Pub Date : 2026-01-10DOI: 10.1016/j.ica.2026.123076
Debashree Das , Sampurna Bhattacharya , Shalmali Basu , Saptydeep Das , Ujjal Das , David J. Morgan , Kamalika Sen
A novel folic acid-conjugated composite nanoparticle containing Cu on TeO2 (FA-NC) was developed via a green synthetic route for targeted cancer theranostics. The nanocomposite exhibited strong fluorescence, enabling sensitive detection of folate receptor-positive HeLa cells with a detection limit of 1.82 × 103 cells/mL. XPS analyses confirmed the transformation of Cu2+ to Cu0, and successful surface modification with folic acid was confirmed using Raman spectroscopy. The nanocomposite demonstrated selective imaging of HeLa cells over HaCaT cells, confirming receptor-specific targeting. Furthermore, FA-NC exhibited antiproliferative activity towards HeLa cells with an IC50 of 15 μg/mL. A moderate DNA binding affinity (Kd = 69.2 μM) suggested groove-binding interaction. These results highlight FA-NC as a cost-effective, biocompatible, and dual-functional nanomaterial for simultaneous imaging and therapy of folate receptor-positive cancer cells.
{"title":"Theranostics of folic acid conjugated cu on Te nanocomposite: Fluorescence sensing, imaging and selective cytotoxicity towards HeLa cells1","authors":"Debashree Das , Sampurna Bhattacharya , Shalmali Basu , Saptydeep Das , Ujjal Das , David J. Morgan , Kamalika Sen","doi":"10.1016/j.ica.2026.123076","DOIUrl":"10.1016/j.ica.2026.123076","url":null,"abstract":"<div><div>A novel folic acid-conjugated composite nanoparticle containing Cu on TeO<sub>2</sub> (FA-NC) was developed via a green synthetic route for targeted cancer theranostics. The nanocomposite exhibited strong fluorescence, enabling sensitive detection of folate receptor-positive HeLa cells with a detection limit of 1.82 × 10<sup>3</sup> cells/mL. XPS analyses confirmed the transformation of Cu<sup>2+</sup> to Cu<sup>0</sup>, and successful surface modification with folic acid was confirmed using Raman spectroscopy. The nanocomposite demonstrated selective imaging of HeLa cells over HaCaT cells, confirming receptor-specific targeting. Furthermore, FA-NC exhibited antiproliferative activity towards HeLa cells with an IC<sub>50</sub> of 15 μg/mL. A moderate DNA binding affinity (K<sub>d</sub> = 69.2 μM) suggested groove-binding interaction. These results highlight FA-NC as a cost-effective, biocompatible, and dual-functional nanomaterial for simultaneous imaging and therapy of folate receptor-positive cancer cells.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123076"},"PeriodicalIF":3.2,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975669","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 : 2026-01-08DOI: 10.1016/j.ica.2026.123067
Baban Dey , SK Safdar Hossain , Hayat Khan , Akbar Niaz , Arup Choudhury , Duck-Joo Yang
Paraquat (PQ) is a poisonous insecticide, even at low concentrations, but it is widely used as an agricultural weed killer. As a consequence, we are constantly exposed to PQ through our diet. Therefore, quantitative and qualitative monitoring of this insecticide in vegetables and fruits before consumption is necessary. In this work, a flexible hybrid film was synthesized by growing manganese metal organic frameworks (Mn-MOFs) on a highly conductive graphene film (GRF) using one-step solvothermal method and was explored as a sensor electrode for the electrochemical detection of PQ for the first time. The as-prepared hybrid films were characterized using different morphological and spectroscopic techniques. Different electrochemical approaches were used to assess the electrocatalytic ability of the Mn-MOF/GRF hybrid. The Mn-MOF@GRF sensor electrode displayed impressive performance in detecting PQ, with a wide linear detection range from 0.05 to 350 μM and an excellent sensitivity of 63.44 μA μM−1 cm−2. The sensor electrode further demonstrated a lower limit of detection (LOD) and quantification (LOQ) of 2.9 and 9.03 nM, respectively, with decent reproducibility, and robust anti-interference characteristics. In real-time samples analysis, the hybrid sensor electrode achieved a recovery rate in the range of 96.4–105.4% for apple juice and hand-pump drinking water samples, which is close to the recovery rate of 95.2–105.7% achieved by HPLC method for the same samples. Therefore, this flexible sensor electrode has the potential to be used to fabricate portable electrochemical biosensors for monitoring paraquat in foods.
