Inorganics

23 pages, 4574 KB

Open AccessArticle

A Heterobimetallic Au(I)–Ru(II) Complex Bridged by dppb: Synthesis, Structural and Solution Characterization, BSA Interaction and In Vivo Toxicity Evaluation in Wistar Rats

by Adnan Zahirović, Sunčica Roca, Muhamed Fočak, Selma Fetahović, Višnja Muzika, Damir Suljević, Anela Topčagić, Maja Mitrašinović-Brulić, Irnesa Osmanković, Debbie C. Crans and Aleksandar Višnjevac

Inorganics 2025, 13(10), 323; https://doi.org/10.3390/inorganics13100323 - 29 Sep 2025

Abstract

A novel heterobimetallic ruthenium(II)–gold(I) complex featuring a bridging bis(diphenylphosphino)butane (dppb) ligand was prepared and fully characterized. Single-crystal X-ray diffraction revealed a piano-stool geometry around Ru(II) with η⁶-cymene, two chlorido ligands, and one phosphorus atom from dppb, while the Au(I) center adopts [...] Read more.

A novel heterobimetallic ruthenium(II)–gold(I) complex featuring a bridging bis(diphenylphosphino)butane (dppb) ligand was prepared and fully characterized. Single-crystal X-ray diffraction revealed a piano-stool geometry around Ru(II) with η⁶-cymene, two chlorido ligands, and one phosphorus atom from dppb, while the Au(I) center adopts a linear P–Au–Cl coordination. Structural integrity in the solution was confirmed by 1D and 2D NMR spectroscopy, while solution behavior was further monitored by variable solvent ³¹P NMR and UV/Vis spectroscopy, indicating that the organometallic Ru–arene core remains intact, whereas the chlorido ligands coordinated to Ru exhibit partial lability. Complementary characterization included elemental analysis, FTIR, and UV/Vis spectroscopy. Spectrofluorimetric and FRET analyses showed that Au(dppb), Ru(dppb), and the heterobimetallic AuRu complex bind to BSA with apparent constants of 1.41 × 10⁵, 5.12 × 10², and 2.66 × 10⁴ M⁻¹, respectively, following a static quenching mechanism. In vivo biological evaluation in Wistar rats revealed no significant hepatotoxicity or nephrotoxicity, with only mild and reversible histological alterations and preserved hepatocyte nuclear morphology. Hematological analysis indicated a statistically significant reduction in leukocyte populations, suggesting immunomodulatory potential, while elevated serum glucose levels point to possible endocrine or metabolic activity. These findings highlight compound structural stability and intriguing bioactivity profile, making it a promising platform for further organometallic drug development and testing. Full article

(This article belongs to the Special Issue Editorial Board Members’ Collection Series in “Featuring Ligands and Their Applications in Coordination Chemistry”, 2nd Edition)

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15 pages, 3394 KB

Open AccessReview

Progress and Prospect of Sm-Fe-N Magnets

by Tetsuji Saito

Inorganics 2025, 13(10), 322; https://doi.org/10.3390/inorganics13100322 - 29 Sep 2025

Abstract

High-performance but expensive neodymium-iron-boron (Nd-Fe-B) magnets are widely used in automotive and electrical applications. Prospective candidates for rare-earth-free magnets include Fe-based magnets such as L1₀-FeNi and α″-Fe₁₆N₂ phase. However, these rare-earth-free magnets cannot replace Nd-Fe-B magnets due to [...] Read more.

High-performance but expensive neodymium-iron-boron (Nd-Fe-B) magnets are widely used in automotive and electrical applications. Prospective candidates for rare-earth-free magnets include Fe-based magnets such as L1₀-FeNi and α″-Fe₁₆N₂ phase. However, these rare-earth-free magnets cannot replace Nd-Fe-B magnets due to their lower coercivity. Thus, the development of Sm-based magnets, using the relatively abundant rare-earth element Sm, has become a focus of attention. A promising, cheaper alternative with excellent magnetic properties is the Samarium-iron-nitride (Sm-Fe-N) magnet. This paper describes the production and magnetic properties of Sm-Fe-N powders with Th₂Zn₁₇ and TbCu₇ phases. The production process and magnetic properties of Sm-Fe-N bonded magnets prepared from the powders are also described. Current approaches for producing Sm-Fe-N sintered magnets are included. Full article

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34 pages, 6474 KB

Open AccessReview

Review on Chemistry of Water-Containing Calcium Carbonates and Their Transformations into Amorphous and Crystalline Carbonate Modifications

by Kende Attila Béres, Péter Németh and László Kótai

Inorganics 2025, 13(10), 321; https://doi.org/10.3390/inorganics13100321 - 28 Sep 2025

Abstract

Calcium carbonate (CaCO₃) is a dominant component of sedimentary rocks and biogenic structures, and is one of the most frequently studied inorganic compounds. It also plays a key role in preparing modern engineered materials. CaCO₃ has three well-known polymorphs, calcite, [...] Read more.

