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Editor’s Choice Articles

Editor’s Choice articles are based on recommendations by the scientific editors of MDPI journals from around the world. Editors select a small number of articles recently published in the journal that they believe will be particularly interesting to readers, or important in the respective research area. The aim is to provide a snapshot of some of the most exciting work published in the various research areas of the journal.

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10 pages, 1494 KiB  
Article
Platinum–Iron Nanoparticles for Oxygen-Enhanced Sonodynamic Tumor Cell Suppression
by Qianya Dong and Zhenqi Jiang
Inorganics 2024, 12(12), 331; https://doi.org/10.3390/inorganics12120331 - 18 Dec 2024
Cited by 87 | Viewed by 1343
Abstract
A type of nanoparticle has been developed to simultaneously alleviate tumor hypoxia and enhance the effectiveness of sonodynamic therapy aimed at improving cancer treatment outcomes. Small-sized iron–platinum nanoparticles were prepared using a thermal reduction method, and their particle size and crystal structure were [...] Read more.
A type of nanoparticle has been developed to simultaneously alleviate tumor hypoxia and enhance the effectiveness of sonodynamic therapy aimed at improving cancer treatment outcomes. Small-sized iron–platinum nanoparticles were prepared using a thermal reduction method, and their particle size and crystal structure were characterized. The ability of these nanoparticles to decompose hydrogen peroxide to produce oxygen and generate singlet oxygen under ultrasound irradiation was further tested. The effect of iron–platinum nanoparticles on inhibition of the proliferation of MCF-7 tumor cells under hypoxic conditions was also evaluated. The prepared iron–platinum nanoparticles effectively decomposed hydrogen peroxide to produce oxygen, reversing the hypoxic environment of tumors. Additionally, they generated singlet oxygen under ultrasound irradiation, which killed tumor cells and inhibited their proliferation. This study successfully developed small-sized iron–platinum nanoparticles that can alleviate tumor hypoxia by decomposing excess hydrogen peroxide in tumor cells to produce oxygen. Under ultrasound irradiation, these nanoparticles generate singlet oxygen, inhibiting tumor growth. The nanoparticles demonstrated good safety and are potentially valuable in enhancing oxygen-enhanced sonodynamic cancer therapy. Full article
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27 pages, 5416 KiB  
Review
Recent Advances in Aluminum Nitride (AlN) Growth by Magnetron Sputtering Techniques and Its Applications
by Nabeel Ahmad Khan Jadoon, Vaigunthan Puvanenthiram, Mayada Ahmed Hassan Mosa, Ashutosh Sharma and Kaiying Wang
Inorganics 2024, 12(10), 264; https://doi.org/10.3390/inorganics12100264 - 7 Oct 2024
Cited by 11 | Viewed by 8637
Abstract
This review explores the processes involved in enhancing AlN film quality through various magnetron sputtering techniques, crucial for optimizing performance and expanding their application scope. It presents recent advancements in growing AlN thin films via magnetron sputtering, elucidating the mechanisms of AlN growth [...] Read more.
This review explores the processes involved in enhancing AlN film quality through various magnetron sputtering techniques, crucial for optimizing performance and expanding their application scope. It presents recent advancements in growing AlN thin films via magnetron sputtering, elucidating the mechanisms of AlN growth and navigating the complexities of thin-film fabrication. Emphasis is placed on different sputtering methods such as DC, RF, pulsed DC, and high-power impulse DC, highlighting how tailored sputtering conditions enhance film characteristics in each method. Additionally, the review discusses recent research findings showcasing the dynamic potential of these techniques. The practical applications of AlN thin films, including wave resonators, energy harvesting devices, and thermal management solutions, are outlined, demonstrating their relevance in addressing real-world engineering challenges. Full article
(This article belongs to the Special Issue Advanced Inorganic Semiconductor Materials, 2nd Edition)
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63 pages, 7584 KiB  
Review
A Review of Ionic Liquids and Their Composites with Nanoparticles for Electrochemical Applications
by José Pereira, Reinaldo Souza and Ana Moita
Inorganics 2024, 12(7), 186; https://doi.org/10.3390/inorganics12070186 - 3 Jul 2024
Cited by 10 | Viewed by 4595
Abstract
The current study focuses on reviewing the actual progress of the use of ionic liquids and derivatives in several electrochemical application. Ionic liquids can be prepared at room temperature conditions and by including a solution that can be a salt in water, or [...] Read more.
The current study focuses on reviewing the actual progress of the use of ionic liquids and derivatives in several electrochemical application. Ionic liquids can be prepared at room temperature conditions and by including a solution that can be a salt in water, or a base or acid, and are composed of organic cations and many charge-delocalized organic or inorganic anions. The electrochemical properties, including the ionic and electronic conductivities of these innovative fluids and hybrids, are addressed in depth, together with their key influencing parameters including type, fraction, functionalization of the nanoparticles, and operating temperature, as well as the incorporation of surfactants or additives. Also, the present review assesses the recent applications of ionic liquids and corresponding hybrids with the addition of nanoparticles in diverse electrochemical equipment and processes, together with a critical evaluation of the related feasibility concerns in different applications. Those ranging from the metal-ion batteries, in which ionic liquids possess a prominent role as electrolytes and reference electrodes passing through the dye of sensitized solar cells and fuel cells, to finishing processes like the ones related with low-grade heat harvesting and supercapacitors. Moreover, the overview of the scientific articles on the theme resulted in the comparatively brief examination of the benefits closely linked with the use of ionic fluids and corresponding hybrids, such as improved ionic conductivity, thermal and electrochemical stabilities, and tunability, in comparison with the traditional solvents, electrolytes, and electrodes. Finally, this work analyzes the fundamental limitations of such novel fluids such as their corrosivity potential, elevated dynamic viscosity, and leakage risk, and highlights the essential prospects for the research and exploration of ionic liquids and derivatives in various electrochemical devices and procedures. Full article
(This article belongs to the Special Issue Advanced Electrode Materials for Energy Storage Devices)
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42 pages, 11578 KiB  
Review
Halide Perovskites’ Multifunctional Properties: Coordination Engineering, Coordination Chemistry, Electronic Interactions and Energy Applications beyond Photovoltaics
by Taame Abraha Berhe, Wei-Nien Su and Bing Joe Hwang
Inorganics 2024, 12(7), 182; https://doi.org/10.3390/inorganics12070182 - 28 Jun 2024
Cited by 7 | Viewed by 2496
Abstract
Halide perovskite materials have gained enormous attention for their semiconducting properties, higher power conversion efficiency and potential applications in a wide range of fields of study, along with their two key limitations: stability and toxicity. Despite great progress made on halide perovskites and [...] Read more.
Halide perovskite materials have gained enormous attention for their semiconducting properties, higher power conversion efficiency and potential applications in a wide range of fields of study, along with their two key limitations: stability and toxicity. Despite great progress made on halide perovskites and many promising research developments, the issues of stability and toxicity have not been fully resolved. Therefore, the coordination engineering of a new framework to obtain alternative new halide perovskite materials and a fundamental understanding of the coordination chemistry and electronic interactions forming the structure of these newly engineered halide perovskite materials are possible ways to overcome the issues related to both stability and toxicity. In this review, we comprehensively review the current development of halide perovskite families, both lead halide perovskites and lead-free halide perovskites, followed by the coordination engineering of the new frameworks to engineer new halide perovskite materials. All concerns regarding the fundamental ideas of coordination chemistry and electronic interactions are vital in forming halide perovskite structures and thus form the main aim of this review. We also discuss recent potential energy applications beyond photovoltaics and thus answer an essential and open question, ‘what could happen in the future of halide perovskites?’ in order to excite commercial enterprises and research institutions again as well as to motivate new predictions on the future continuity of this field. Full article
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16 pages, 3119 KiB  
Review
Review on Preparation of Perovskite Solar Cells by Pulsed Laser Deposition
by Xinyu Lu, Xingjian Fan, Hao Zhang, Qingyu Xu and Mohsin Ijaz
Inorganics 2024, 12(5), 128; https://doi.org/10.3390/inorganics12050128 - 24 Apr 2024
Cited by 11 | Viewed by 3528
Abstract
Pulsed laser deposition (PLD) is a simple and extremely versatile technique to grow thin films and nanomaterials from a wide variety of materials. Compared to traditional fabrication methods, PLD is a clean physical vapour deposition approach that avoids complicated chemical reactions and by-products, [...] Read more.
Pulsed laser deposition (PLD) is a simple and extremely versatile technique to grow thin films and nanomaterials from a wide variety of materials. Compared to traditional fabrication methods, PLD is a clean physical vapour deposition approach that avoids complicated chemical reactions and by-products, achieving a precise stochiometric transfer of the target material onto the substrate and providing control over the film thickness. Halide perovskite materials have attracted extensive attention due to their excellent photoelectric and photovoltaic properties. In this paper, we present an overview of the fundamental and practical aspects of PLD. The properties and preparation methods of the halide perovskite materials are briefly discussed. Finally, we will elaborate on recent research on the preparation of perovskite solar cells by PLD, summarize the advantages and disadvantages of the PLD preparation, and prospect the all-vacuum PLD-grown solar cells in a full solar cell structure. Full article
(This article belongs to the Special Issue New Semiconductor Materials for Energy Conversion)
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22 pages, 6407 KiB  
Review
An Old Material for a New World: Prussian Blue and Its Analogues as Catalysts for Modern Needs
by Isabella Concina
Inorganics 2024, 12(4), 124; https://doi.org/10.3390/inorganics12040124 - 22 Apr 2024
Cited by 6 | Viewed by 3341
Abstract
Prussian blue analogues (PBAs) have recently emerged as effective materials in different functional applications, ranging from energy storage to electrochemical water splitting, thence to more “traditional” heterogeneous catalysis. Their versatility is due to their open framework, compositional variety, and fast and efficient internal [...] Read more.
Prussian blue analogues (PBAs) have recently emerged as effective materials in different functional applications, ranging from energy storage to electrochemical water splitting, thence to more “traditional” heterogeneous catalysis. Their versatility is due to their open framework, compositional variety, and fast and efficient internal charge exchange, coupled with a self-healing ability that makes them unique. This review paper presents and discusses the findings of the last decade in the field of the catalytic and photocatalytic application of PBAs in water remediation (via the degradation of organic pollutants and heavy metal removal) and the catalytic oxidation of organics and production or organic intermediates for industrial synthesis. Analysis of the catalytic processes is approached from a critical perspective, highlighting both the achievements of the research community and the limits still affecting this field. Full article
(This article belongs to the Special Issue Recent Advances in Biological and Catalytic Applications of Metal Complexes)
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16 pages, 3699 KiB  
Article
SCAPS-1D Simulation for Device Optimization to Improve Efficiency in Lead-Free CsSnI3 Perovskite Solar Cells
by Hyun-Jae Park, Hyojung Son and Byoung-Seong Jeong
Inorganics 2024, 12(4), 123; https://doi.org/10.3390/inorganics12040123 - 21 Apr 2024
Cited by 25 | Viewed by 7111
Abstract
In this study, a novel systematic analysis was conducted to explore the impact of various parameters, including acceptor density (NA), individual layer thickness, defect density, interface defect density, and the metal electrode work function, on efficiency within the FTO/ZnO/CsSnI3/NiO [...] Read more.