{"title":"Manganese MOF deposited on graphene film for effective electrochemical detection of paraquat in drinking water and fruit juice","authors":"Baban Dey , SK Safdar Hossain , Hayat Khan , Akbar Niaz , Arup Choudhury , Duck-Joo Yang","doi":"10.1016/j.ica.2026.123067","DOIUrl":"10.1016/j.ica.2026.123067","url":null,"abstract":"<div><div>Paraquat (PQ) is a poisonous insecticide, even at low concentrations, but it is widely used as an agricultural weed killer. As a consequence, we are constantly exposed to PQ through our diet. Therefore, quantitative and qualitative monitoring of this insecticide in vegetables and fruits before consumption is necessary. In this work, a flexible hybrid film was synthesized by growing manganese metal organic frameworks (Mn-MOFs) on a highly conductive graphene film (GRF) using one-step solvothermal method and was explored as a sensor electrode for the electrochemical detection of PQ for the first time. The as-prepared hybrid films were characterized using different morphological and spectroscopic techniques. Different electrochemical approaches were used to assess the electrocatalytic ability of the Mn-MOF/GRF hybrid. The Mn-MOF@GRF sensor electrode displayed impressive performance in detecting PQ, with a wide linear detection range from 0.05 to 350 μM and an excellent sensitivity of 63.44 μA μM<sup>−1</sup> cm<sup>−2</sup>. The sensor electrode further demonstrated a lower limit of detection (LOD) and quantification (LOQ) of 2.9 and 9.03 nM, respectively, with decent reproducibility, and robust anti-interference characteristics. In real-time samples analysis, the hybrid sensor electrode achieved a recovery rate in the range of 96.4–105.4% for apple juice and hand-pump drinking water samples, which is close to the recovery rate of 95.2–105.7% achieved by HPLC method for the same samples. Therefore, this flexible sensor electrode has the potential to be used to fabricate portable electrochemical biosensors for monitoring paraquat in foods.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123067"},"PeriodicalIF":3.2,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145950249","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 : 2026-01-06DOI: 10.1016/j.ica.2026.123066
Sung Kwang Lee , Dongseong Park , Heenang Choi , Ji Yeon Ryu , Seung Uk Son , Bo Keun Park , Taek-Mo Chung
Bis(imido)molybdenum (VI) complexes have been studied for application as precursors in the molybdenum thin film deposition process, because of their structural stability and volatility. In this study, we introduced N-alkoxy carboxamide ligands to bis(tert-butylimido)molybdenum complex for synthesis of novel heteroleptic molybdenum(VI) complexes. Complexes, Mo(NtBu)2(mdpa)2 (mdpaH = N-methoxy-2,2-dimethylpropanamide) (1), Mo(NtBu)2(edpa)2 (edpaH = N-ethoxy-2,2-dimethylpropanamide) (2), Mo(NtBu)2(empa)2 (empaH = N-ethoxy-2-methylpropanamide) (3), Mo(NtBu)2(mpa)2 (mpaH = N-methoxypropanamide) (4), Mo(NtBu)2(bdpa)2 (bdpaH = N-tert-butoxy-2,2-dimethylpropanamide) (5) and Mo(NtBu)2(etfa)2 (etfaH = N-ethoxy-2,2,2-trifluoroacetamide) (6) were synthesized by double substitution reactions of Mo(NtBu)2Cl2(DME) (DME = 1,2-dimethoxyethane) and sodium salt of N-alkoxy carboxamide in hexane. All new complexes were then characterized by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FT-IR) and elemental analysis (EA). To confirm the precise structure, complex 1 was analyzed by single crystal X-ray diffraction (SC-XRD). An X-ray single crystallographic study showed that complex 1 exists in a distorted octahedral molecular geometry, in which molybdenum is bound to the N- and O- atoms of the respective ligand. Thermal properties of the complexes were investigated by thermogravimetric analysis (TGA). It showed that all complexes were both vaporized and decomposed in the analysis range. The volatility of complex 4 was measured by vapor pressure measurement and it indicates that complex 4 has enough volatility (1 Torr @ 74.8 °C) for the vapor-phase deposition process.
双（亚胺）钼（VI）配合物由于其结构稳定性和易挥发性，被研究作为钼薄膜沉积过程中的前驱物。在本研究中，我们将n -烷氧基羧酰胺配体引入到双（叔丁基氨基）钼配合物上，合成了新型杂电性钼（VI）配合物。配合物Mo(NtBu)2(mdpa)2 （mdpaH = n -甲氧基-2,2-二甲基丙酰胺）(1)、Mo(NtBu)2(edpa)2 （edpaH = n -乙氧基-2,2-二甲基丙酰胺）(2)、Mo(NtBu)2(empa)2 （empaH = n -乙氧基-2-甲基丙酰胺）(3)、Mo(NtBu)2(mpa)2 （mpaH = n -甲氧基丙酰胺）(4)、以Mo(NtBu)2Cl2(DME) （DME = 1,2-二甲氧基乙烷）与n -烷氧基羧酰胺钠盐在己烷中进行双取代反应，合成Mo(NtBu)2(bdpa)2 （bdpaH = n -叔丁基-2,2-二甲基丙酰胺）(5)和Mo(NtBu)2(etfa)2 （etfaH = n -乙氧基-2,2,2-三氟乙酰胺）(6)。然后用核磁共振光谱（NMR）、傅里叶变换红外光谱（FT-IR）和元素分析（EA）对所有新配合物进行了表征。为确定配合物1的精确结构，采用单晶x射线衍射（SC-XRD）对其进行了分析。x射线单晶学研究表明，配合物1存在于扭曲的八面体分子几何结构中，其中钼与相应配体的N和O原子结合。用热重分析（TGA）研究了配合物的热性能。结果表明，在分析范围内，所有配合物均发生汽化和分解。通过蒸汽压测定了配合物4的挥发性，表明配合物4具有足够的挥发性（1 Torr @ 74.8°C），适合气相沉积过程。