Calcium carbonate (CaCO₃) is a dominant component of sedimentary rocks and biogenic structures, and is one of the most frequently studied inorganic compounds. It also plays a key role in preparing modern engineered materials. CaCO₃ has three well-known polymorphs, calcite, aragonite, and vaterite, and four solvatomorphs with diverse crystallographic arrangements, hydration states, reactivity, and stability. Its solvatomorphs include the variable water-containing amorphous calcium carbonate (ACC—CaCO₃·xH₂O) and the crystalline monohydrocalcite (MHC—CaCO₃·H₂O), calcium carbonate hexahydrate (ikaite—CaCO₃·6H₂O), and the recently reported hemihydrate (CCHH—CaCO₃·0.5H₂O). Here, we review the preparation, crystal structure, and properties of these solvatomorphs and discuss their mutual transformations. Full article

(This article belongs to the Special Issue Metal Carbonates—from Amorphous Carbonates to Carbonate Complexes)

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21 pages, 5252 KB

Open AccessArticle

Photoactive TiO₂ Nanotubes and SILAR-Synthesized PbS/TiO₂ Heterojunctions for Tetracycline Antibiotic Photodegradation

by Safa Jemai, Karim Choubani, Anouar Hajjaji, Syrine Sassi, Mohamed Ben Rabha, Mohammed A. Almeshaal, Bernabé Mari Soucase and Brahim Bessais

Inorganics 2025, 13(10), 320; https://doi.org/10.3390/inorganics13100320 - 27 Sep 2025

Abstract

Titanium dioxide nanotubes (TiO₂ NTs) decorated with lead sulfide nanoparticles (PbS NPs) were synthesized using the Successive Ionic Layer Adsorption and Reaction (SILAR) method at different number (n) of cycles (where n = 3, 5, and 8) and evaluated for [...] Read more.

Titanium dioxide nanotubes (TiO₂ NTs) decorated with lead sulfide nanoparticles (PbS NPs) were synthesized using the Successive Ionic Layer Adsorption and Reaction (SILAR) method at different number (n) of cycles (where n = 3, 5, and 8) and evaluated for tetracycline (TC) photodegradation under UV light. PbS NPs/TiO₂ NTs heterojunctions prepared with 5 SILAR cycles showed optimal photocatalytic activity. Also, under optimized conditions, pure TiO₂ NTs achieved complete TC photodegradation (99%) within 5 h under UV irradiation, with a proposed degradation mechanism based on holes (h⁺) and hydroxyl radicals (•OH) as dominant reactive species. Full article

(This article belongs to the Special Issue Advances in Inorganic–Organic Composite Photocatalysts for Energy and Environmental Applications)

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30 pages, 5345 KB

Open AccessReview

Recent Advances in Graphitic Carbon Nitride-Based Materials in the Photocatalytic Degradation of Emerging Contaminants

by Dan Xu, Heshan Cai, Daguang Li, Feng Chen, Shuwen Han, Xiaojuan Chen, Zhenyi Li, Zebang He, Zhuhong Chen, Jiabao He, Weiyu Huang, Xinyi Tang, Yihuan Wen and Yejun Feng

Inorganics 2025, 13(10), 319; https://doi.org/10.3390/inorganics13100319 - 26 Sep 2025

Abstract

The increasing presence of emerging contaminants (ECs) has attracted considerable attention due to their potential harm to human health and ecosystems. Graphitic carbon nitride (g-C₃N₄), a semiconductor devoid of metals, stands out due to its distinctive optical properties and [...] Read more.

The increasing presence of emerging contaminants (ECs) has attracted considerable attention due to their potential harm to human health and ecosystems. Graphitic carbon nitride (g-C₃N₄), a semiconductor devoid of metals, stands out due to its distinctive optical properties and strong resistance to chemical degradation, which holds significant promise in the photocatalytic degradation of ECs. However, the inherent limitations of g-C₃N₄, such as its reduced specific surface area and the swift recombination of photogenerated electron-hole pairs, have prompted extensive research on modification strategies to enhance its photocatalytic performance. Current research on g-C₃N₄-based materials is often constrained in scope, with most reviews focusing solely on modification strategies or its application in degrading a single category of emerging contaminants (ECs). In this review, a systematic overview of synthesis methods and advanced modification strategies for g-C₃N₄-based materials is discussed, highlighting their recent advances in the photocatalytic degradation of various ECs using g-C₃N₄-based materials, which underscores their potential for environmental remediation. Moreover, this article critically examines the current challenges and outlines future research directions, with particular emphasis on integrating artificial intelligence and machine learning to accelerate the development of g-C₃N₄-based photocatalysts and optimize degradation processes, thereby promoting their efficient application in the photocatalytic degradation of ECs. Full article

(This article belongs to the Special Issue Novel Photo(electro)catalytic Degradation)

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15 pages, 3809 KB

Open AccessArticle

Co-Polymerized P(AN-co-IA)-Derived Electrospun Nanofibers with Improved Graphitization via Dual-Metallocene Integration at Low Temperature

by Taewoo Kim, Tae Hoon Ko, Byoung-Suhk Kim, Yong-Sik Chung and Hak Yong Kim

Inorganics 2025, 13(10), 318; https://doi.org/10.3390/inorganics13100318 - 26 Sep 2025

Abstract

In this study, COOH-functionalized co-polymer of acrylonitrile and itaconic acid (P(AN-co-IA)) is synthesized via free radical copolymerization using DMSO as solvent. The continuous non-aligned carbon nanofibers (CNFs) with different amounts of metallocene (zirconocene and ferrocene) are fabricated through electrospinning, followed by a series [...] Read more.