In this study, a novel systematic analysis was conducted to explore the impact of various parameters, including acceptor density (NA), individual layer thickness, defect density, interface defect density, and the metal electrode work function, on efficiency within the FTO/ZnO/CsSnI3/NiOx/Au perovskite solar cell structure through the SCAPS-1D (Solar Cell Capacitance Simulator in 1 Dimension) simulation. ZnO served as the electron transport layer (ETL), CsSnI3 as the perovskite absorption layer (PAL), and NiOx as the hole transport layer (HTL), all contributing to the optimization of device performance. To achieve the optimal power conversion efficiency (PCE), we determined the ideal PAL acceptor density (NA) to be 2 × 1019 cm−3 and the optimal thicknesses to be 20 nm for the ETL (ZnO), 700 nm for the PAL (CsSnI3), and 10 nm for the HTL (NiOx), with the metal electrode remaining as Au. As a result of the optimization process, efficiency increased from 11.89% to 23.84%. These results are expected to contribute to the performance enhancement of eco-friendly, lead-free inorganic hybrid solar cells with Sn-based perovskite as the PAL. Full article
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32 pages, 20927 KiB  
Review
Structure, Properties, and Preparation of MXene and the Application of Its Composites in Supercapacitors
by Mingming Sun, Wen Ye, Jingyao Zhang and Kaining Zheng
Inorganics 2024, 12(4), 112; https://doi.org/10.3390/inorganics12040112 - 12 Apr 2024
Cited by 21 | Viewed by 6729
Abstract
Two-dimensional transition metal carbides/nitrides (MXenes) are emerging members of the two-dimensional material family, obtained by removing the A layer of the MAX phase through methods such as liquid-phase etching. This article summarizes the structure and properties of MXenes, as well as several preparation [...] Read more.
Two-dimensional transition metal carbides/nitrides (MXenes) are emerging members of the two-dimensional material family, obtained by removing the A layer of the MAX phase through methods such as liquid-phase etching. This article summarizes the structure and properties of MXenes, as well as several preparation methods, including etching with hydrofluoric acid and fluoride salts, alkali-based etching, electrochemical etching, Lewis acid molten salt etching, and direct synthesis. Due to their unique two-dimensional structure and surface chemistry, MXenes exhibit good metallic conductivity, hydrophilicity, excellent flexibility, and ion intercalation properties, showing great potential in the research and application of supercapacitors and attracting widespread attention. The combination of MXene with other types of materials, including polymers, metal hydroxides, metal oxides, and carbon materials, takes advantage of composites to improve energy storage performance and shows great potential in the research and application of supercapacitors. This article provides a detailed summary of MXene composite materials and capacitor performance and introduces the research progress of MXene materials in the field of supercapacitor energy storage applications, aiming to provide references for the preparation of high-performance MXene supercapacitor electrode materials. Full article
(This article belongs to the Special Issue Recent Advances in Energy Storage and Conversion)
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21 pages, 2005 KiB  
Review
Regulatory and Sensing Iron–Sulfur Clusters: New Insights and Unanswered Questions
by Anna M. SantaMaria and Tracey A. Rouault
Inorganics 2024, 12(4), 101; https://doi.org/10.3390/inorganics12040101 - 30 Mar 2024
Cited by 5 | Viewed by 3459
Abstract
Iron is an essential nutrient and necessary for biological functions from DNA replication and repair to transcriptional regulation, mitochondrial respiration, electron transfer, oxygen transport, photosynthesis, enzymatic catalysis, and nitrogen fixation. However, due to iron’s propensity to generate toxic radicals which can cause damage [...] Read more.
Iron is an essential nutrient and necessary for biological functions from DNA replication and repair to transcriptional regulation, mitochondrial respiration, electron transfer, oxygen transport, photosynthesis, enzymatic catalysis, and nitrogen fixation. However, due to iron’s propensity to generate toxic radicals which can cause damage to DNA, proteins, and lipids, multiple processes regulate the uptake and distribution of iron in living systems. Understanding how intracellular iron metabolism is optimized and how iron is utilized to regulate other intracellular processes is important to our overall understanding of a multitude of biological processes. One of the tools that the cell utilizes to regulate a multitude of functions is the ligation of the iron–sulfur (Fe-S) cluster cofactor. Fe-S clusters comprised of iron and inorganic sulfur are ancient components of living matter on earth that are integral for physiological function in all domains of life. FeS clusters that function as biological sensors have been implicated in a diverse group of life from mammals to bacteria, fungi, plants, and archaea. Here, we will explore the ways in which cells and organisms utilize Fe-S clusters to sense changes in their intracellular environment and restore equilibrium. Full article
(This article belongs to the Special Issue Iron-Sulfur Clusters: Assembly and Biological Roles)
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12 pages, 2960 KiB  
Article
Quantum Yield Enhancement of Carbon Quantum Dots Using Chemical-Free Precursors for Sensing Cr (VI) Ions
by Karthiga Anpalagan, Hong Yin, Ivan Cole, Tian Zhang and Daniel T. H. Lai
Inorganics 2024, 12(4), 96; https://doi.org/10.3390/inorganics12040096 - 28 Mar 2024
Cited by 12 | Viewed by 3334
Abstract
Quantum yield illustrates the efficiency that a fluorophore converts the excitation light into fluorescence emission. The quantum yield of carbon quantum dots (CQDs) can be altered via precursors, fabrication conditions, chemical doping, and surface modifications. In this study, CQDs were first fabricated from [...] Read more.
Quantum yield illustrates the efficiency that a fluorophore converts the excitation light into fluorescence emission. The quantum yield of carbon quantum dots (CQDs) can be altered via precursors, fabrication conditions, chemical doping, and surface modifications. In this study, CQDs were first fabricated from whole-meal bread using a chemical-free hydrothermal route, and a low quantum yield (0.81%) was obtained. The combination of whole-meal bread, soybean flour, and lemon juice generated CQDs with almost four folds of enhancement in quantum yield. Detailed characterization suggested that these CQDs were subjected to more complete hydrothermal reactions and had zwitterionic surfaces. The CQDs could selectively detect Cr (VI) ions with a limit of detection (LOD) of 8 ppm. This study shows that the enhancement of the quantum yield of CQDs does not need chemicals, and it is achievable with food precursors. Full article
(This article belongs to the Special Issue Synthesis and Application of Luminescent Materials)
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13 pages, 2523 KiB  
Article
Alkane Elimination Preparation of Heterobimetallic MoAl Tetranuclear and Binuclear Complexes Promoting THF Ring Opening
by Léon Escomel, Erwann Jeanneau, Chloé Thieuleux and Clément Camp
Inorganics 2024, 12(3), 72; https://doi.org/10.3390/inorganics12030072 - 28 Feb 2024
Cited by 3 | Viewed by 2391
Abstract
We report a straightforward alkane elimination strategy to prepare well-defined heterobimetallic Al/Mo species. Notably, the reaction of the monohydride complex of molybdenum, Cp*MoH(CO)3, with triisobutyl aluminum affords a new heterobimetallic [MoAl]2 tetranuclear compound, [Cp*Mo(CO)(µ-CO)2Al(iBu)2] [...] Read more.
We report a straightforward alkane elimination strategy to prepare well-defined heterobimetallic Al/Mo species. Notably, the reaction of the monohydride complex of molybdenum, Cp*MoH(CO)3, with triisobutyl aluminum affords a new heterobimetallic [MoAl]2 tetranuclear compound, [Cp*Mo(CO)(µ-CO)2Al(iBu)2]2, (1), featuring a 12-membered C4O4Mo2Al2 ring in which isocarbonyls bridge the Mo and Al centers. The addition of pyridine to this complex successfully results in the dissociation of the dimer into a new discrete binuclear complex, [Cp*Mo(CO)2(µ-CO)Al(Py)(iBu)2], (2). Switching the nature of the Lewis base from pyridine to tetrahydrofuran does not lead to the THF analogue of adduct 2, but rather to a complex reaction where one of the identified products corresponds to a tetranuclear species, [Cp*Mo(CO)3(μ-CH2CH2CH2CH2O)Al(iBu)2]2, (3), featuring two bridging alkoxybutyl fragments originating from the C-O ring opening of THF. Compound 3 adds to the unusual occurrences of THF ring opening by heterobimetallic complexes, which is evocative of masked metal-only frustrated Lewis pair behavior and highlights the high reactivity of these Al/Mo assemblies. Full article
(This article belongs to the Special Issue Binuclear Complexes II)
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19 pages, 3030 KiB  
Article
ZnO–Doped CaO Binary Core–Shell Catalysts for Biodiesel Production via Mexican Palm Oil Transesterification
by M. G. Arenas-Quevedo, M. E. Manríquez, J. A. Wang, O. Elizalde-Solís, J. González-García, A. Zúñiga-Moreno and L. F. Chen
Inorganics 2024, 12(2), 51; https://doi.org/10.3390/inorganics12020051 - 3 Feb 2024
Cited by 6 | Viewed by 2840
Abstract
This work investigates biodiesel production via transesterification of Mexican palm oil with methanol catalyzed by binary solid base core–shell catalysts with improved catalytic stability. A series of CaO–ZnO mixed solids were prepared using an inexpensive co–precipitation method by varying ZnO content from 5 [...] Read more.
This work investigates biodiesel production via transesterification of Mexican palm oil with methanol catalyzed by binary solid base core–shell catalysts with improved catalytic stability. A series of CaO–ZnO mixed solids were prepared using an inexpensive co–precipitation method by varying ZnO content from 5 to 20 mol%. Several factors, such as surface basicity, ZnO content, phase compositions, and thermal treatment of the catalysts, were all proven to be crucial for the production of biodiesel with good quality. Thermal treatment could effectively remove the surface adsorbed water and impurities and improved the catalytic activity. The addition of ZnO to CaO significantly enhanced the catalysts’ stability; however, it led to lower surface basicity and slightly diminished catalytic activity. ZnO doping inhibited the formation of surface Ca(OH)2 and promoted the formation of Ca–Zn–O or CaZn2(OH)6 phase as the core and a surface CaCO3 shell, which effectively decreased Ca2+ leaching by approximately 74% in methanol and 65% in a methanol–glycerol (4:1) mixture. A combined method of separation and purification for obtaining clean biodiesel with high quality was proposed. The biodiesel obtained under the control conditions exhibited properties which satisfied the corresponding standards well. Full article
(This article belongs to the Special Issue 10th Anniversary of Inorganics: Inorganic Materials)
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23 pages, 14000 KiB  
Review
Application of Infrared Free-Electron Laser Irradiation of Protein Complexes Binding to Salen-Type Schiff Base Zn(II) Complexes Using Secondary Conformational Changes in the Proteins for the Treatment of Alzheimer’s Disease
by Hiroshi Takashima, Daisuke Nakane and Takashiro Akitsu
Inorganics 2024, 12(2), 50; https://doi.org/10.3390/inorganics12020050 - 3 Feb 2024
Cited by 2 | Viewed by 2563
Abstract
Alzheimer’s disease causes the destruction of cranial nerve cells and is said to be caused by neuronal cell death due to the accumulation of amyloid-β protein. One method for the treatment of Alzheimer’s disease is to reduce the toxicity of the amyloid beta [...] Read more.