{"title":"Synthesis and structural analysis of heteroleptic molybdenum(VI) complexes with N-alkoxy carboxamide ligands","authors":"Sung Kwang Lee , Dongseong Park , Heenang Choi , Ji Yeon Ryu , Seung Uk Son , Bo Keun Park , Taek-Mo Chung","doi":"10.1016/j.ica.2026.123066","DOIUrl":"10.1016/j.ica.2026.123066","url":null,"abstract":"<div><div>Bis(imido)molybdenum (VI) complexes have been studied for application as precursors in the molybdenum thin film deposition process, because of their structural stability and volatility. In this study, we introduced <em>N</em>-alkoxy carboxamide ligands to bis(<em>tert</em>-butylimido)molybdenum complex for synthesis of novel heteroleptic molybdenum(VI) complexes. Complexes, Mo(N<sup>t</sup>Bu)<sub>2</sub>(mdpa)<sub>2</sub> (mdpaH = <em>N</em>-methoxy-2,2-dimethylpropanamide) (<strong>1</strong>), Mo(N<sup>t</sup>Bu)<sub>2</sub>(edpa)<sub>2</sub> (edpaH = <em>N</em>-ethoxy-2,2-dimethylpropanamide) (<strong>2</strong>), Mo(N<sup>t</sup>Bu)<sub>2</sub>(empa)<sub>2</sub> (empaH = <em>N</em>-ethoxy-2-methylpropanamide) (<strong>3</strong>), Mo(N<sup>t</sup>Bu)<sub>2</sub>(mpa)<sub>2</sub> (mpaH = <em>N</em>-methoxypropanamide) (<strong>4</strong>), Mo(N<sup>t</sup>Bu)<sub>2</sub>(bdpa)<sub>2</sub> (bdpaH = <em>N</em>-<em>tert</em>-butoxy-2,2-dimethylpropanamide) (<strong>5</strong>) and Mo(N<sup>t</sup>Bu)<sub>2</sub>(etfa)<sub>2</sub> (etfaH = <em>N</em>-ethoxy-2,2,2-trifluoroacetamide) (<strong>6</strong>) were synthesized by double substitution reactions of Mo(N<sup>t</sup>Bu)<sub>2</sub>Cl<sub>2</sub>(DME) (DME = 1,2-dimethoxyethane) and sodium salt of <em>N</em>-alkoxy carboxamide in hexane. All new complexes were then characterized by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FT-IR) and elemental analysis (EA). To confirm the precise structure, complex <strong>1</strong> was analyzed by single crystal X-ray diffraction (SC-XRD). An X-ray single crystallographic study showed that complex <strong>1</strong> exists in a distorted octahedral molecular geometry, in which molybdenum is bound to the N- and O- atoms of the respective ligand. Thermal properties of the complexes were investigated by thermogravimetric analysis (TGA). It showed that all complexes were both vaporized and decomposed in the analysis range. The volatility of complex <strong>4</strong> was measured by vapor pressure measurement and it indicates that complex <strong>4</strong> has enough volatility (1 Torr @ 74.8 °C) for the vapor-phase deposition process.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123066"},"PeriodicalIF":3.2,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939889","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 : 2026-01-05DOI: 10.1016/j.ica.2026.123065
Yanqin Shen , Lifeng Tan
To investigate the interaction and stabilizing effect of Ru-dppz-derived chiral ruthenium(II) polypyridyl complexes on RNA triplexes, a pair of optically pure enantiomers Δ/Λ-[Ru(bpy)2(bidppz)]2+ (Δ/Λ-1; bpy = 2,2′-bipyridine, bidppz = 11-(1H-benzo[d]imidazol-2-yl)dipyrido[3,2-a:2′,3′-c]phenazine) were synthesized and characterized. The binding characteristics of the enantiomers to RNA triplex poly(U-A*U) (where “-” indicates Watson-Crick base pairing and “⁎” signifies Hoogsteen base pairing) were investigated by spectroscopic and hydrodynamic techniques. Absorption spectrophotometric measurements revealed that Λ-1 exhibited a slightly higher binding affinity to triplex poly(U-A*U) than Δ-1. This observation was further supported by emission spectroscopy and viscosity measurements, confirming that Λ-1 interacted more effectively with RNA triplex than Δ-1. Thermal melting studies revealed that Δ-1 and Λ-1 significantly stabilized the third-strand of RNA triplex, with Λ-1 exhibiting a slightly stronger stabilizing effect than Δ-1. The RNA triplex adopts a right-handed A-type helix. Consequently, the Δ-enantiomer generally exhibits higher binding affinity than the Λ-enantiomer due to superior spatial compatibility. This study highlights that not all enantiomers adhere to the Δ-preference when interacting with RNA triplex, suggesting that Ru-dppz derivatives as RNA triplex stabilizers constitutes an important step in understanding how metal complexes can be designed to target RNA structures.