In this study, COOH-functionalized co-polymer of acrylonitrile and itaconic acid (P(AN-co-IA)) is synthesized via free radical copolymerization using DMSO as solvent. The continuous non-aligned carbon nanofibers (CNFs) with different amounts of metallocene (zirconocene and ferrocene) are fabricated through electrospinning, followed by a series of heat treatments under an inert atmosphere. The influence of metallocenes on electrospun carbon nanofiber diameter, alignment, and structural ordering was systematically investigated using FESEM, XRD, Raman spectroscopy, and TEM. Incorporation of dual metallocenes significantly alters the fiber diameter, improves orientation, and promotes graphitic domain formation at 1100 °C, a much lower temperature than conventional graphitization. The optimized sample (Zr-Fe)₁-P(AN-co-IA)-eGNF) exhibited the lowest I_D/I_G ratio compared to pristine and all prepared samples, indicating an improved degree of graphitization due to the uniform distribution of metallocene nanofiber matrix. Furthermore, the electrical conductivity of optimized (Zr-Fe)₁-P(AN-co-IA)-eGNF reached the highest value (1654.5 S/m) due to the high degree of graphitization of carbon nanofibers. These results show that integrating dual metallocene is an efficient pathway for tailoring nanofiber morphology and achieving conductive, structurally ordered electrospun eGNFs at reduced temperatures, with potential applications in various fields. Full article

(This article belongs to the Special Issue Carbon-Based Hybrid Materials for Environmental and Energy Applications)

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13 pages, 25374 KB

Open AccessArticle

Low-Temperature Formation of Aluminum Nitride Powder from Amorphous Aluminum Oxalate via Carbothermal Reduction

by Wenjing Tang, Yaling Yu, Zixuan Huang, Weijie Wang, Shaomin Lin, Ji Luo, Chenyang Zhang and Zhijie Zhang

Inorganics 2025, 13(10), 317; https://doi.org/10.3390/inorganics13100317 - 25 Sep 2025

Abstract

Aluminum nitride (AlN) powder, a cornerstone material for advanced ceramics. This study examines the low-temperature formation of AlN crystals as well as their phase transformation by employing amorphous aluminum oxalate (AAO) as a novel precursor for carbothermal reduction, contrasting it with conventional aluminum [...] Read more.

Aluminum nitride (AlN) powder, a cornerstone material for advanced ceramics. This study examines the low-temperature formation of AlN crystals as well as their phase transformation by employing amorphous aluminum oxalate (AAO) as a novel precursor for carbothermal reduction, contrasting it with conventional aluminum hydroxide (Al(OH)₃). Through characterization using X-ray diffraction (XRD), scanning electron microscopy (SEM), High-Resolution Transmission Electron Microscope (HRTEM), ²⁷Al Magic-Angle Spinning Nuclear Magnetic Resonance (²⁷Al-MAS-NMR) energy-dispersive spectroscopy (EDS), and Fourier-transform infrared spectroscopy (FTIR), we unraveled the phase evolution pathways and the formation of AlN. Key findings reveal striking differences between the two precursors. When Al(OH)₃ was used, no AlN phase was detected at 1350 °C, and even at 1500 °C, the AlN obtained with significant residual alumina impurities. In contrast, the AAO precursor demonstrated exceptional efficiency: nano-sized α-Al₂O₃ formed at 1050 °C, followed by the emergence of AlN phases at 1200 °C, ultimately gaining the pure AlN at 1500 °C. The phase transformation sequence—Al(OH)₃ → γ-Al₂O₃ (950 °C) → (α-Al₂O₃ + δ-Al₂O₃) (1050 °C) → (AlN + α-Al₂O₃) (1200 °C~ 1350 °C) → AlN (≥1500 °C)—highlights the pivotal role of nano-sized α-Al₂O₃ in enabling low-temperature nano AlN synthesis. By leveraging the unique properties of AAO, we offer a transformative strategy for synthesizing nano-sized AlN powders, with profound implications for the ceramics industry. Full article

(This article belongs to the Special Issue New Advances into Nanostructured Oxides, 3rd Edition)

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10 pages, 2681 KB

Open AccessArticle

Theoretical Study on the Ortho–Para Reactivity Difference in Ru-Catalyzed Amination of Aminopyridines via η⁶-Coordination: Role of Meisenheimer Intermediate Coordination Ability

by Cheng Wang, Shuo-Qing Zhang and Xin Hong

Inorganics 2025, 13(10), 316; https://doi.org/10.3390/inorganics13100316 - 25 Sep 2025

Abstract

η⁶-Coordination catalysis has emerged as an effective strategy for activating electron-rich (hetero)arenes toward nucleophilic substitution. Recent experimental studies on Ru(II)-catalyzed amination of aminopyridines revealed a striking ortho–para reactivity difference, with ortho-substituted substrates undergoing efficient amination while para analogs [...] Read more.