Alzheimer’s disease causes the destruction of cranial nerve cells and is said to be caused by neuronal cell death due to the accumulation of amyloid-β protein. One method for the treatment of Alzheimer’s disease is to reduce the toxicity of the amyloid beta protein. Among the possibilities is to reduce toxicity by changing the secondary structure of the protein. In this study, the secondary structure of the protein was verified by binding a zinc complex to the protein and irradiating it with an infrared free-electron laser (IR-FEL). By binding Salen-Type zinc complexes to human serum albumin (HSA) and irradiating it with IR-FEL, structural changes were observed in the α-helix and β-sheet, the secondary structure of HSA. In addition to researching the possibility of binding zinc complexes to small proteins, docking simulations were examined. GOLD docking simulations showed that it is possible to bind zinc complexes to lysozyme (Lyz), a small protein. These results suggest that binding zinc complexes to amyloid-β and inducing a secondary conformational change through IR-FEL irradiation could be used for the treatment of Alzheimer’s disease by making the complexes lose their toxicity. Full article
(This article belongs to the Special Issue Rational Design of Pharmacologically Active Metal-Based Compounds)
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13 pages, 6616 KiB  
Article
A Core and Valence-Level Spectroscopy Study of the Enhanced Reduction of CeO2 by Iron Substitution—Implications for the Thermal Water-Splitting Reaction
by Hicham Idriss
Inorganics 2024, 12(2), 42; https://doi.org/10.3390/inorganics12020042 - 27 Jan 2024
Cited by 6 | Viewed by 2393
Abstract
The reduction of Ce cations in CeO2 can be enhanced by their partial substitution with Fe cations. The enhanced reduction of Ce cations results in a considerable increase in the reaction rates for the thermal water-splitting reaction when compared to CeO2 [...] Read more.
The reduction of Ce cations in CeO2 can be enhanced by their partial substitution with Fe cations. The enhanced reduction of Ce cations results in a considerable increase in the reaction rates for the thermal water-splitting reaction when compared to CeO2 alone. This mixed oxide has a smaller crystallite size when compared to CeO2, in addition to a smaller lattice size. In this work, two Fe-substituted Ce oxides are studied (Ce0.95Fe0.05O2-δ and Ce0.75Fe0.25O2-δ; δ < 0.5) by core and valence level spectroscopy in their as-prepared and Ar-ion-sputtered states. Ar ion sputtering substantially increases Ce4f lines at about 1.5 eV below the Fermi level. In addition, it is found that the XPS Ce5p/O2s ratio is sensitive to the degree of reduction, most likely due to a higher charge transfer from the oxygen to Ce ions upon reduction. Quantitatively, it is also found that XPS Ce3d of the fraction of Ce3+ (uo, u′ and vo, v′) formed upon Ar ion sputtering and the ratio of Ce5p/O2s lines are higher for reduced Ce0.95Fe0.05O2-δ than for reduced Ce0.75Fe0.25O2-δ. XPS Fe2p showed, however, no preferential increase for Fe3+ reduction to Fe0 with increasing time for both oxides. Since water splitting was higher on Ce0.95Fe0.05O2-δ when compared to Ce0.75Fe0.25O2-δ, it is inferred that the reaction centers for the thermal water splitting to hydrogen are the reduced Ce cations and not the reduced Fe cations. These reduced Ce cations can be tracked by their XPS Ce5p/O2s ratio in addition to the common XPS Ce3d lines. Full article
(This article belongs to the Special Issue Nano-Design of Transition Metal Oxides for Energy Storage and Catalytic Application)
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23 pages, 6950 KiB  
Article
Self-Cleaning and Charge Transport Properties of Foils Coated with Acrylic Paint Containing TiO2 Nanoparticles
by Sanja J. Armaković, Maria M. Savanović, Mirjana V. Šiljegović, Milica Kisić, Maja Šćepanović, Mirjana Grujić-Brojčin, Nataša Simić, Lazar Gavanski and Stevan Armaković
Inorganics 2024, 12(1), 35; https://doi.org/10.3390/inorganics12010035 - 22 Jan 2024
Cited by 10 | Viewed by 3323
Abstract
The study comprehensively investigates the design and performance of self-cleaning surfaces fabricated by coating aluminum foil with an acrylic paint matrix enriched with different content of titanium dioxide (TiO2) nanoparticles. The main goal was to assess the self-cleaning characteristics of the [...] Read more.
The study comprehensively investigates the design and performance of self-cleaning surfaces fabricated by coating aluminum foil with an acrylic paint matrix enriched with different content of titanium dioxide (TiO2) nanoparticles. The main goal was to assess the self-cleaning characteristics of the surfaces obtained. This study employs scanning electron microscopy (SEM) to analyze the morphology of TiO2-modified acrylic surfaces, revealing spherical particles. Raman spectroscopy elucidates signatures characterizing TiO2 incorporation within the acrylic matrix, providing comprehensive insights into structural and compositional changes for advanced surface engineering. Alternating current (AC) impedance spectroscopy was used to assess selected charge transport properties of produced self-cleaning surfaces, allowing us to gain valuable insights into the material’s conductivity and its potential impact on photocatalytic performance. The self-cleaning properties of these tiles were tested against three frequently used textile dyes, which are considered to pose a serious environmental threat. Subsequently, improving self-cleaning properties was achieved by plasma treatment, utilizing a continuous plasma arc. The plasma treatment led to enhanced charge separation and surface reactivity, crucial factors in the self-cleaning mechanism. To deepen our comprehension of the reactive properties of dye molecules and their degradation dynamics, we employed a combination of density functional tight binding (DFTB) and density functional theory (DFT) calculations. This investigation lays the foundation for advancing self-cleaning materials with extensive applications, from architectural coatings to environmental remediation technologies. Full article
(This article belongs to the Special Issue Recent Advances in Ceramic Materials)
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24 pages, 5563 KiB  
Review
Tip of the Iceberg: A New Wave of Iron–Sulfur Cluster Proteins Found in Viruses
by Audrey L. Heffner and Nunziata Maio
Inorganics 2024, 12(1), 34; https://doi.org/10.3390/inorganics12010034 - 18 Jan 2024
Cited by 3 | Viewed by 3584
Abstract
Viruses rely on host cells to replicate their genomes and assemble new viral particles. Thus, they have evolved intricate mechanisms to exploit host factors. Host cells, in turn, have developed strategies to inhibit viruses, resulting in a nuanced interplay of co-evolution between virus [...] Read more.
Viruses rely on host cells to replicate their genomes and assemble new viral particles. Thus, they have evolved intricate mechanisms to exploit host factors. Host cells, in turn, have developed strategies to inhibit viruses, resulting in a nuanced interplay of co-evolution between virus and host. This dynamic often involves competition for resources crucial for both host cell survival and virus replication. Iron and iron-containing cofactors, including iron–sulfur clusters, are known to be a heavily fought for resource during bacterial infections, where control over iron can tug the war in favor of the pathogen or the host. It is logical to assume that viruses also engage in this competition. Surprisingly, our knowledge about how viruses utilize iron (Fe) and iron–sulfur (FeS) clusters remains limited. The handful of reviews on this topic primarily emphasize the significance of iron in supporting the host immune response against viral infections. The aim of this review, however, is to organize our current understanding of how viral proteins utilize FeS clusters, to give perspectives on what questions to ask next and to propose important avenues for future investigations. Full article
(This article belongs to the Special Issue Iron-Sulfur Clusters: Assembly and Biological Roles)
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18 pages, 2053 KiB  
Article
Deciphering Interactions Involved in Immobilized Metal Ion Affinity Chromatography and Surface Plasmon Resonance for Validating the Analogy between Both Technologies
by Rachel Irankunda, Jairo Andrés Camaño Echavarría, Cédric Paris, Katalin Selmeczi, Loïc Stefan, Sandrine Boschi-Muller, Laurence Muhr and Laetitia Canabady-Rochelle
Inorganics 2024, 12(1), 31; https://doi.org/10.3390/inorganics12010031 - 16 Jan 2024
Cited by 5 | Viewed by 2818
Abstract
Various peptides can be obtained through protein enzymatic hydrolysis. Immobilized metal ion affinity chromatography (IMAC) is one of the methods which can be used to separate metal chelating peptides (MCPs) in a hydrolysate mixture. In this context, this work aims to understand deeply [...] Read more.
Various peptides can be obtained through protein enzymatic hydrolysis. Immobilized metal ion affinity chromatography (IMAC) is one of the methods which can be used to separate metal chelating peptides (MCPs) in a hydrolysate mixture. In this context, this work aims to understand deeply the interactions in IMAC and surface plasmon resonance (SPR) in order to validate experimentally the analogy between both technologies and to be further able to perform IMAC modeling in the next work using peptide sorption isotherm parameters obtained from SPR. Indeed, chromatography modeling can be used to predict separation of MCPs in IMAC and the knowledge of peptide sorption isotherm obtained from SPR is a crucial step. For this purpose, 22 peptides were selected and investigated in IMAC using HisTrap X-Ni2+ and HiFliQ NTA-Ni2+ columns and were also studied in SPR as well. Results showed that peptides with histidine residues had good affinity to Ni2+, while the high positive charge of peptides was responsible of ionic interactions. Further, most of the peptides with good retention time in IMAC showed a good affinity in SPR as well, which validated experimentally the SPR-IMAC analogy. Full article
(This article belongs to the Special Issue Women’s Special Issue Series: Inorganics)
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28 pages, 3165 KiB  
Review
Survey of Main Group Metals and Metalloids in Cancer Treatment
by Irena Kostova
Inorganics 2024, 12(1), 29; https://doi.org/10.3390/inorganics12010029 - 12 Jan 2024
Cited by 3 | Viewed by 3197
Abstract
Cancer is one of the leading causes of human death among all major diseases. Metal-based complexes are considered as the most promising vital part in the existing arsenal of cytotoxic candidates used in cancer therapy and diagnostics. The efforts of many scientific groups [...] Read more.
Cancer is one of the leading causes of human death among all major diseases. Metal-based complexes are considered as the most promising vital part in the existing arsenal of cytotoxic candidates used in cancer therapy and diagnostics. The efforts of many scientific groups resulted in the development of numerous metal-based compounds featuring different biologically active organic ligands in order to modulate their bioactivity. Along with the main representatives as potential therapeutic agents, such as the complexes Pt(II)/Pt(IV), Pd(II), Ru(II)/Ru(III), Ag(I), Au(I)/Au(III), Ti(IV), V(IV) and Ga(III), many other transition metal and lanthanide complexes possessing antiproliferative activity are widely discussed in the literature. However, such drugs remain outside the scope of this review. The main purpose of the current study is to review the potential activity of main group metal- and metalloid-based complexes against the most common cancer cell types, such as carcinomas (lung, liver, breast, kidney, gastric, colorectal, bladder, ovarian, cervical, prostate, etc.); sarcomas; blastomas; lymphomas; multiple myeloma; and melanoma. Overcoming the long disregard of organometallic compounds of metals and metalloids from the main groups, a growing number of emerging anticancer agents remarkably prove this field offers an extensive variety of new options for the design of innovative unexplored chemopharmaceutics. Moreover, some of the metal complexes and organometallic compounds from these elements can exhibit entirely different, specific modes of action and biological targets. Obviously, exploitation of their distinct properties deserves more attention. Full article
(This article belongs to the Special Issue Rational Design of Pharmacologically Active Metal-Based Compounds)
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23 pages, 3440 KiB  
Review
The Importance of Being Casiopeina as Polypharmacologycal Profile (Mixed Chelate–Copper (II) Complexes and Their In Vitro and In Vivo Activities)
by Zenayda Aguilar-Jiménez, Adrián Espinoza-Guillén, Karen Resendiz-Acevedo, Inés Fuentes-Noriega, Carmen Mejía and Lena Ruiz-Azuara
Inorganics 2023, 11(10), 394; https://doi.org/10.3390/inorganics11100394 - 7 Oct 2023
Cited by 27 | Viewed by 4315
Abstract
In this review, we present a timeline that shows the origin of mixed chelate copper (II) complexes, registered as Mark Title Casiopeínas®, as the first copper (II) compounds proposed as anticancer drugs in 1988 and 1992. In the late twentieth century, [...] Read more.