为了研究Ru-dppz衍生的手性钌（II）多吡啶配合物对RNA三络合物的相互作用和稳定作用，合成了一对光学纯对映体Δ/Λ-[Ru(bpy)2(bidppz)]2+ （Δ/Λ-1; bpy = 2,2 ' -联吡啶，bidppz = 11-（1h -苯并[d]咪唑-2-基）双吡啶[3,2-a:2 ',3 ' -c]非那嗪）。对映体与RNA三聚体（U- a *U）（“-”表示Watson-Crick碱基配对，“”表示Hoogsteen碱基配对）的结合特性通过波谱和流体动力学技术进行了研究。吸收分光光度测定结果表明，Λ-1对三聚体（U- a *U）的结合亲和力略高于Δ-1。发射光谱和粘度测量进一步支持了这一观察结果，证实Λ-1与RNA三联体的相互作用比Δ-1更有效。热熔研究表明，Δ-1和Λ-1显著稳定了RNA三联体的第三链，其中Λ-1的稳定作用略强于Δ-1。RNA三联体采用右手a型螺旋结构。因此，由于优越的空间相容性，Δ-enantiomer通常比Λ-enantiomer具有更高的结合亲和力。这项研究强调，当与RNA三联体相互作用时，并非所有对映体都坚持Δ-preference，这表明Ru-dppz衍生物作为RNA三联体稳定剂是理解金属配合物如何设计靶向RNA结构的重要一步。
{"title":"Binding and stabilizing effects of chiral Ru(II) polypyridyl complexes Δ- and Λ-[Ru(bpy)2(bidppz)]2+ toward RNA triplex poly(U-A*U)","authors":"Yanqin Shen , Lifeng Tan","doi":"10.1016/j.ica.2026.123065","DOIUrl":"10.1016/j.ica.2026.123065","url":null,"abstract":"<div><div>To investigate the interaction and stabilizing effect of Ru-dppz-derived chiral ruthenium(II) polypyridyl complexes on RNA triplexes, a pair of optically pure enantiomers Δ/Λ-[Ru(bpy)<sub>2</sub>(bidppz)]<sup>2+</sup> (Δ/Λ-<strong>1</strong>; bpy = 2,2′-bipyridine, bidppz = 11-(1H-benzo[<em>d</em>]imidazol-2-<em>yl)</em>dipyrido[3,2-<em>a</em>:2′,3′-<em>c</em>]phenazine) were synthesized and characterized. The binding characteristics of the enantiomers to RNA triplex poly(U-A*U) (where “-” indicates Watson-Crick base pairing and “⁎” signifies Hoogsteen base pairing) were investigated by spectroscopic and hydrodynamic techniques. Absorption spectrophotometric measurements revealed that Λ-<strong>1</strong> exhibited a slightly higher binding affinity to triplex poly(U-A*U) than Δ-<strong>1</strong>. This observation was further supported by emission spectroscopy and viscosity measurements, confirming that Λ-<strong>1</strong> interacted more effectively with RNA triplex than Δ-<strong>1</strong>. Thermal melting studies revealed that Δ-<strong>1</strong> and Λ-<strong>1</strong> significantly stabilized the third-strand of RNA triplex, with Λ-<strong>1</strong> exhibiting a slightly stronger stabilizing effect than Δ-<strong>1</strong>. The RNA triplex adopts a right-handed A-type helix. Consequently, the Δ-enantiomer generally exhibits higher binding affinity than the Λ-enantiomer due to superior spatial compatibility. This study highlights that not all enantiomers adhere to the Δ-preference when interacting with RNA triplex, suggesting that Ru-dppz derivatives as RNA triplex stabilizers constitutes an important step in understanding how metal complexes can be designed to target RNA structures.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123065"},"PeriodicalIF":3.2,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145950250","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 : 2026-01-03DOI: 10.1016/j.ica.2025.123057
Susovan Bera , Antonio Frontera , Shouvik Chattopadhyay
Three cobalt complexes, [CoIII(HL1)2(N3)2]ClO4 (1), [CoIII(L2)(HL2)(N3)]ClO4(2) and [CoIII(L3)(bzan)(N3)] (3), where HL1=2-(3-(cyclohexylamino)propyliminomethyl)-6-ethoxyphenol, HL2 = 2-(2-(dimethylamino)ethyliminomethyl)-6-methoxyphenol, HL3 = 2-((2-(diethylamino)ethylimino)methyl)-4,6-dichlorophenol and Hbzan = 1-benzoylacetone, were synthesized and characterized. Complexes 1 and 2 crystallize as cationic mononuclear units with perchlorate counter ions, while complex 3 is a neutral mononuclear species. Structural analyses reveal diverse supramolecular features, including hydrogen bonding, CH⋯O, and CH⋯π interactions. To better understand the role of these noncovalent interactions in directing crystal packing, density functional theory (DFT) calculations were performed. In complex 1, QTAIM analysis was applied to assess the strength and topology of hydrogen-bonded chains and cation⋯anion⋯cation motifs involving perchlorate. In complexes 2 and 3, supramolecular dimerization energies were evaluated, revealing dominant CH⋯O and CH⋯π interactions, respectively. Notably, in complex 3, a comparative study between conventional CH⋯π(arene) and unconventional CH⋯π(azide) interactions was carried out using a model system. Molecular electrostatic potential (MEP) surfaces and QTAIM analyses further support the presence and strength of these interactions. This combined experimental–theoretical approach highlights the structural relevance of weak forces in shaping the solid-state organization of Co(III) complexes.