η⁶-Coordination catalysis has emerged as an effective strategy for activating electron-rich (hetero)arenes toward nucleophilic substitution. Recent experimental studies on Ru(II)-catalyzed amination of aminopyridines revealed a striking ortho–para reactivity difference, with ortho-substituted substrates undergoing efficient amination while para analogs are unreactive under identical conditions. Herein, we present a density functional theory investigation to elucidate the origin of this divergence. Computed free-energy profiles show that both substitution patterns follow a similar stepwise mechanism involving Ru-bound Meisenheimer intermediates and a proton-transfer relay, with C–N bond cleavage/rearomatization as the rate-determining step. However, the para pathway suffers from a substantially higher overall barrier, originating from the intrinsically less stable Meisenheimer intermediates. Energy decomposition analysis indicates that the decisive factor is weaker orbital interaction between the CpRu(II) fragment and the para-substituted Meisenheimer intermediate, whereas electrostatics and dispersion play negligible roles. These findings highlight the key role of metal–substrate orbital interactions in stabilizing dearomatized intermediates, offering mechanistic insights for rational design of η⁶-coordination catalysis with enhanced reactivity and selectivity. Full article

(This article belongs to the Special Issue Transition Metal Catalysts: Design, Synthesis and Applications)

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19 pages, 2194 KB

Open AccessArticle

Hidden Magnetic-Field-Induced Multiferroic States in A-Site-Ordered Quadruple Perovskites RMn₃Ni₂Mn₂O₁₂: Dielectric Studies

by Alexei A. Belik, Ran Liu and Kazunari Yamaura

Inorganics 2025, 13(10), 315; https://doi.org/10.3390/inorganics13100315 - 25 Sep 2025

Abstract

The appearance of spin-induced ferroelectric polarization in the so-called type-II multiferroic materials has received a lot of attention. The nature and mechanisms of such polarization were intensively studied using perovskite rare-earth manganites, RMnO₃, as model systems. Later, multiferroic properties were discovered [...] Read more.

The appearance of spin-induced ferroelectric polarization in the so-called type-II multiferroic materials has received a lot of attention. The nature and mechanisms of such polarization were intensively studied using perovskite rare-earth manganites, RMnO₃, as model systems. Later, multiferroic properties were discovered in some RFeO₃ perovskites and possibly in some RCrO₃ perovskites. However, R₂NiMnO₆ double perovskites have ferromagnetic structures that do not break the inversion symmetry. It was found recently that more complex magnetic structures are realized in A-site-ordered quadruple perovskites, RMn₃Ni₂Mn₂O₁₂. Therefore, they have the potential to be multiferroics. In this work, dielectric properties in magnetic fields up to 9 T were investigated for such perovskites as RMn₃Ni₂Mn₂O₁₂ with R = Ce to Ho and for BiMn₃Ni₂Mn₂O₁₂. The samples with R = Bi, Ce, and Nd showed no dielectric anomalies at all magnetic fields, and the dielectric constant decreases with decreasing temperature. The samples with R = Sm to Ho showed qualitatively different behavior when the dielectric constant started increasing with decreasing temperature below certain temperatures close to the magnetic ordering temperatures, T_N. This difference could suggest different magnetic ground states. The samples with R = Eu, Dy, and Ho still showed no anomalies on the dielectric constant. On the other hand, peaks emerged at T_N on the dielectric constant in the R = Sm sample from about 2 T up to the maximum available field of 9 T. The Gd sample showed peaks on dielectric constant at T_N between about 1 T and 7 T. Transition temperatures increase with increasing magnetic fields for R = Sm and decrease for R = Gd. These findings suggest the presence of magnetic-field-induced multiferroic states in the R = Sm and Gd samples with intermediate ionic radii. Dielectric properties at different magnetic fields are also reported for Lu₂NiMnO₆ for comparison. Full article

(This article belongs to the Special Issue Recent Progress in Perovskites)

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13 pages, 2257 KB

Open AccessArticle

Scalable High-Yield Exfoliation of Hydrophilic h-BN Nanosheets via Gallium Intercalation

by Sungsan Kang, Dahun Kim, Seonyou Park, Sung-Tae Lee, John Hong, Sanghyo Lee and Sangyeon Pak

Inorganics 2025, 13(10), 314; https://doi.org/10.3390/inorganics13100314 - 25 Sep 2025

Abstract

Hexagonal boron nitride (h-BN) possesses a unique combination of a wide bandgap, high thermal conductivity, and chemical inertness, making it a key insulating and thermal management material for advanced electronics and nanocomposites. However, its intrinsic hydrophobicity and strong interlayer van der Waals forces [...] Read more.