In this review, we present a timeline that shows the origin of mixed chelate copper (II) complexes, registered as Mark Title Casiopeínas®, as the first copper (II) compounds proposed as anticancer drugs in 1988 and 1992. In the late twentieth century, the use of essential metals as anticancer agents was not even considered, except for their antifungal or antibacterial effects; also, copper, as gold salts, was used for arthritis problems. The use of essential metals as anticancer drugs to diminish the secondary toxic effects of Cisplatin was our driving force: to find less toxic and even more economical compounds under the rational design of metal chelate complexes. Due to their chemical properties, copper compounds were the choice to continue anticancer drug development. In this order of ideas, the rational designs of mixed chelate–copper (II) complexes (Casiopeínas, (Cas) homoleptic or heteroleptic, depending on the nature of the secondary ligand) were synthesized and fully characterized. In the search for new, more effective, and less toxic drugs, Casiopeína® (Cas) emerged as a family of approximately 100 compounds synthesized from coordinated Cu(II) complexes with proven antineoplastic potential through cytotoxic action. The Cas have the general formula [Cu(N–N)(N–O)]NO3 and [Cu(N–N)(O–O)]NO3, where N–N is an aromatic substituted diimine (1,10-phenanthroline or 2,2′-bipyridine), and the oxygen donor (O–O) is acetylacetonate or salicylaldehyde. Lately, some similar compounds have been developed by other research groups considering a similar hypothesis after Casiopeína’s discoveries had been published, as described herein. As an example of translational medicine criteria, we have covered each step of the established normative process for drug development, and consequently, one of the molecules (Casiopeína III ia (CasIIIia)) has reached the clinical phase I. For these copper compounds, other activities, such as antibacterial, antiparasitic and antiviral, have been discovered. Full article
(This article belongs to the Special Issue Editorial Board Members’ Collection Series in “Bioinorganic Chemistry of Copper”)
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15 pages, 3317 KiB  
Article
Sn(IV)porphyrin-Anchored TiO2 Nanoparticles via Axial-Ligand Coordination for Enhancement of Visible Light-Activated Photocatalytic Degradation
by Nirmal Kumar Shee and Hee-Joon Kim
Inorganics 2023, 11(8), 336; https://doi.org/10.3390/inorganics11080336 - 15 Aug 2023
Cited by 14 | Viewed by 2663
Abstract
A visible-light-active photocatalyst, SnP/AA@TiO2, was fabricated by utilizing the coordination chemistry between the axial hydroxo-ligand in the (trans-dihydroxo)(5,10,15,20-tetraphenylporphyrinato)Sn(IV) complex (SnP) and adipic acid (AA) on the surface of TiO2 nanoparticles. The SnP center was strongly bonded to the [...] Read more.
A visible-light-active photocatalyst, SnP/AA@TiO2, was fabricated by utilizing the coordination chemistry between the axial hydroxo-ligand in the (trans-dihydroxo)(5,10,15,20-tetraphenylporphyrinato)Sn(IV) complex (SnP) and adipic acid (AA) on the surface of TiO2 nanoparticles. The SnP center was strongly bonded to the surface of the TiO2 nanoparticles via the adipic acid linkage in SnP/AA@TiO2, as confirmed by various instrumental techniques. SnP/AA@TiO2 exhibited remarkably enhanced photocatalytic activity toward the degradation of rhodamine B dye (RhB) in aqueous solution under visible-light irradiation. The RhB degradation efficiency of SnP/AA@TiO2 was 95% within 80 min, with a rate constant of 0.0366 min−1. The high degradation efficiency, low catalyst loading and high reusability make SnP-anchored photocatalysts more efficient than other photocatalysts, such as TiO2 and SnP@TiO2. Full article
(This article belongs to the Special Issue Nanocomposites for Photocatalysis)
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13 pages, 1153 KiB  
Article
Redox Targets for Phosphine–Boranes
by Yonatan Morocz, Rachel E. Greben and Leonard A. Levin
Inorganics 2023, 11(7), 310; https://doi.org/10.3390/inorganics11070310 - 22 Jul 2023
Cited by 1 | Viewed by 1950
Abstract
Understanding the complex mechanisms underlying redox-mediated biological processes is a fundamental pillar of cellular biology. We describe the identification and quantification of disulfide formation and reduction in response to phosphine–borane complexes. We illustrate the specific cysteine reduction effects of the novel phosphine–borane complex [...] Read more.
Understanding the complex mechanisms underlying redox-mediated biological processes is a fundamental pillar of cellular biology. We describe the identification and quantification of disulfide formation and reduction in response to phosphine–borane complexes. We illustrate the specific cysteine reduction effects of the novel phosphine–borane complex bis(3-propionic acid methyl ester) phenylphosphine–borane complex (PB1) on cultured 661W cells. A total of 1073 unique protein fragments from 628 unique proteins were identified and quantified, of which 13 were found to be statistically significant in comparison to control cells. Among the 13 identified proteins were Notch1, HDAC1, UBA1, USP7, and subunits L4 and L7 of the 60S ribosomal subunit, all of which are involved in redox or cell death-associated pathways. Leveraging the ability of tandem mass tagging mass spectrometry to provide quantitative data in an exploratory manner provides insight into the effect PB1 and other phosphine–borane compounds may have on the cysteine redoxome. Full article
(This article belongs to the Special Issue Synthesis and Innovative Biological Activity of Boron-Containing Compounds)
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20 pages, 2848 KiB  
Review
Carbon Quantum Dots: The Role of Surface Functional Groups and Proposed Mechanisms for Metal Ion Sensing
by Hasan Shabbir, Edit Csapó and Marek Wojnicki
Inorganics 2023, 11(6), 262; https://doi.org/10.3390/inorganics11060262 - 20 Jun 2023
Cited by 82 | Viewed by 11339
Abstract
Carbon dots (CDs) are zero-dimensional nanomaterials composed of carbon and surface groups attached to their surface. CDs have a size smaller than 10 nm and have potential applications in different fields such as metal ion detection, photodegradation of pollutants, and bio-imaging, in this [...] Read more.
Carbon dots (CDs) are zero-dimensional nanomaterials composed of carbon and surface groups attached to their surface. CDs have a size smaller than 10 nm and have potential applications in different fields such as metal ion detection, photodegradation of pollutants, and bio-imaging, in this review, the capabilities of CDs in metal ion detection will be described. Quantum confinement is generally viewed as the key factor contributing to the uniqueness of CDs characteristics due to their small size and the lack of attention on the surface functional groups and their roles is given, however, in this review paper, the focus will be on the functional group and the composition of CDs. The surface functional groups depend on two parameters: (i) the oxidation of precursors and (ii) their composition. The mechanism of metal ion detection is still being studied and is not fully understood. This review article emphasizes the current development and progress of CDs, focusing on metal ion detection based on a new perspective. Full article
(This article belongs to the Special Issue 10th Anniversary of Inorganics: Organometallic Chemistry)
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12 pages, 3812 KiB  
Article
Improved Oxide Ion Conductivity of Hexagonal Perovskite-Related Oxides Ba3W1+xV1−xO8.5+x/2
by Yugo Kikuchi, Yuta Yasui, James R. Hester and Masatomo Yashima
Inorganics 2023, 11(6), 238; https://doi.org/10.3390/inorganics11060238 - 29 May 2023
Cited by 6 | Viewed by 2195
Abstract
Hexagonal perovskite-related oxides such as Ba3WVO8.5 have attracted much attention due to their unique crystal structures and significant oxide ion conduction. However, the oxide ion conductivity of Ba3WVO8.5 is not very high. Herein, we report new hexagonal [...] Read more.
Hexagonal perovskite-related oxides such as Ba3WVO8.5 have attracted much attention due to their unique crystal structures and significant oxide ion conduction. However, the oxide ion conductivity of Ba3WVO8.5 is not very high. Herein, we report new hexagonal perovskite-related oxides Ba3W1+xV1−xO8.5+x/2 (x = −0.1, −0.05, 0.05, 0.1, 0.25, 0.4, 0.5, 0.6, and 0.75). The bulk conductivity of Ba3W1.6V0.4O8.8 was found to be 21 times higher than that of the mother material Ba3WVO8.5 at 500 °C. Maximum entropy method (MEM) neutron scattering length density (NSLD) analyses of neutron diffraction data at 800 °C experimentally visualized the oxide ion diffusion pathways through the octahedral O2 and tetrahedral O3 sites in intrinsically oxygen-deficient layers. By increasing the excess W content x in Ba3W1+xV1−xO8.5+x/2, the excess oxygen content x/2 increases, which leads to more oxygen atoms at the O2 and O3 oxygen sites, a higher minimum NSLD on the O2–O3 path, and a higher level of conductivity. Another reason for the increased conductivity of Ba3W1.6V0.4O8.8 is the lower activation energy for oxide ion conduction, which can be ascribed to the longer (W/V)–O2 and (W/V)–O3 distances due to the substitution of V atoms with large-sized W species. The present findings open new avenues in the science and technology of oxide ion conductors. Full article
(This article belongs to the Special Issue Layered Perovskites: Synthesis, Properties and Structures)
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17 pages, 5497 KiB  
Article
Chalcogen Bonds, Halogen Bonds and Halogen···Halogen Contacts in Di- and Tri-iododiorganyltellurium(IV) Derivatives
by Sergi Burguera, Rosa M. Gomila, Antonio Bauzá and Antonio Frontera
Inorganics 2023, 11(5), 209; https://doi.org/10.3390/inorganics11050209 - 12 May 2023
Cited by 5 | Viewed by 2245
Abstract
In this manuscript, we have examined the CSD (Cambridge Structural Database) to investigate the relative ability of Te and I (in practice, the heaviest chalcogen and halogen atoms) in di- and tri-iododiorganyltellurium(IV) derivatives to establish σ-hole interactions. The geometry around the Te(IV) in [...] Read more.