{"title":"Noncovalent interaction-driven supramolecular organization in cobalt(III) azide complexes: Experimental and theoretical insights","authors":"Susovan Bera , Antonio Frontera , Shouvik Chattopadhyay","doi":"10.1016/j.ica.2025.123057","DOIUrl":"10.1016/j.ica.2025.123057","url":null,"abstract":"<div><div>Three cobalt complexes, <em>[Co</em><sup><em>III</em></sup><em>(HL</em><sup><em>1</em></sup><em>)</em><sub><em>2</em></sub><em>(N</em><sub><em>3</em></sub><em>)</em><sub><em>2</em></sub><em>]ClO</em><sub><em>4</em></sub> (<strong>1</strong>), <em>[Co</em><sup><em>III</em></sup><em>(L</em><sup><em>2</em></sup><em>)(HL</em><sup><em>2</em></sup><em>)(N</em><sub><em>3</em></sub><em>)]ClO</em><sub><em>4</em></sub> <em>(</em><strong>2</strong><em>) and [Co</em><sup><em>III</em></sup><em>(L</em><sup><em>3</em></sup><em>)(bzan)(N</em><sub><em>3</em></sub><em>)]</em> (<strong>3</strong>), where <em>HL</em><sup><em>1</em></sup> <em>=</em> <em>2-(3-(cyclohexylamino)propyliminomethyl)-6-ethoxyphenol, HL</em><sup><em>2</em></sup> = <em>2-(2-(dimethylamino)ethyliminomethyl)-6-methoxyphenol, HL</em><sup><em>3</em></sup> = <em>2-((2-(diethylamino)ethylimino)methyl)-4,6-dichlorophenol and</em> Hbzan = 1-benzoylacetone<em>,</em> were synthesized and characterized. Complexes <strong>1</strong> and <strong>2</strong> crystallize as cationic mononuclear units with perchlorate counter ions, while complex <strong>3</strong> is a neutral mononuclear species. Structural analyses reveal diverse supramolecular features, including hydrogen bonding, C<img>H⋯O, and C<img>H⋯π interactions. To better understand the role of these noncovalent interactions in directing crystal packing, density functional theory (DFT) calculations were performed. In complex <strong>1</strong>, QTAIM analysis was applied to assess the strength and topology of hydrogen-bonded chains and cation⋯anion⋯cation motifs involving perchlorate. In complexes <strong>2</strong> and <strong>3</strong>, supramolecular dimerization energies were evaluated, revealing dominant C<img>H⋯O and C<img>H⋯π interactions, respectively. Notably, in complex <strong>3</strong>, a comparative study between conventional C<img>H⋯π(arene) and unconventional C<img>H⋯π(azide) interactions was carried out using a model system. Molecular electrostatic potential (MEP) surfaces and QTAIM analyses further support the presence and strength of these interactions. This combined experimental–theoretical approach highlights the structural relevance of weak forces in shaping the solid-state organization of Co(III) complexes.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123057"},"PeriodicalIF":3.2,"publicationDate":"2026-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145976028","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 : 2026-01-03DOI: 10.1016/j.ica.2026.123061
Saeed S. Samman , Aly Abdou , Abdulrahman A. Alsimaree , Munirah M. Al-Rooqi , Abdulaziz M. Almohyawi , Rabab.S. Jassas , Ziad Moussa , Sultan I. Alkubaysi , A. Timoumi , Saleh A. Ahmed
Two new low-spin iron(III) and cobalt(II) mixed-ligand complexes, FeSBMB [Fe(MB)(SB)(Cl)₂] and CoSBMB [Co(MB)(SB)(Cl)(H2O)], were synthesized from 1-isopropyl-1H-benzimidazole-2-carbaldehyde (MB) and 1-([(4-methylphenyl)imino]methyl)naphthalen-2-ol (SB). The structures and octahedral geometries were established by CHN analysis, FT-IR, UV–Vis, mass spectrometry, magnetic susceptibility, conductivity, TG/DTG, and Job's method. Conductivity values of 10.15 S cm2 mol−1 (FeSBMB) and 9.86 S cm2 mol−1 (CoSBMB) confirmed their non-electrolytic nature. Magnetic moments of 1.79 B.M. (FeSBMB) and 1.83 B.M. (CoSBMB) were consistent with low-spin octahedral configurations. Spectroscopic data indicated coordination through the imine nitrogen and phenolic oxygen atoms of SB, together with the imidazole ring nitrogen and carbonyl oxygen of MB. FeSBMB exhibited the strongest antibacterial performance, producing its largest inhibition zone against K. pneumoniae (25.0 ± 0.09 mm), while showing the highest activity index against E. coli (97.51 %), as derived from comparative analysis with the reference drug, 19.6 ± 0.11 mm against E. coli, 23.6 ± 0.11 mm against C. albicans, and 13.8 ± 0.20 mm against A. flavus. CoSBMB showed slightly lower but comparable activity, with zones of 22.5 ± 0.08 mm (K. pneumoniae), 17.2 ± 0.12 mm (E. coli), 21.8 ± 0.09 mm (C. albicans), and 12.9 ± 0.14 mm (A. flavus). Anti-inflammatory IC50 values were 21.26 μg mL−1 (FeSBMB) and 25.08 μg mL−1 (CoSBMB), both outperforming the uncoordinated ligands SB (54.50 μg mL−1) and MB (55.28 μg mL−1). DFT calculations confirmed the octahedral geometries and showed that FeSBMB had the smallest HOMO–LUMO gap (1.47 eV), the lowest hardness (0.74 eV), and the highest softness (0.68 eV−1), indicating greater reactivity compared with CoSBMB (ΔE = 1.64 eV, η = 0.82 eV, σ = 0.61 eV−1). TD-DFT spectra reproduced the experimental UV–Vis transitions. Docking studies demonstrated strong binding of FeSBMB and CoSBMB to FabH-CoA (−8.50 and −8.10 kcal/mol, respectively) and COX-2 (−9.90 and −9.50 kcal/mol), consistent with their antimicrobial and anti-inflammatory activity.