Hexagonal boron nitride (h-BN) possesses a unique combination of a wide bandgap, high thermal conductivity, and chemical inertness, making it a key insulating and thermal management material for advanced electronics and nanocomposites. However, its intrinsic hydrophobicity and strong interlayer van der Waals forces severely limit exfoliation efficiency and dispersion stability, particularly in scalable liquid-phase processes. Here, we report a synergistic exfoliation strategy that integrates acid-induced hydroxylation with gallium (Ga) intercalation to achieve high-yield (>80%) production of ultrathin (<4 nm) hydrophilic h-BN nanosheets. Hydroxylation introduces abundant -OH groups, expanding interlayer spacing and significantly increasing surface polarity, while Ga intercalation leverages its native Ga₂O₃ shell to form strong interfacial interactions with hydroxylated basal planes. This oxide-mediated adhesion facilitates efficient layer separation under mild sonication, yielding nanosheets with well-preserved lateral dimensions and exceptional dispersion stability in polar solvents. Comprehensive characterization confirms the sequential chemical and structural modifications, revealing the crucial roles of hydroxylation-induced activation and Ga₂O₃ assisted wettability enhancement. This combined chemical activation–soft metallic intercalation approach provides a scalable, solution-processable route to high-quality h-BN nanosheets, opening new opportunities for their integration into dielectric, thermal interface, and multifunctional composite systems. Full article

(This article belongs to the Special Issue Physicochemical Characterization of 2D Materials)

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18 pages, 3204 KB

Open AccessArticle

Calcium Phosphate Ceramic Powders Prepared from Mechanochemically Activated Precursors

by Kostadinka Sezanova, Yordanka Tuparova, Pavletta Shestakova, Pavel Markov, Daniela Kovacheva and Diana Rabadjieva

Inorganics 2025, 13(10), 313; https://doi.org/10.3390/inorganics13100313 - 24 Sep 2025

Abstract

The chemical and structural similarity of calcium orthophosphates to hard tissues in the human body makes them suitable as biomaterials for bone implants, cements, injection systems, etc., for bone regeneration and reconstruction. Tetracalcium phosphate (Ca₄(PO₄)₂O, TTCP) is [...] Read more.

The chemical and structural similarity of calcium orthophosphates to hard tissues in the human body makes them suitable as biomaterials for bone implants, cements, injection systems, etc., for bone regeneration and reconstruction. Tetracalcium phosphate (Ca₄(PO₄)₂O, TTCP) is a promising component for such biomaterials due to its high calcium content and alkaline nature. The former makes it suitable for promoting mineralization, while the latter supports neutralization of the acidic environment, helping to prevent inflammation and improve the biocompatibility of the materials. However, it is the least used calcium orthophosphate due to the difficulties in its synthesis. This study examines the effect of high-energy mechanochemical activation on the phase evolution, particle morphology, and thermal behaviour of equimolar mixtures of Ca(OH)₂ and CaHPO₄, with the aim of optimizing precursor conditions for the synthesis of (TTCP)-rich ceramic materials. The results demonstrate that mechanochemical activation effectively induces structural disorder, promotes the formation of amorphous and nanocrystalline phases, and facilitates subsequent phase transitions upon calcination. The combined use of solid-state NMR, XRD, TEM, and thermal analysis provides a comprehensive understanding of the transformation pathways. Ultimately, 24 h of activation under the experimental conditions was identified as optimal for producing a precursor with a favorable phase composition for obtaining TTCP-rich ceramic materials after calcination at 1350 °C. Full article

(This article belongs to the Special Issue Featured Papers in Inorganic Materials 2025)

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19 pages, 4073 KB

Open AccessArticle

Single-Atom Cobalt-Doped 2D Graphene: Electronic Design for Multifunctional Applications in Environmental Remediation and Energy Storage

by Zhongkai Huang, Yue Zhang, Chunjiang Li, Liang Deng, Bo Song, Maolin Bo, Chuang Yao, Haolin Lu and Guankui Long

Inorganics 2025, 13(10), 312; https://doi.org/10.3390/inorganics13100312 - 24 Sep 2025

Abstract

Through atomic-scale characterization of a single cobalt atom anchored in a pyridinic N₃ vacancy of graphene (Co-N₃-gra), this study computationally explores three interconnected functionalities mediated by cobalt’s electronic configuration. Quantum-confined molecular prototypes extend prior bulk models, achieving a competitive catalytic [...] Read more.