In this manuscript, we have examined the CSD (Cambridge Structural Database) to investigate the relative ability of Te and I (in practice, the heaviest chalcogen and halogen atoms) in di- and tri-iododiorganyltellurium(IV) derivatives to establish σ-hole interactions. The geometry around the Te(IV) in this type of compound is trigonal bipyramidal where the stereoactive lone pair at Te(IV) occupies one of the equatorial positions. In the solid state, Te(IV) tends to form pseudo-octahedral coordination by establishing strong noncovalent interactions opposite to the two covalent bonds of the equatorial plane. Such contacts can also be classified as chalcogen bonds following the recommendation of the International Union of Pure and Applied Chemistry (IUPAC). Such contacts have been analyzed energetically in this work using density functional theory (DFT) calculations, rationalized using molecular electrostatic potential (MEP) surface analysis and characterized using a combination of the quantum theory of atoms in molecules (QTAIM) and noncovalent interaction plot (NCIplot) computational tools. Finally, the observation of halogen bonds and type I halogen···halogen contacts is also emphasized and compared to the chalcogen bonds. Energy decomposition analysis has also been performed to compare the physical nature of chalcogen, halogen and type I interactions. Full article
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15 pages, 9033 KiB  
Article
Crystal Structure and XPS Study of Titanium-Substituted M-Type Hexaferrite BaFe12−xTixO19
by Kim-Isabelle Mehnert, Manuel Häßner, Yanina Mariella Dreer, Indro Biswas and Rainer Niewa
Inorganics 2023, 11(5), 207; https://doi.org/10.3390/inorganics11050207 - 10 May 2023
Cited by 14 | Viewed by 2884
Abstract
The M-type barium hexaferrite substituted with titanium, BaFe12−xTixO19, was synthesized from sodium carbonate flux and the obtained single crystals with a maximum degree of substitution of up to about x = 0.9 were characterized. XPS [...] Read more.
The M-type barium hexaferrite substituted with titanium, BaFe12−xTixO19, was synthesized from sodium carbonate flux and the obtained single crystals with a maximum degree of substitution of up to about x = 0.9 were characterized. XPS measurements were carried out for the identification of side products and in particular in order to assign the valence states of the transition-metal constituents. Due to the aliovalent exchange of iron(III) with titanium(IV), an additional charge balance needs to occur. No titanium(III) was detected, while the amount of iron(II) increased in the same order of magnitude as the amount of titanium(IV); thus, the major charge balancing is attributed to the reduction of iron(III) to iron(II). According to the XPS data, the amount of titanium(IV) typically is slightly higher than that of iron(II). This is in line with a tendency to a minor formation of vacancies on the transition-metal sites becoming more important at higher substitution levels according to PXRD and WDS measurements, completing the picture of the charge-balance mechanism. XRD taken on single crystals indicates the distribution of titanium and vacancies over three of the five transition-metal sites. Full article
(This article belongs to the Special Issue 10th Anniversary of Inorganics: Inorganic Solid State Chemistry)
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13 pages, 8083 KiB  
Article
First-Principles Calculations to Investigate Structural, Electronic, Optical and Magnetic Properties of Pyrochlore Oxides Eu2Tm2O7 (Tm = Hf, Sn, Zr) for Energy Applications
by Zeesham Abbas, Adeela Naz, Sajjad Hussain, Shabbir Muhammad, H. Algarni, Ahsan Ali and Jongwan Jung
Inorganics 2023, 11(5), 193; https://doi.org/10.3390/inorganics11050193 - 29 Apr 2023
Cited by 23 | Viewed by 2435
Abstract
Three newly designed pyrochlore oxides, Eu2Tm2O7 (Tm = Hf, Sn, Zr), are analyzed for their magnetic, optical and electronic properties using ab-initio calculations within the context of density functional theory (DFT). We can refer these compounds as direct [...] Read more.
Three newly designed pyrochlore oxides, Eu2Tm2O7 (Tm = Hf, Sn, Zr), are analyzed for their magnetic, optical and electronic properties using ab-initio calculations within the context of density functional theory (DFT). We can refer these compounds as direct bandgap materials because there is a very slight difference between the height of bands at the Γ- and M-point. It is observed that bandgap engineering can be performed by replacing Hf with Sn and Zr. It is observed from total density of states (TDOS) plots that shape and height of curves is not the same in spin up and spin down channels, showing significant magnetic moment in these compounds. It is evident from magnetic properties that a major portion of total magnetic moment (mtot) comes from Eu-atoms. In all compounds, the magnetic moment of O, Hf, Sn and Zr atoms is negative, whereas the magnetic moment of Eu-atoms is positive, showing their antiparallel arrangement. In both spin channels, significant absorption of the incoming photons is also shown by these compounds in the ultraviolet (UV) region. We can conclude on the basis of Rω that these compounds can be utilized in applications such as anti-reflecting coatings. These compounds are potential candidates for photovoltaic applications, such as solar cells, due to efficient absorption of incoming photons in visible and UV regions. Full article
(This article belongs to the Section Inorganic Solid-State Chemistry)
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23 pages, 11040 KiB  
Review
Co(III) Intermediates in Cobalt-Catalyzed, Bidentate Chelation Assisted C(sp2)-H Functionalizations
by Aleksandrs Cizikovs and Liene Grigorjeva
Inorganics 2023, 11(5), 194; https://doi.org/10.3390/inorganics11050194 - 29 Apr 2023
Cited by 12 | Viewed by 3246
Abstract
The C-H bond activation and functionalization is a powerful tool that provides efficient access to various organic molecules. The cobalt-catalyzed oxidative C-H bond activation and functionalization has earned enormous interest over the past two decades. Since then, a wide diversity of synthetic protocols [...] Read more.
The C-H bond activation and functionalization is a powerful tool that provides efficient access to various organic molecules. The cobalt-catalyzed oxidative C-H bond activation and functionalization has earned enormous interest over the past two decades. Since then, a wide diversity of synthetic protocols have been published for C-C, C-Het, and C-Hal bond formation reactions. To gain some insights into the reaction mechanism, the authors performed a series of experiments and collected evidence. Several groups have successfully isolated reactive Co(III) intermediates to elucidate the reaction mechanism. In this review, we will summarize information concerning the isolated and synthesized Co(III) intermediates in cobalt-catalyzed, bidentate chelation assisted C-H bond functionalization and their reactivity based on the current knowledge about the general reaction mechanism. Full article
(This article belongs to the Special Issue Recent Highlights Using Cobalt Catalysis)
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14 pages, 2933 KiB  
Article
X-ray Absorption Spectroscopy of Phosphine-Capped Au Clusters
by Shailendra K. Sharma, Bernt Johannessen, Vladimir B. Golovko and Aaron T. Marshall
Inorganics 2023, 11(5), 191; https://doi.org/10.3390/inorganics11050191 - 28 Apr 2023
Cited by 3 | Viewed by 2842
Abstract
The structural determination of ultrasmall clusters remains a challenge due to difficulties in crystallisation. Often the atomically precise clusters undergo structural change under the influence of the environment. X-ray absorption spectroscopy (XAS) can be an attractive tool to study the electronic and geometric [...] Read more.
The structural determination of ultrasmall clusters remains a challenge due to difficulties in crystallisation. Often the atomically precise clusters undergo structural change under the influence of the environment. X-ray absorption spectroscopy (XAS) can be an attractive tool to study the electronic and geometric properties of such clusters deposited onto various supports under in situ conditions. Herein, [Au6(dppp)4](NO3)2, [Au9(PPh3)8](NO3)3, [Au13(dppe)5Cl2]Cl3, and Au101(PPPh3)21Cl5 clusters were studied using XAS. The clusters exhibited distinct features compared to bulk gold. XANES results show a systematic increase in the absorption edge energy and white line intensity, with a decrease in cluster nuclearity. The EXAFS of clusters are sensitive to nuclearity and ligands and were fitted with their known crystal structures. This study advances the understanding of the phosphine-ligated metal clusters relevant to practical applications in catalysis and sensing. Full article
(This article belongs to the Special Issue Phosphorus Ligands for the Stabilization of Unusual and Elusive Structures in Transition Metal Complexes)
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17 pages, 1734 KiB  
Review
Metal Hydride Composite Structures for Improved Heat Transfer and Stability for Hydrogen Storage and Compression Applications
by Liang Liu, Alexander Ilyushechkin, Daniel Liang, Ashleigh Cousins, Wendy Tian, Cherry Chen, Jon Yin and Liezl Schoeman
Inorganics 2023, 11(5), 181; https://doi.org/10.3390/inorganics11050181 - 24 Apr 2023
Cited by 13 | Viewed by 4808
Abstract
Metal alloys and intermetallic compounds offer an attractive method for safely storing hydrogen (H2). The metal alloys absorb H2 into their structure, often swelling and fracturing as a result of phase transformation during hydride formation/decomposition cycles. The absorption of H [...] Read more.
Metal alloys and intermetallic compounds offer an attractive method for safely storing hydrogen (H2). The metal alloys absorb H2 into their structure, often swelling and fracturing as a result of phase transformation during hydride formation/decomposition cycles. The absorption of H2 is an exothermic process, requiring the effective and efficient removal of heat. This can be challenging as heat transfer to/from powdered beds is notoriously difficult, and often limited by poor thermal conductivity. Hence, the observed reaction kinetics for absorption and desorption of H2 is dominated by heat flow. The most common method for improving the thermal conductivity of the alloy powders is to prepare them into composite structures with other high thermal conductivity materials, such as carbons and expanded natural graphite. Such composite structures, some also combined with polymers/resins, can also mitigate safety issues related to swelling and improve cyclic durability. This paper reviews the methods that have been used to prepare such composite structures and evaluates the observed impact on thermal conductivity. Full article
(This article belongs to the Special Issue State-of-the-Art and Progress in Metal-Hydrogen Systems)
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19 pages, 2502 KiB  
Article
C–H Metalation of Terpyridine Stereoisomers with Ni(II), Pd(II), and Pt(II)
by Leo Payen, Lukas Kletsch, Tobias Lapić, Mathias Wickleder and Axel Klein
Inorganics 2023, 11(4), 174; https://doi.org/10.3390/inorganics11040174 - 21 Apr 2023
Cited by 6 | Viewed by 3136
Abstract
Ni(II), Pd(II), and Pt(II) complexes [M(Y-terpy)X] (X = Cl or Br) containing the tridentate N^C^N-cyclometalating 2,3′:5′,2″and 2,2′:4′,2″ stereoisomers of the well-known tridentate N^N^N ligand 2,2′:6′,2″-terpyridine (terpy) were synthesised in moderate to good yields through C–H activation. For the Pt complexes, the phenyl ethynide [...] Read more.