{"title":"Low-spin Fe(III)/Co(II) mixed-ligand benzimidazole/Schiff-base complexes: structural, electronic reactivity, and correlated antimicrobial and anti-inflammatory bioactivity against FabH-CoA and COX-2","authors":"Saeed S. Samman , Aly Abdou , Abdulrahman A. Alsimaree , Munirah M. Al-Rooqi , Abdulaziz M. Almohyawi , Rabab.S. Jassas , Ziad Moussa , Sultan I. Alkubaysi , A. Timoumi , Saleh A. Ahmed","doi":"10.1016/j.ica.2026.123061","DOIUrl":"10.1016/j.ica.2026.123061","url":null,"abstract":"<div><div>Two new low-spin iron(III) and cobalt(II) mixed-ligand complexes, FeSBMB [Fe(MB)(SB)(Cl)₂] and CoSBMB [Co(MB)(SB)(Cl)(H<sub>2</sub>O)], were synthesized from 1-isopropyl-1H-benzimidazole-2-carbaldehyde (MB) and 1-([(4-methylphenyl)imino]methyl)naphthalen-2-ol (SB). The structures and octahedral geometries were established by CHN analysis, FT-IR, UV–Vis, mass spectrometry, magnetic susceptibility, conductivity, TG/DTG, and Job's method. Conductivity values of 10.15 S cm<sup>2</sup> mol<sup>−1</sup> (FeSBMB) and 9.86 S cm<sup>2</sup> mol<sup>−1</sup> (CoSBMB) confirmed their non-electrolytic nature. Magnetic moments of 1.79 B.M. (FeSBMB) and 1.83 B.M. (CoSBMB) were consistent with low-spin octahedral configurations. Spectroscopic data indicated coordination through the imine nitrogen and phenolic oxygen atoms of SB, together with the imidazole ring nitrogen and carbonyl oxygen of MB. FeSBMB exhibited the strongest antibacterial performance, producing its largest inhibition zone against <em>K. pneumoniae</em> (25.0 ± 0.09 mm), while showing the highest activity index against <em>E. coli</em> (97.51 %), as derived from comparative analysis with the reference drug, 19.6 ± 0.11 mm against <em>E. coli</em>, 23.6 ± 0.11 mm against <em>C. albicans</em>, and 13.8 ± 0.20 mm against <em>A. flavus</em>. CoSBMB showed slightly lower but comparable activity, with zones of 22.5 ± 0.08 mm (<em>K. pneumoniae</em>), 17.2 ± 0.12 mm (<em>E. coli</em>), 21.8 ± 0.09 mm (<em>C. albicans</em>), and 12.9 ± 0.14 mm (<em>A. flavus</em>). Anti-inflammatory IC<sub>50</sub> values were 21.26 μg mL<sup>−1</sup> (FeSBMB) and 25.08 μg mL<sup>−1</sup> (CoSBMB), both outperforming the uncoordinated ligands SB (54.50 μg mL<sup>−1</sup>) and MB (55.28 μg mL<sup>−1</sup>). DFT calculations confirmed the octahedral geometries and showed that FeSBMB had the smallest HOMO–LUMO gap (1.47 eV), the lowest hardness (0.74 eV), and the highest softness (0.68 eV<sup>−1</sup>), indicating greater reactivity compared with CoSBMB (ΔE = 1.64 eV, η = 0.82 eV, σ = 0.61 eV<sup>−1</sup>). TD-DFT spectra reproduced the experimental UV–Vis transitions. Docking studies demonstrated strong binding of FeSBMB and CoSBMB to FabH-CoA (−8.50 and −8.10 kcal/mol, respectively) and COX-2 (−9.90 and −9.50 kcal/mol), consistent with their antimicrobial and anti-inflammatory activity.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123061"},"PeriodicalIF":3.2,"publicationDate":"2026-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939817","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 : 2026-01-03DOI: 10.1016/j.ica.2026.123063
Medhavi D. Khatavkar , Rishukumar Panday , Mayank U. Singh , Sreekumar Kurungot , Avinash S. Kumbhar
A dinuclear complex of copper(II) and bipyridine glycoluril (BPG) ligand is synthesized, characterized, and structurally examined by single-crystal X-ray diffraction. The complex [Cu2(BPG)2(NO3)2(H2O)4](NO3)2ꞏ5H2O (complex (1)) further forms a supramolecular network sustained by H-bonds between NH/C=O of BPG, coordinated/free water molecules, and nitrate anions. The complex exhibits a proton conductivity of 5.99 × 10−3 Sꞏcm−1 at 90 °C and 95 % relative humidity (RH) with activation energy value Ea 0.35 eV, suggesting the Grötthuss proton transport mechanism. This value is consistent with those reported for proton-conducting systems in which coordinated water molecules play a critical role in facilitating efficient proton hopping across hydrogen-bonded networks.