Through atomic-scale characterization of a single cobalt atom anchored in a pyridinic N₃ vacancy of graphene (Co-N₃-gra), this study computationally explores three interconnected functionalities mediated by cobalt’s electronic configuration. Quantum-confined molecular prototypes extend prior bulk models, achieving a competitive catalytic activity for CO oxidation via Langmuir–Hinshelwood pathways with a 0.85 eV barrier. These molecular prototypes’ discrete energy states facilitate single-electron transistor operation, enabling sensitive detection of NO, NO₂, SO₂, and CO₂ through adsorption-induced conductance modulation. When applied to lithium–sulfur batteries using periodic Co-N₃-gra, cobalt sites enhance polysulfide conversion kinetics and suppress the shuttle effect, with the Li₂S₂→Li₂S step identified as the rate-limiting process. Density functional simulations provide atomic-scale physicochemical characterization of Co-N₃-gra, revealing how defect engineering in 2D materials modulates electronic structures for multifunctional applications. Full article

(This article belongs to the Special Issue Physicochemical Characterization of 2D Materials)

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11 pages, 578 KB

Open AccessArticle

Biophysical Characterization of Membrane Interactions of 3-Hydroxy-4-Pyridinone Vanadium Complexes: Insights for Antidiabetic Applications

by Luísa M. P. F. Amaral, Tânia Moniz and Maria Rangel

Inorganics 2025, 13(10), 311; https://doi.org/10.3390/inorganics13100311 - 24 Sep 2025

Abstract

The development of metallopharmaceuticals for diabetes treatment has garnered increasing attention due to its insulin-mimetic properties, particularly in vanadium complexes. In this study, we report the biophysical evaluation of a series of 3-hydroxy-4-pyridinone (3,4-HPO) vanadium complexes, designed to improve lipophilicity and biological cytocompatibility. [...] Read more.

The development of metallopharmaceuticals for diabetes treatment has garnered increasing attention due to its insulin-mimetic properties, particularly in vanadium complexes. In this study, we report the biophysical evaluation of a series of 3-hydroxy-4-pyridinone (3,4-HPO) vanadium complexes, designed to improve lipophilicity and biological cytocompatibility. Dynamic light scattering (DLS) was used to get insight on the size of the liposomes and Differential Scanning Calorimetry (DSC) was employed to investigate the interaction of these complexes with model biological membranes made from dimyristoylphosphatidylcholine (DMPC) unilamellar liposomes. The thermotropic phase behavior of the lipid bilayers was analyzed in the presence of vanadium complexes. The results reveal that the alkyl chain length of the 3,4-HPO ligands modulates membrane interaction of the respective vanadium compounds, with specific complexes inducing significant shifts in the lipid phase transition temperature (T_m), suggesting alterations in membrane fluidity and packing. These findings provide valuable insight into the membrane affinity of vanadium-based drug candidates and support their potential as next-generation antidiabetic agents. Full article

(This article belongs to the Special Issue New Trends in Vanadium Chemistry, Biochemistry, and Medicinal Chemistry, 2nd Edition)

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10 pages, 7542 KB

Open AccessArticle

Thermoelectric Figure of Merit in a One-Dimensional Model with k⁴-Dispersion: An Extension of the Theory by Hicks and Dresselhaus

by Hiroyasu Matsuura and Masao Ogata

Inorganics 2025, 13(9), 310; https://doi.org/10.3390/inorganics13090310 - 22 Sep 2025

Abstract

Motivated by the strategy developed by Hicks and Dresselhaus in a quantum wire corresponding to a single-chain model with

k^{2}

-dispersion, we study a one-dimensional double-chain model with two carriers of electrons and holes, characterized by

k^{4}

-dispersion. To understand the [...] Read more.

Motivated by the strategy developed by Hicks and Dresselhaus in a quantum wire corresponding to a single-chain model with

k^{2}

-dispersion, we study a one-dimensional double-chain model with two carriers of electrons and holes, characterized by

k^{4}

-dispersion. To understand the role of the enhancement of the density of state derived from

k^{4}

-dispersion, we calculate an optimized dimensionless thermoelectric figure of merit (

Z T

) depending on the side length of the cross section, a, in the same way as discussed by Hicks and Dresselhaus. We find that

Z T

enhances as a decreases similarly to the results obtained in the single-chain model, while the enhancement of

Z T

is smaller than that of single-chain model. We discuss the reason in connection with the difference of electronic state between the single- and double-chain models. Full article

(This article belongs to the Special Issue Advances in Thermoelectric Materials, 2nd Edition)

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10 pages, 2220 KB

Open AccessArticle

Fibroblast Response to Cyclo- and Organic Phosphate Solutions: A Cytotoxicity Study

by Leonardo Antônio de Morais, Alberto Carlos Botazzo Delbem, Caio Sampaio, Vitória Bittencourt de Aguiar, Luigi Pedrini Guisso, Lucas Fernando Oliveira Tomáz Ferraresso, Juliano Pelim Pessan and Thayse Yumi Hosida

Inorganics 2025, 13(9), 309; https://doi.org/10.3390/inorganics13090309 - 18 Sep 2025

Abstract

Although the anticaries properties of phosphate-based compounds have been extensively investigated in recent years, their potential cytotoxic effects remain underexplored. This study evaluated the cytotoxicity of solutions containing sodium trimetaphosphate (TMP), sodium hexametaphosphate (HMP), or calcium glycerophosphate (CaGP). NIH/3T3 fibroblasts were cultured in [...] Read more.

