (fluorometric spectroscopy) and 13.5 × 10<sup>−8</sup> M (UV–Visible spectroscopy), both well below the WHO's permissible level for Sn(II) in drinking water. Its effectiveness was further validated in real water samples, showing recovery rates above 97%, thereby confirming its practical applicability. Moreover, molecular docking and molecular dynamics simulations revealed effective inhibition of the Matrix metalloproteinase-2 (MMP-2) enzyme with a binding energy of −9.41 kcal mol<sup>−1</sup>, and confirmed the interaction stability of probe <strong>5</strong> with the protein, supporting its potential as an anticancer drug candidate in the pharmaceutical domain.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"592 ","pages":"Article 123008"},"PeriodicalIF":3.2,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734151","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号