{"title":"Proton conductivity in a copper(II) bipyridine glycoluril complex: The synergistic role of coordinated water and hydrogen-bonded networks.","authors":"Medhavi D. Khatavkar , Rishukumar Panday , Mayank U. Singh , Sreekumar Kurungot , Avinash S. Kumbhar","doi":"10.1016/j.ica.2026.123063","DOIUrl":"10.1016/j.ica.2026.123063","url":null,"abstract":"<div><div>A dinuclear complex of copper(II) and bipyridine glycoluril (BPG) ligand is synthesized, characterized, and structurally examined by single-crystal X-ray diffraction. The complex [Cu<sub>2</sub>(BPG)<sub>2</sub>(NO<sub>3</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>](NO<sub>3</sub>)<sub>2</sub>ꞏ5H<sub>2</sub>O (complex (<strong>1</strong>)) further forms a supramolecular network sustained by H-bonds between NH/C=O of BPG, coordinated/free water molecules, and nitrate anions. The complex exhibits a proton conductivity of 5.99 × 10<sup>−3</sup> Sꞏcm<sup>−1</sup> at 90 °C and 95 % relative humidity (RH) with activation energy value E<sub>a</sub> 0.35 eV, suggesting the Grötthuss proton transport mechanism. This value is consistent with those reported for proton-conducting systems in which coordinated water molecules play a critical role in facilitating efficient proton hopping across hydrogen-bonded networks.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"594 ","pages":"Article 123063"},"PeriodicalIF":3.2,"publicationDate":"2026-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145976029","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 : 2026-01-02DOI: 10.1016/j.ica.2026.123062
Yetkin Gök , Gül Özkan , Ali Kuruçay , Burhan Ateş , Aydın Aktaş , Özlem Demirci , Muhittin Aygün
A series of morpholine(Morp.)-liganded palladium(II) complexes (1a–c) and triphenylphosphine(PPh3)-liganded palladium(II) complexes (2a–c) bearing 4-fluorobenzyl substituted N-heterocyclic carbene (NHC) were synthesized from NHC-Pd(II)-pyridine and Morp./PPh3 by ligand exchange method. The new complexes were fully characterized using 1H NMR, 13C NMR, 19F NMR, 31P NMR, FTIR spectroscopy and elemental analysis techniques. Furthermore, single crystal X-ray diffraction was used to elucidate the structures of complexes 1a and 2b. The anticancer activities of the new complexes against MCF-7 (Human Breast Cancer) cell line were investigated. With an IC50 value of 37.54 for complex 1a, it can be said that it is more cytotoxic to MCF-7 cells compared to other complexes, while the least cytotoxicity was observed in complex 1b.
{"title":"New morpholine or triphenylphosphine-liganded palladium(II) N-heterocyclic carbene complexes: Synthesis, characterization, crystal structure, and anticancer activity","authors":"Yetkin Gök , Gül Özkan , Ali Kuruçay , Burhan Ateş , Aydın Aktaş , Özlem Demirci , Muhittin Aygün","doi":"10.1016/j.ica.2026.123062","DOIUrl":"10.1016/j.ica.2026.123062","url":null,"abstract":"<div><div>A series of morpholine(Morp.)-liganded palladium(II) complexes (<strong>1a–c</strong>) and triphenylphosphine(PPh<sub>3</sub>)-liganded palladium(II) complexes (<strong>2a–c</strong>) bearing 4-fluorobenzyl substituted <em>N</em>-heterocyclic carbene (NHC) were synthesized from NHC-Pd(II)-pyridine and Morp./PPh<sub>3</sub> by ligand exchange method. The new complexes were fully characterized using <sup>1</sup>H NMR, <sup>13</sup>C NMR, <sup>19</sup>F NMR, <sup>31</sup>P NMR, FTIR spectroscopy and elemental analysis techniques. Furthermore, single crystal X-ray diffraction was used to elucidate the structures of complexes <strong>1a</strong> and <strong>2b</strong>. The anticancer activities of the new complexes against MCF-7 (Human Breast Cancer) cell line were investigated. With an IC50 value of 37.54 for complex <strong>1a</strong>, it can be said that it is more cytotoxic to MCF-7 cells compared to other complexes, while the least cytotoxicity was observed in complex <strong>1b</strong>.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123062"},"PeriodicalIF":3.2,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939948","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 : 2025-12-30DOI: 10.1016/j.ica.2025.123058
Harsha S. Karnamkkott, Sonam Suthar, Kartik Chandra Mondal
The diborane(4) (B2H4) and diborene(2) (B2H2) are the captivating chemical species which have been already stabilized by donor base ligands [L = carbene; (L)BH=BH(L)] and also by metal-carbonyls. Although the BB bonding in (L)BH=BH(L) has been examined using EDA-NOCV, the stabilizing influence of metal-carbonyl fragments on the related B2H4 and B2H2 species remains unexplored. Thus the bonding interactions between B2H4/B2H2 and homo/hetero- di-/tri-nuclear metal-carbonyl in [{CpMo(CO)2}2{B2H4}] (1) and three isostructural transition-metal-carbonyl compounds of diborene(2) [{CpMo(CO)2}2B2H2W(CO)4] (2), [{CpW(CO)2}2B2H2Mo(CO)4] (3) and [{CpW(CO)2}2B2H2W(CO)4] (4) were investigated using the EDA-NOCV analyses. The calculations provide key insights into the bonding features that account for their remarkable stability. The bonding interactions in 1–4 are primarily governed by electrostatic forces (ΔEelec) with notable covalent contributions (ΔEorb). Although 2–4 is isostructural diborene(2) compounds, EDA–NOCV reveals that the metal–carbonyl fragment dictates the preferred bonding mode. Compounds 2-3 show the interaction of fragments with charged doublet states (D+E) while the nature of bonds in 4 [M = M′ = W] shifts predominantly to dative interaction (D), similar to homo-dinuclear compound 1. The B2H2 metal-carbonyl bonding interaction is much stronger in 2–3 (∼80–90 kcal/mol higher) compared to 4. Orbital analysis indicates predominant σ-donation from B2H4/B2H2, and in 4, additional π-backdonation from the metal centers strengthens the BB bond.