Although the anticaries properties of phosphate-based compounds have been extensively investigated in recent years, their potential cytotoxic effects remain underexplored. This study evaluated the cytotoxicity of solutions containing sodium trimetaphosphate (TMP), sodium hexametaphosphate (HMP), or calcium glycerophosphate (CaGP). NIH/3T3 fibroblasts were cultured in Dulbecco’s Modified Eagle Medium (DMEM) supplemented with 10% fetal bovine serum and maintained at 37 °C, 100% humidity, and 5% CO₂. The cells were seeded in 96-well plates at a density of 10⁴ cells per well and incubated for 24 h. Subsequently, different dilutions of 10% TMP, HMP, or CaGP solutions were applied to the cells. Cell viability was assessed at 24/48 h using the MTT assay. The data were subjected to two-way ANOVA and Fisher’s LSD test. Spearman’s rank correlation was performed. HMP dilutions led to significantly lower cell viability compared to the other compounds, regardless of the incubation period. TMP maintained higher cell viability from 1/8 dilution onwards, regardless of the incubation time. For CaGP, an increase in cell viability was observed at 1/8 dilution after 24 h. In conclusion, TMP and CaGP demonstrated reduced cytotoxicity at higher dilutions compared to HMP, suggesting their potential as promising candidates for the development of novel biomaterials. Full article

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18 pages, 5409 KB

Open AccessArticle

Upconversion and Downconversion Luminescence of CaLaLiTeO₆:Mn⁴⁺/Er³⁺ Phosphors for Dual-Mode Optical Thermometry and Anti-Counterfeiting Application

by Zheng-Rong Xia, Rong-Qing Li, Fang-Fang Liu, Yue Tong, Qing-Hua Zheng, Zhao-Yan Ping, Wang Zhao, Wei-Wei Zhou and Ming-Jun Song

Inorganics 2025, 13(9), 308; https://doi.org/10.3390/inorganics13090308 - 13 Sep 2025

Abstract

Multifunctional phosphors that integrate optical temperature measurement and counterfeit detection capabilities have garnered considerable interest owing to their diverse application potential. In this study, novel CaLaLiTeO₆:Mn⁴⁺/Er³⁺ phosphors were prepared via the high-temperature solid-phase method. The phase structure and [...] Read more.

Multifunctional phosphors that integrate optical temperature measurement and counterfeit detection capabilities have garnered considerable interest owing to their diverse application potential. In this study, novel CaLaLiTeO₆:Mn⁴⁺/Er³⁺ phosphors were prepared via the high-temperature solid-phase method. The phase structure and morphology characterization confirmed the successful synthesis of CaLaLiTeO₆ material with effective doping of Mn⁴⁺ and Er³⁺ into the host lattice. Upon excitation at 379 nm, the CaLaLiTeO₆:Mn⁴⁺/Er³⁺ material exhibits far-red emission at 716 nm (Mn⁴⁺:²E_g → ⁴A_2g) and green emission at 525/548 nm (Er³⁺:²H_11/2/⁴S_3/2 → ⁴I_15/2). The emission peak intensities of Er³⁺ and Mn⁴⁺ ions in the CaLaLiTeO₆:0.015Mn⁴⁺/0.01Er³⁺ sample displayed distinct variations with temperature under different excitation wavelengths (325 nm, 379 nm, and 980 nm). Subsequently, a dual-mode optical temperature sensing system was developed based on the fluorescence intensity ratio and the dual excitation single-band ratiometric method, which achieved a maxed relative sensitivity of 1.12% K⁻¹ at 343 K. Moreover, the excitation-dependent luminescence color changes of CaLaLiTeO₆:Mn⁴⁺/Er³⁺ make it particularly suitable for anti-counterfeiting applications. The present study underscores the dual-functional capabilities in sophisticated non-contact optical temperature measurement and anti-counterfeiting applications. Full article

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10 pages, 1482 KB

Open AccessReview

Functional Diversity of the Oxidative Stress Sensor and Transcription Factor SoxR: Mechanism of [2Fe-2S] Cluster Oxidation

by Kazuo Kobayashi

Inorganics 2025, 13(9), 307; https://doi.org/10.3390/inorganics13090307 - 12 Sep 2025

Abstract

The [2Fe-2S] transcription activator SoxR, a member of the MerR family, functions as a bacterial stress response sensor. The response governed by SoxR is activated by the oxidation of the [2Fe-2S]. In this review, I describe functional differences between Escherichia coli SoxR (EcSoxR) [...] Read more.