Ni(II), Pd(II), and Pt(II) complexes [M(Y-terpy)X] (X = Cl or Br) containing the tridentate N^C^N-cyclometalating 2,3′:5′,2″and 2,2′:4′,2″ stereoisomers of the well-known tridentate N^N^N ligand 2,2′:6′,2″-terpyridine (terpy) were synthesised in moderate to good yields through C–H activation. For the Pt complexes, the phenyl ethynide derivatives [Pt(Y-terpy)(C≡CPh)] were also obtained under Sonogashira conditions. In contrast to this, C^N^N cyclometalated complexes using the 2,2′:6′,3″- and 2,2′:6′4″-terpy isomers were not obtained. Comparison of the N^C^N complexes of the cyclometalated 2,3′:5′,2″- and 2,2′:4′,2″-terpy ligands with complexes [M(dpb)Cl] of the prototypical N^C^N cyclometalating ligand dpb− (Hdpb = 2,6-diphenyl-pyridine) showed higher potentials for the terpy complexes for the ligand-centred reductions in line with the superior π-accepting properties of the terpy ligands compared with dpb. Metal-centred oxidations were facilitated by the dpb ligand carrying a central σ-donating phenyl group instead of a metalated pyridine moiety. The same trends were found for the long-wavelength absorptions and the derived electrochemical and optical band gaps. The lower σ-donating capacities of the cyclometalated terpy derivatives is also confirmed by a reduced trans influence in the structure of [Ni(2,3′:5′,2″-terpy)Br0.14/OAc0.86]. Attempts to re-crystallise some poorly soluble Pd(II) and Pt(II) complexes of this series under solvothermal conditions (HOAc) gave two structures with N-protonated cyclometalated pyridine moieties, [Pt(2,3′:5′,2″-terpyH)Cl].Cl and [Pd(2,3′:5′,2″-terpyH)Cl2]. Full article
(This article belongs to the Special Issue Revealing Reaction Mechanisms in Homogeneous Transition Metal Catalysis, 2nd Edition)
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12 pages, 1967 KiB  
Article
Surface Passivation of Organic-Inorganic Hybrid Perovskites with Methylhydrazine Iodide for Enhanced Photovoltaic Device Performance
by Chongzhu Hu, Zhuangzhuang Zhang, Jun Chen and Peng Gao
Inorganics 2023, 11(4), 168; https://doi.org/10.3390/inorganics11040168 - 16 Apr 2023
Cited by 8 | Viewed by 3488
Abstract
Organic-inorganic hybrid perovskites are highly efficient in photovoltaic applications, making the commercialization of perovskite solar cells (PSCs) possible. However, the high density of defects on the surface significantly affects the performance of PSCs. To address this issue, we have demonstrated a facile post-treatment [...] Read more.
Organic-inorganic hybrid perovskites are highly efficient in photovoltaic applications, making the commercialization of perovskite solar cells (PSCs) possible. However, the high density of defects on the surface significantly affects the performance of PSCs. To address this issue, we have demonstrated a facile post-treatment strategy utilizing methylhydrazine iodide (MHyI) to passivate the surface of the perovskite film. MHyI could co-ordinate with the dangling bonds on the surface of perovskite films, effectively passivating defects in the film and suppressing carrier non-radiative recombination. As a result, PSCs with MHyI modification exhibit a champion power conversion efficiency (PCE) of 23.19% and a high open-circuit voltage (VOC) of 1.14 V (0.43 V voltage deficit). Moreover, unencapsulated solar cells maintain their initial efficiency of 88% after 30 days of exposure to ambient air with 30% humidity, and the devices with encapsulation retained 57% of their initial efficiency after 200 h of maximum power point (MPP) loading under constant light irradiation in ambient air. Overall, our results provide a facile method for improving the performance and stability of PSCs. Full article
(This article belongs to the Section Inorganic Materials)
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12 pages, 1089 KiB  
Article
Dibromo–Isonitrile and N-acyclic Carbene Complexes of Platinum(II): Synthesis and Reactivity
by Anna Farasat, Francesca Nerli, Luca Labella, Marco Taddei and Simona Samaritani
Inorganics 2023, 11(4), 137; https://doi.org/10.3390/inorganics11040137 - 23 Mar 2023
Cited by 1 | Viewed by 1986
Abstract
A series of dibromo-N-acyclic (NAC) carbene complexes of platinum(II) were synthesized, starting from trans-[Pt(μ-Br)Br(PPh3)]2 and according to a protocol previously optimized for the preparation of analogous chlorinated compounds. In the first step of the synthesis, the ring opening of [...] Read more.
A series of dibromo-N-acyclic (NAC) carbene complexes of platinum(II) were synthesized, starting from trans-[Pt(μ-Br)Br(PPh3)]2 and according to a protocol previously optimized for the preparation of analogous chlorinated compounds. In the first step of the synthesis, the ring opening of the dinuclear precursor was carried out using suitable isonitrile ligands, while the following step consisted of the addition of N,N-diethylamine to the products obtained in the first step. The two reactions were separately investigated, and attention was given to the differences between brominated and chlorinated systems. Full article
(This article belongs to the Special Issue Phosphorus Ligands for the Stabilization of Unusual and Elusive Structures in Transition Metal Complexes)
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23 pages, 4800 KiB  
Article
Comparative Spectroscopic and Electrochemical Study of V(V)-Substituted Keggin-Type Phosphomolybdates and -Tungstates
by Jan-Christian Raabe, José Aceituno Cruz, Jakob Albert and Maximilian J. Poller
Inorganics 2023, 11(4), 138; https://doi.org/10.3390/inorganics11040138 - 23 Mar 2023
Cited by 19 | Viewed by 3243
Abstract
Vanadium-substituted Keggin-type heteropolyanions have been studied for a wide variety of applications, ranging from catalysis to antiviral/antimicrobial agents. While the V-substituted phosphomolybdates [PVxMo12−xO40](3+x)− have been well investigated in this context, comparatively little is known about [...] Read more.
Vanadium-substituted Keggin-type heteropolyanions have been studied for a wide variety of applications, ranging from catalysis to antiviral/antimicrobial agents. While the V-substituted phosphomolybdates [PVxMo12−xO40](3+x)− have been well investigated in this context, comparatively little is known about the corresponding phosphotungstates [PVxW12-xO40](3+x)−. We have succeeded in synthesizing the sodium salts of the whole series [PVxW12−xO40](3+x)−, for x = 1 to 6, and characterised them spectroscopically (FT-IR, UV-Vis, 31P-, and 51V-NMR) and electrochemically (CV and SWV). Thereby, direct comparisons between the vanadium-substituted phosphomolybdates and -tungstates, with substitution degrees from 1 to 6, can be established, which provides a solid basis for further investigations of potential applications. Full article
(This article belongs to the Section Coordination Chemistry)
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30 pages, 10177 KiB  
Article
The Electronic Nature of Cationic Group 10 Ylidyne Complexes
by Leonard R. Maurer, Jens Rump and Alexander C. Filippou
Inorganics 2023, 11(3), 129; https://doi.org/10.3390/inorganics11030129 - 18 Mar 2023
Cited by 11 | Viewed by 3013
Abstract
We report a broad theoretical study on [(PMe3)3MER]+ complexes, with M = Ni, Pd, Pt, E = C, Si, Ge, Sn, Pb, and R = ArMes, Tbb, (ArMes = 2,6-dimesitylphenyl; Tbb = C6H [...] Read more.
We report a broad theoretical study on [(PMe3)3MER]+ complexes, with M = Ni, Pd, Pt, E = C, Si, Ge, Sn, Pb, and R = ArMes, Tbb, (ArMes = 2,6-dimesitylphenyl; Tbb = C6H2-2,6-[CH(SiMe3)2]2-4-tBu). A few years ago, our group succeeded in obtaining heavier homologues of cationic group 10 carbyne complexes via halide abstraction of the tetrylidene complexes [(PMe3)3M=E(X)R] (X = Cl, Br) using a halide scavenger. The electronic structure and the M-E bonds of the [(PMe3)3MER]+ complexes were analyzed utilizing quantum-chemical tools, such as the Pipek–Mezey orbital localization method, the energy decomposition analysis (EDA), and the extended-transition state method with natural orbitals of chemical valence (ETS-NOCV). The carbyne, silylidyne complexes, and the germylidyne complex [(PMe3)3NiGeArMes]+ are suggested to be tetrylidyne complexes featuring donor–acceptor metal tetrel triple bonds, which are composed of two strong π(M→E) and one weaker σ(E→M) interaction. In comparison, the complexes with M = Pd, Pt; E = Sn, Pb; and R = ArMes are best described as metallotetrylenes and exhibit considerable M−E−C bending, a strong σ(M→E) bond, weakened M−E π-components, and lone pair density at the tetrel atoms. Furthermore, bond cleavage energy (BCE) and bond dissociation energy (BDE) reveal preferred splitting into [M(PMe3)3]+ and [ER] fragments for most complex cations in the range of 293.3–618.3 kJ·mol−1 and 230.4–461.6 kJ·mol−1, respectively. Finally, an extensive study of the potential energy hypersurface varying the M−E−C angle indicates the presence of isomers with M−E−C bond angles of around 95°. Interestingly, these isomers are energetically favored for M = Pd, Pt; E = Sn, Pb; and R = ArMes over the less-bent structures by 13–29 kJ·mol−1. Full article
(This article belongs to the Special Issue Density Functional Theory (DFT) and Semi-empirical Quantum Mechanical (SQM) Methods in Organometallic Chemistry)
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29 pages, 8462 KiB  
Article
Structural and Biological Properties of Heteroligand Copper Complexes with Diethylnicotinamide and Various Fenamates: Preparation, Structure, Spectral Properties and Hirshfeld Surface Analysis
by Milan Piroš, Martin Schoeller, Katarína Koňariková, Jindra Valentová, Ľubomír Švorc, Ján Moncoľ, Marian Valko and Jozef Švorec
Inorganics 2023, 11(3), 108; https://doi.org/10.3390/inorganics11030108 - 6 Mar 2023
Cited by 12 | Viewed by 3360
Abstract
Herein, we discuss the synthesis, structural and spectroscopic characterization, and biological activity of five heteroligand copper(II) complexes with diethylnicotinamide and various fenamates, as follows: flufenamate (fluf), niflumate (nifl), tolfenamate (tolf), clonixinate (clon), mefenamate (mef) and N, N-diethylnicotinamide (dena). The complexes of [...] Read more.
Herein, we discuss the synthesis, structural and spectroscopic characterization, and biological activity of five heteroligand copper(II) complexes with diethylnicotinamide and various fenamates, as follows: flufenamate (fluf), niflumate (nifl), tolfenamate (tolf), clonixinate (clon), mefenamate (mef) and N, N-diethylnicotinamide (dena). The complexes of composition: [Cu(fluf)2(dena)2(H2O)2] (1), [Cu(nifl)2(dena)2] (2), [Cu(tolf)2(dena)2(H2O)2] (3), [Cu(clon)2(dena)2] (4) and [Cu(mef)2(dena)2(H2O)2] (5), were synthesized, structurally (single-crystal X-ray diffraction) and spectroscopically characterized (IR, EA, UV-Vis and EPR). The studied complexes are monomeric, forming a distorted tetragonal bipyramidal stereochemistry around the central copper ion. The crystal structures of all five complexes were determined and refined with an aspheric model using the Hirshfeld atom refinement method. Hirshfeld surface analysis and fingerprint plots were used to investigate the intermolecular interactions in the crystalline state. The redox properties of the complexes were studied and evaluated via cyclic voltammetry. The complexes exhibited good superoxide scavenging activity as determined by an NBT assay along with a copper-based redox-cycling mechanism, resulting in the formation of ROS, which, in turn, predisposed the studied complexes for their anticancer activity. The ability of complexes 1–4 to interact with calf thymus DNA was investigated using absorption titrations, viscosity measurements and an ethidium-bromide-displacement-fluorescence-based method, suggesting mainly the intercalative binding of the complexes to DNA. The affinity of complexes 1–4 for bovine serum albumin was determined via fluorescence emission spectroscopy and was quantitatively characterized with the corresponding binding constants. The cytotoxic properties of complexes 1–4 were studied using the cancer cell lines A549, MCF-7 and U-118MG, as well as healthy MRC-5 cells. Complex 4 exhibited moderate anticancer activity on the MCF-7 cancer cells with IC50 = 57 μM. Full article
(This article belongs to the Special Issue Recent Progress in Coordination Chemistry)
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13 pages, 12547 KiB  
Article
Operando CO Infrared Spectroscopy and On-Line Mass Spectrometry for Studying the Active Phase of IrO2 in the Catalytic CO Oxidation Reaction
by Phillip Timmer, Tim Weber, Lorena Glatthaar and Herbert Over
Inorganics 2023, 11(3), 102; https://doi.org/10.3390/inorganics11030102 - 28 Feb 2023
Cited by 4 | Viewed by 2556
Abstract
We combine operando diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) with on-line mass spectrometry (MS) to study the correlation between the oxidation state of titania-supported IrO2 catalysts (IrO2@TiO2) and their catalytic activity in the prototypical CO oxidation reaction. [...] Read more.