{"title":"Nature of bonding between B2H4/B2H2 with Homo-/hetero- Di/tri-nuclear-metal-carbonyls","authors":"Harsha S. Karnamkkott, Sonam Suthar, Kartik Chandra Mondal","doi":"10.1016/j.ica.2025.123058","DOIUrl":"10.1016/j.ica.2025.123058","url":null,"abstract":"<div><div>The diborane(4) (B<sub>2</sub>H<sub>4</sub>) and diborene(2) (B<sub>2</sub>H<sub>2</sub>) are the captivating chemical species which have been already stabilized by donor base ligands [L = carbene; (L)BH=BH(L)] and also by metal-carbonyls. Although the B<img>B bonding in (L)BH=BH(L) has been examined using EDA-NOCV, the stabilizing influence of metal-carbonyl fragments on the related B<sub>2</sub>H<sub>4</sub> and B<sub>2</sub>H<sub>2</sub> species remains unexplored. Thus the bonding interactions between B<sub>2</sub>H<sub>4</sub>/B<sub>2</sub>H<sub>2</sub> and homo/hetero- di-/tri-nuclear metal-carbonyl in [{CpMo(CO)<sub>2</sub>}<sub>2</sub>{B<sub>2</sub>H<sub>4</sub>}] (<strong>1</strong>) and three isostructural transition-metal-carbonyl compounds of diborene(2) [{CpMo(CO)<sub>2</sub>}<sub>2</sub>B<sub>2</sub>H<sub>2</sub>W(CO)<sub>4</sub>] (<strong>2</strong>), [{CpW(CO)<sub>2</sub>}<sub>2</sub>B<sub>2</sub>H<sub>2</sub>Mo(CO)<sub>4</sub>] (<strong>3</strong>) and [{CpW(CO)<sub>2</sub>}<sub>2</sub>B<sub>2</sub>H<sub>2</sub>W(CO)<sub>4</sub>] (<strong>4</strong>) were investigated using the EDA-NOCV analyses. The calculations provide key insights into the bonding features that account for their remarkable stability. The bonding interactions in <strong>1–4</strong> are primarily governed by electrostatic forces (Δ<em>E</em><sub>elec</sub>) with notable covalent contributions (Δ<em>E</em><sub>orb</sub>). Although <strong>2–4</strong> is isostructural diborene(2) compounds, EDA–NOCV reveals that the metal–carbonyl fragment dictates the preferred bonding mode. Compounds <strong>2-3</strong> show the interaction of fragments with charged doublet states (D+E) while the nature of bonds in <strong>4</strong> [M = M′ = W] shifts predominantly to dative interaction (D), similar to homo-dinuclear compound <strong>1</strong>. The B<sub>2</sub>H<sub>2</sub> metal-carbonyl bonding interaction is much stronger in <strong>2</strong>–<strong>3</strong> (∼80–90 kcal/mol higher) compared to <strong>4</strong>. Orbital analysis indicates predominant σ-donation from B<sub>2</sub>H<sub>4</sub>/B<sub>2</sub>H<sub>2</sub>, and in <strong>4</strong>, additional π-backdonation from the metal centers strengthens the B<img>B bond.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123058"},"PeriodicalIF":3.2,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939884","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 addition of calcium phosphate to lead silicate glasses K2O-PbO-SiO2 results in phase separation. In this study, we synthesized glass samples doped with gold to investigate the mutual influence of phase separation on the formation and growth of gold nanoparticles. It was found that phase separation occurs prior to nanoparticle formation, with the nanoparticles forming within droplets of the phosphate-rich glass phase. Conversely, the presence of gold nanoparticles promotes the enlargement of calcium phosphate droplets dispersed within the silicate matrix. In the presence of europium ions in K2O-PbO-SiO2 glass the spherical form of gold nanoparticles converts to elliptical, but in the glass containing phosphate gold is distributed between the two phases. These processes provide a means to control the coloration of glasses induced by gold nanoparticles.
{"title":"The phase separation in K2O-PbO-CaO-P2O5-SiO2 glass doped by gold and Eu3+ ions","authors":"Ilya Salakheev , Andrey Drozdov , Maksim Andreev , Claudio Pettinari","doi":"10.1016/j.ica.2025.123048","DOIUrl":"10.1016/j.ica.2025.123048","url":null,"abstract":"<div><div>The addition of calcium phosphate to lead silicate glasses K<sub>2</sub>O-PbO-SiO<sub>2</sub> results in phase separation. In this study, we synthesized glass samples doped with gold to investigate the mutual influence of phase separation on the formation and growth of gold nanoparticles. It was found that phase separation occurs prior to nanoparticle formation, with the nanoparticles forming within droplets of the phosphate-rich glass phase. Conversely, the presence of gold nanoparticles promotes the enlargement of calcium phosphate droplets dispersed within the silicate matrix. In the presence of europium ions in K<sub>2</sub>O-PbO-SiO<sub>2</sub> glass the spherical form of gold nanoparticles converts to elliptical, but in the glass containing phosphate gold is distributed between the two phases. These processes provide a means to control the coloration of glasses induced by gold nanoparticles.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"593 ","pages":"Article 123048"},"PeriodicalIF":3.2,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145939885","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}
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