The [2Fe-2S] transcription activator SoxR, a member of the MerR family, functions as a bacterial stress response sensor. The response governed by SoxR is activated by the oxidation of the [2Fe-2S]. In this review, I describe functional differences between Escherichia coli SoxR (EcSoxR) and Pseudomonas aeruginosa SoxR (PaSoxR). Pulse radiolysis demonstrated that the reduced form of EcSoxR reacts directly with O₂⁻ with a second-order rate constant of 5.0 × 10⁸ M⁻¹s⁻¹. PaSoxR was found to undergo a similar reaction, although with a 10-fold smaller rate constant (4.0 × 10⁷ M⁻¹s⁻¹). This difference in rate constants may reflect distinct regulatory features of EcSoxR and PaSoxR. Specifically, mutagenesis studies have shown that Lysine residues―which are located close to [2Fe-2S] clusters, in EcSoxR, but are not conserved in PaSoxR―are essential for EcSoxR activation. In contrast, both EcSoxR and PaSoxR were found to react with various redox-active compounds (RACs), including viologens, phenazines, and quinones, with no apparent differences in the kinetic behavior or specificity of the two proteins. Importantly, both O₂⁻ and RACs oxidize SoxR with the same rate constants. soxR regulon may be induced through multiple pathways, and the activation may depend on the cellular concentration of O₂⁻ and RACs. Full article

(This article belongs to the Section Bioinorganic Chemistry)

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24 pages, 19167 KB

Open AccessArticle

Mixed-Valence Pentadecavanadate with Ca²⁺-ATPase Inhibition Potential and Anti-Breast Cancer Activity

by Bianca R. Brito, Heloísa de S. Camilo, Anderson F. da Cruz, Ronny R. Ribeiro, Eduardo L. de Sá, Carolina Camargo de Oliveira, Gil Fraqueza, Giseli Klassen, Manuel Aureliano and Giovana G. Nunes

Inorganics 2025, 13(9), 306; https://doi.org/10.3390/inorganics13090306 - 12 Sep 2025

Abstract

Polyoxovanadates are a subclass of polyoxometalates (POMs) known to interact with proteins and to present anticancer, antimicrobial, and antiviral activities. Herein, we aimed to pursue the study of the breast anticancer activity of a mixed-valence polyoxovanadate, [Cl@V^V₇V^IV₈O [...] Read more.

Polyoxovanadates are a subclass of polyoxometalates (POMs) known to interact with proteins and to present anticancer, antimicrobial, and antiviral activities. Herein, we aimed to pursue the study of the breast anticancer activity of a mixed-valence polyoxovanadate, [Cl@V^V₇V^IV₈O₃₆]⁶⁻ (V₁₅) against MCF-7 and MDA-MB-231 cancer cell lines and to analyze its Ca²⁺-ATPase inhibition potential. ⁵¹V NMR and UV-Vis/NIR studies of V₁₅ indicated its stability in HEPES and RPMI media. For the Ca²⁺-ATPase activity, V₁₅ showed an IC₅₀ value of 14.2 μM and a mixed type of inhibition. The electrostatic potential map of V₁₅ and other POMs were correlated with the enzyme activity inhibition. V₁₅ also exhibited cytotoxicity against MDA-MB-231 (IC₅₀ = 17.2 μM) and MCF-7 (IC₅₀ = 15.1 μM) breast cancer cell lines. Using V₁₅ concentrations equivalent to half and 1/4 of the IC_50, it was observed that MDA-MB-231 cell migration was reduced by 90 and 70%, after 24 h, respectively. Moreover, V₁₅ caused morphological changes from fusiform to an epithelial-like (amoeboid) shape. Finally, V₁₅ induced the increase in RIPK1, MLKL, and RIPK3 gene expression, up to 3, 10, and 15-fold, respectively, pointing out that the mechanisms of cell death in the triple-negative breast cancer cell line may occur by necroptosis. Full article

(This article belongs to the Special Issue New Trends in Vanadium Chemistry, Biochemistry, and Medicinal Chemistry, 2nd Edition)

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35 pages, 5920 KB

Open AccessReview

Advances in the Mechanism and Application of Nanoparticles in Concrete Property Modification

by Huaming Li, Yuhan Zhao, Yan Zhao, Min Zhang, Yanan Niu and Xi Cao

Inorganics 2025, 13(9), 305; https://doi.org/10.3390/inorganics13090305 - 12 Sep 2025

Abstract

Nanoparticles leverage their unique nanoscale effects to optimize concrete performance through synergistic multi-mechanism interactions. Core mechanisms include micro-filling effects (graded pore filling, optimized pore structure), nucleation (promoting crystallization of hydration products, refining microstructure), chemical reactivity (e.g., pozzolanic reaction of nano-SiO₂, enhancing [...] Read more.

Nanoparticles leverage their unique nanoscale effects to optimize concrete performance through synergistic multi-mechanism interactions. Core mechanisms include micro-filling effects (graded pore filling, optimized pore structure), nucleation (promoting crystallization of hydration products, refining microstructure), chemical reactivity (e.g., pozzolanic reaction of nano-SiO₂, enhancing interfacial transition zones), and interfacial strengthening (improving ITZ structure and stress transfer). Common nanomaterials (e.g., nano-SiO₂, Al₂O₃, carbon nanotubes) significantly enhance concrete’s mechanical properties, durability, and functionalities (e.g., self-sensing, electromagnetic shielding). However, nano-modified concrete still faces challenges such as poor dispersion, high cost, and environmental/health risks. Future efforts should focus on multi-scale mechanism research, green low-cost synthesis processes, and intelligent composite systems development to advance the engineering applications pf nano-modified concrete. Full article

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