We combine operando diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) with on-line mass spectrometry (MS) to study the correlation between the oxidation state of titania-supported IrO2 catalysts (IrO2@TiO2) and their catalytic activity in the prototypical CO oxidation reaction. Here, the stretching vibration of adsorbed COad serves as the probe. DRIFTS provides information on both surface and gas phase species. Partially reduced IrO2 is shown to be significantly more active than its fully oxidized counterpart, with onset and full conversion temperatures being about 50 °C lower for reduced IrO2. By operando DRIFTS, this increase in activity is traced to a partially reduced state of the catalysts, as evidenced by a broad IR band of adsorbed CO reaching from 2080 to 1800 cm−1. Full article
(This article belongs to the Special Issue Recent Advancements of Metal Oxide in Catalysis)
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27 pages, 5842 KiB  
Review
Green Energy by Hydrogen Production from Water Splitting, Water Oxidation Catalysis and Acceptorless Dehydrogenative Coupling
by Jesús Antonio Luque-Urrutia, Thalía Ortiz-García, Miquel Solà and Albert Poater
Inorganics 2023, 11(2), 88; https://doi.org/10.3390/inorganics11020088 - 20 Feb 2023
Cited by 20 | Viewed by 5225
Abstract
In this review, we want to explain how the burning of fossil fuels is pushing us towards green energy. Actually, for a long time, we have believed that everything is profitable, that resources are unlimited and there are no consequences. However, the reality [...] Read more.
In this review, we want to explain how the burning of fossil fuels is pushing us towards green energy. Actually, for a long time, we have believed that everything is profitable, that resources are unlimited and there are no consequences. However, the reality is often disappointing. The use of non-renewable resources, the excessive waste production and the abandonment of the task of recycling has created a fragile thread that, once broken, may never restore itself. Metaphors aside, we are talking about our planet, the Earth, and its unique ability to host life, including ourselves. Our world has its balance; when the wind erodes a mountain, a beach appears, or when a fire devastates an area, eventually new life emerges from the ashes. However, humans have been distorting this balance for decades. Our evolving way of living has increased the number of resources that each person consumes, whether food, shelter, or energy; we have overworked everything to exhaustion. Scientists worldwide have already said actively and passively that we are facing one of the biggest problems ever: climate change. This is unsustainable and we must try to revert it, or, if we are too late, slow it down as much as possible. To make this happen, there are many possible methods. In this review, we investigate catalysts for using water as an energy source, or, instead of water, alcohols. On the other hand, the recycling of gases such as CO2 and N2O is also addressed, but we also observe non-catalytic means of generating energy through solar cell production. Full article
(This article belongs to the Special Issue Inorganics for Catalysts: Design, Synthesis and Applications)
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21 pages, 1840 KiB  
Review
Effects of Boron-Containing Compounds on Liposoluble Hormone Functions
by Elizabeth Estevez-Fregoso, Ahmet Kilic, Diana Rodríguez-Vera, Luis E. Nicanor-Juárez, C. Elena M. Romero-Rizo, Eunice D. Farfán-García and Marvin A. Soriano-Ursúa
Inorganics 2023, 11(2), 84; https://doi.org/10.3390/inorganics11020084 - 17 Feb 2023
Cited by 18 | Viewed by 15778
Abstract
Boron-containing compounds (BCC), particularly boronic acids and derivatives, are being increasingly tested as diagnostic and therapeutic agents. Some effects of BCC involve phenomena linked to the action of steroid or thyroid hormones; among these, are the effects on muscle mass or basal metabolism. [...] Read more.
Boron-containing compounds (BCC), particularly boronic acids and derivatives, are being increasingly tested as diagnostic and therapeutic agents. Some effects of BCC involve phenomena linked to the action of steroid or thyroid hormones; among these, are the effects on muscle mass or basal metabolism. Additionally, some toxicology reports on mammals, including humans, sound an alert concerning damage to several systems, among which are the negative effects on the induction of male infertility. Systemic and local mechanisms to explain changes in metabolism and impaired fertility were collected and presented. Then, we presented the putative pharmacodynamic and pharmacokinetic mechanisms involved and demonstrated in these events. In addition, it is proposed that there are adducts of some oxygenated BCC with cis-diols in fructose, an essential source of energy for sperm–cell motility, an uncoupling of sex hormone-binding globulin (SHBG) and its ligands, and the modulation of the DNA synthetic rate. These effects share the reactivity of boron-containing compounds on the cis-diols of key molecules. Moreover, data reporting no DNA damage after BCC administration are included. Further studies are required to support the clear role of BCC through these events to disrupt metabolism or fertility in mammals. If such phenomena are confirmed and elucidated, an advance could be useful to design strategies for avoiding BCC toxicity after BCC administration, and possibly for designing metabolism regulators and contraceptive drugs, among other purposes. Boronic derivatives and carboranes have been proposed and studied in this field. Full article
(This article belongs to the Special Issue Synthesis and Innovative Biological Activity of Boron-Containing Compounds)
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18 pages, 3646 KiB  
Article
Main Issues in the Synthesis and Testing of Thermocatalytic Ce-Doped SrFeO3 Perovskites for Wastewater Pollutant Removal
by Davide Palma, Francesca Deganello, Leonarda Francesca Liotta, Valeria La Parola, Alessandra Bianco Prevot, Mery Malandrino, Enzo Laurenti, Vittorio Boffa and Giuliana Magnacca
Inorganics 2023, 11(2), 85; https://doi.org/10.3390/inorganics11020085 - 17 Feb 2023
Cited by 7 | Viewed by 2723
Abstract
The effect of the synthesis and processing parameters on the thermocatalytic performance of Ce-doped SrFeO3 inorganic perovskites was investigated to improve the reproducibility and reliability of the synthetic methodology and of the testing procedure. A structural, surface and redox characterization was performed [...] Read more.
The effect of the synthesis and processing parameters on the thermocatalytic performance of Ce-doped SrFeO3 inorganic perovskites was investigated to improve the reproducibility and reliability of the synthetic methodology and of the testing procedure. A structural, surface and redox characterization was performed to check the extent of variability in the chemical–physical properties of the prepared materials, revealing that a strict control of the synthesis parameters is indeed crucial to optimize the thermocatalytic properties of Ce-doped SrFeO3 inorganic perovskites. The thermocatalytic tests, aimed to degrade organic pollutants in water, were performed using Orange II and Bisphenol A as target compounds, in view of a later technological application. The main issues in the synthesis and testing of Ce-doped SrFeO3 perovskite thermocatalysts are highlighted and described, giving specific instructions for the resolution of each of them. A limited number of prepared materials showed an efficient thermocatalytic effect, indicating that a full gelification of the sol, an overstoichiometric reducer-to-oxidizer ratio, a nominal cerium content of 15 mol%, slightly higher than its solubility limit (i.e., 14 mol%), a pH of 6 and a thermal treatment at 800 °C/2 h are the best synthesis conditions to obtain an effective Ce-doped SrFeO3 perovskite. Regarding the testing conditions, the best procedure is to follow the degradation reaction without any preconditioning with the pollutant at room temperature. The severe leaching of the active perovskite phase during tests conducted at acidic pH is discussed. Briefly, we suggest confining the application of these materials to a limited pH range. Variability between thermocatalysts prepared in two different laboratories was also checked. The issues discussed and the proposed solutions overcome some of the obstacles to achieving a successful scale up of the synthesis process. Our results were favorable in comparison to those in the literature, and our approach can be successfully extended to other perovskite catalysts. Full article
(This article belongs to the Special Issue New Advances into Nanostructured Oxides)
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22 pages, 6586 KiB  
Review
Carbon-Based Materials and Their Applications in Sensing by Electrochemical Voltammetry
by Trong Danh Nguyen, My Thi Ngoc Nguyen and Jun Seop Lee
Inorganics 2023, 11(2), 81; https://doi.org/10.3390/inorganics11020081 - 15 Feb 2023
Cited by 31 | Viewed by 6652
Abstract
In recent years, society has paid great attention to health care and environmental safety. Thus, research on advanced sensors for detecting substances that can harm health and the environment has been developed rapidly. Another popular target for detection techniques is disease-expressing materials that [...] Read more.
In recent years, society has paid great attention to health care and environmental safety. Thus, research on advanced sensors for detecting substances that can harm health and the environment has been developed rapidly. Another popular target for detection techniques is disease-expressing materials that can be collected from body fluids. Carbon, which has outstanding electrochemical properties, can come from a variety of sources and has many morphological shapes, is nevertheless an environmentally friendly material. While carbon nanomaterial has become one of the most common targets for high-tech development, electrochemical voltammetry has proven to be an effective measurement method. Herein, the paper proposes a currently developed carbon nanomaterial along with research on a modified carbon material. Moreover, four common voltammetry methods and related works are also introduced. Full article
(This article belongs to the Section Inorganic Materials)
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11 pages, 1564 KiB  
Article
Synthesis of Novel Multifunctional bora-Ibuprofen Derivatives
by Randika T. Abeysinghe, Alexis C. Ravenscroft, Steven W. Knowlden, Novruz G. Akhmedov, Brian S. Dolinar and Brian V. Popp
Inorganics 2023, 11(2), 70; https://doi.org/10.3390/inorganics11020070 - 2 Feb 2023
Cited by 4 | Viewed by 4061
Abstract
A unique class of β-boron-functionalized non-steroidal anti-inflammatory compound (pinB-NSAID) was previously synthesized via copper-catalyzed 1,2-difunctionalization of the respective vinyl arene with CO2 and B2pin2 reagents. Here, pinacolylboron-functionalized ibuprofen (pinB-ibuprofen) was used as a model substrate to develop the conditions [...] Read more.
A unique class of β-boron-functionalized non-steroidal anti-inflammatory compound (pinB-NSAID) was previously synthesized via copper-catalyzed 1,2-difunctionalization of the respective vinyl arene with CO2 and B2pin2 reagents. Here, pinacolylboron-functionalized ibuprofen (pinB-ibuprofen) was used as a model substrate to develop the conditions for pinacol deprotection and subsequent boron functionalization. Initial pinacol-boronic ester deprotection was achieved by transesterification with diethanolamine (DEA) from the boralactonate organic salt. The resulting DEA boronate adopts a spirocyclic boralactonate structure rather than a diazaborocane–DABO boronate structure. The subsequent acid-mediated hydrolysis of DEA and transesterification/transamination provided a diverse scope of new boron-containing ibuprofen derivatives. Full article
(This article belongs to the Special Issue Synthesis and Innovative Biological Activity of Boron-Containing Compounds)
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19 pages, 6775 KiB  
Article
Coordination Chemistry of Polynitriles, Part XII—Serendipitous Synthesis of the Octacyanofulvalenediide Dianion and Study of Its Coordination Chemistry with K+ and Ag+
by Patrick Nimax, Yannick Kunzelmann and Karlheinz Sünkel
Inorganics 2023, 11(2), 71; https://doi.org/10.3390/inorganics11020071 - 2 Feb 2023
Cited by 1 | Viewed by 1850
Abstract
The reaction of diazotetracyanocyclopentadiene with copper powder in the presence of NEt4Cl yields, unexpectedly, besides the known NEt4[C5H(CN)4] (3), the NEt4 salt of octacyanofulvalenediide (NEt4)2[C10(CN)8] ( [...] Read more.
The reaction of diazotetracyanocyclopentadiene with copper powder in the presence of NEt4Cl yields, unexpectedly, besides the known NEt4[C5H(CN)4] (3), the NEt4 salt of octacyanofulvalenediide (NEt4)2[C10(CN)8] (5), which can be transformed via reaction with AgNO3 to the corresponding Ag+ salt (4), which in turn can be reacted with KCl to yield the corresponding K+ salt 6. The molecular and crystal structures of 4–6 could be determined, and show a significantly twisted aromatic dianion which uses all its nitrile groups for coordination to the metals; 4 and 6 form three-dimensional coordination polymers with fourfold coordinated Ag+ and eightfold coordinated K+ cations. Full article
(This article belongs to the Special Issue Recent Progress in Coordination Chemistry)
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18 pages, 3303 KiB  
Article
Interactions of an Artificial Zinc Finger Protein with Cd(II) and Hg(II): Competition and Metal and DNA Binding
by Bálint Hajdu, Éva Hunyadi-Gulyás and Béla Gyurcsik
Inorganics 2023, 11(2), 64; https://doi.org/10.3390/inorganics11020064 - 29 Jan 2023
Cited by 2 | Viewed by 3542
Abstract
Cys2His2 zinc finger proteins are important for living organisms, as they—among other functions—specifically recognise DNA when Zn(II) is coordinated to the proteins, stabilising their ββα secondary structure. Therefore, competition with other metal ions may alter their original function. Toxic metal ions such as [...] Read more.
Cys2His2 zinc finger proteins are important for living organisms, as they—among other functions—specifically recognise DNA when Zn(II) is coordinated to the proteins, stabilising their ββα secondary structure. Therefore, competition with other metal ions may alter their original function. Toxic metal ions such as Cd(II) or Hg(II) might be especially dangerous because of their similar chemical properties to Zn(II). Most competition studies carried out so far have involved small zinc finger peptides. Therefore, we have investigated the interactions of toxic metal ions with a zinc finger proteins consisting of three finger units and the consequences on the DNA binding properties of the protein. Binding of one Cd(II) per finger subunit of the protein was shown by circular dichroism spectroscopy, fluorimetry and electrospray ionisation mass spectrometry. Cd(II) stabilised a similar secondary structure to that of the Zn(II)-bound protein but with a slightly lower affinity. In contrast, Hg(II) could displace Zn(II) quantitatively (logβ′ ≥ 16.7), demolishing the secondary structure, and further Hg(II) binding was also observed. Based on electrophoretic gel mobility shift assays, the Cd(II)-bound zinc finger protein could recognise the specific DNA target sequence similarly to the Zn(II)-loaded form but with a ~0.6 log units lower stability constant, while Hg(II) could destroy DNA binding completely. Full article
(This article belongs to the Special Issue Recent Progress in Coordination Chemistry)
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30 pages, 3363 KiB  
Review
The Role of Complexes of Biogenic Metals in Living Organisms
by Irena Kostova
Inorganics 2023, 11(2), 56; https://doi.org/10.3390/inorganics11020056 - 25 Jan 2023
Cited by 40 | Viewed by 7021
Abstract
Biogenic metals and their various inorganic, organometallic, and coordination compounds are comprehensively studied and extensively used in medical practice. Since the biogenic metals have various chemical properties corresponding to their position in the periodic table, their biological functions are different. Almost all of [...] Read more.
Biogenic metals and their various inorganic, organometallic, and coordination compounds are comprehensively studied and extensively used in medical practice. Since the biogenic metals have various chemical properties corresponding to their position in the periodic table, their biological functions are different. Almost all of the discussed biogenic elements have an ability to form coordination complexes. Furthermore, the different accessible oxidation states occupied by most of these elements enables the body to catalyze oxy-reduction interactions, depending on the biological conditions. As they are biogenic in nature, their deficiency or their excess in the body leads to numerous pathological obstructions. The application of metal-based compounds as medications is connected with the oxy-reduction properties and the capability to form coordination complexes, which are involved in many bioreactions. The usefulness of these metals as therapeutic and diagnostic agents is also pointed out. Full article
(This article belongs to the Special Issue Bioactivity of Transition Metal-Based Complexes)
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21 pages, 5621 KiB  
Review
The Applications of Metallacycles and Metallacages
by Changfeng Yin, Jiaxing Du, Bogdan Olenyuk, Peter J. Stang and Yan Sun
Inorganics 2023, 11(2), 54; https://doi.org/10.3390/inorganics11020054 - 22 Jan 2023
Cited by 14 | Viewed by 3878
Abstract
Metallacycles and metallacages constitute a class of coordination compounds composed of metal ions and organic ligands. Because of their precise stoichiometry, the flexibility and viability of design, metallacycles and metallacages have attracted considerable attention as supramolecular assemblies. Various two-dimensional polygons, three-dimensional polyhedra, and [...] Read more.
Metallacycles and metallacages constitute a class of coordination compounds composed of metal ions and organic ligands. Because of their precise stoichiometry, the flexibility and viability of design, metallacycles and metallacages have attracted considerable attention as supramolecular assemblies. Various two-dimensional polygons, three-dimensional polyhedra, and other nanoscale materials have been constructed and applied. The highly diverse structures, sizes, and shapes endow metallacycles and metallacages with unique physical and chemical properties and make them suitable for various applications such as encapsulation, separation, catalysis, and biological science. Herein, we review the recent developments in various metallacycles and metallacages in different fields. The text highlights biomedical applications involving molecular recognition and binding, antibacterial activity, and especially cancer diagnosis and treatment, including imaging, chemotherapy, PDT, and PTT. Full article
(This article belongs to the Special Issue Metallamacrocycles and Metallacages: Foundations and Applications)
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12 pages, 3788 KiB  
Article
The Influence of Different Recombination Pathways on Hysteresis in Perovskite Solar Cells with Ion Migration
by Biao Li, Kun Chen, Pengjie Hang, Yuxin Yao, Chenxia Kan, Zechen Hu, Ying Wang, Yiqiang Zhang, Deren Yang and Xuegong Yu
Inorganics 2023, 11(2), 52; https://doi.org/10.3390/inorganics11020052 - 19 Jan 2023
Viewed by 3624
Abstract
The impact of hysteresis on the power conversion efficiency (PCE) of perovskite solar cells (PSCs) still faces uncertainties despite the rapid development of perovskite photovoltaics. Although ion migration in perovskites is regarded as the chief culprit for hysteresis, charge carrier recombination pathways in [...] Read more.
The impact of hysteresis on the power conversion efficiency (PCE) of perovskite solar cells (PSCs) still faces uncertainties despite the rapid development of perovskite photovoltaics. Although ion migration in perovskites is regarded as the chief culprit for hysteresis, charge carrier recombination pathways in PSCs are proposed to be necessary for the occurrence of hysteresis. Here, the impact of both bulk recombination and interface recombination on hysteresis in PSCs is investigated via drift–diffusion modeling. The simulation results demonstrate a direct correlation between recombination pathways and hysteresis in PSCs with ion migration. The simulation reveals that recombination pathways in PSCs will react to the variation in charge carrier distribution under different voltage scanning directions induced by ion migration in absorber layers, which leads to hysteresis in PSCs. Moreover, the hysteresis in normal (N-I-P) PSCs with different electron transport layers (ETLs) including sintered SnO2, SnO2 nano crystals and TiO2 is experimentally explored. The results demonstrate that multiple recombination pathways coupled with ion migration can lead to obvious hysteresis in fabricated PSCs which is consistent with simulation results. This work provides great insight into hysteresis management upon composition, additive and interface engineering in PSCs. Full article
(This article belongs to the Special Issue Inorganics: 10th Anniversary)
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18 pages, 4081 KiB  
Article
Latonduine-1-Amino-Hydantoin Hybrid, Triazole-Fused Latonduine Schiff Bases and Their Metal Complexes: Synthesis, X-ray and Electron Diffraction, Molecular Docking Studies and Antiproliferative Activity
by Christopher Wittmann, Tim Gruene, Alexander Prado-Roller, Sandra Aranđelović, Jóhannes Reynisson and Vladimir B. Arion
Inorganics 2023, 11(1), 30; https://doi.org/10.3390/inorganics11010030 - 3 Jan 2023
Cited by 4 | Viewed by 2868
Abstract
A series of latonduine derivatives, namely 11-nitro-indolo[2,3-d]benzazepine-7-(1-amino-hydantoin) (B), triazole-fused indolo[2,3-d]benzazepine-based Schiff bases HL1 and HL2 and metal complexes [M(p-cymene)(HL1)Cl]Cl, where M = Ru (1), Os (2), and [...] Read more.
A series of latonduine derivatives, namely 11-nitro-indolo[2,3-d]benzazepine-7-(1-amino-hydantoin) (B), triazole-fused indolo[2,3-d]benzazepine-based Schiff bases HL1 and HL2 and metal complexes [M(p-cymene)(HL1)Cl]Cl, where M = Ru (1), Os (2), and [Cu(HL2)Cl2] (3) were synthesized and characterized by spectroscopic techniques (UV–vis, 1H, 13C, 15N–1H HSQC NMR) and ESI mass spectrometry. The molecular structures of B and HL1 were confirmed by single-crystal X-ray diffraction, while that of 3 by electron diffraction of nanometer size crystalline sample. Molecular docking calculations of species B in the binding pocket of PIM-1 enzyme revealed that the 1-amino-hydantoin moiety is not involved in any hydrogen-bonding interactions, even though a good accommodation of the host molecule in the ATP binding pocket of the enzyme was found. The antiproliferative activity of organic compounds B, HL1 and HL2, as well as complexes 1–3 was investigated in lung adenocarcinoma A549, colon adenocarcinoma LS-174 and triple-negative breast adenocarcinoma MDA-MB-231 cells and normal human lung fibroblast cells MRC-5 by MTT assays; then, the results are discussed. Full article
(This article belongs to the Special Issue Inorganics: 10th Anniversary)
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20 pages, 5136 KiB  
Article
Cryogels with Noble Metal Nanoparticles as Catalyst for “Green” Decomposition of Chlorophenols
by Dmitriy A. Berillo and Irina N. Savina
Inorganics 2023, 11(1), 23; https://doi.org/10.3390/inorganics11010023 - 2 Jan 2023
Cited by 6 | Viewed by 2494
Abstract
Pollution of the aquatic environment by halogen derivatives widely used as antiseptic compounds, as well as chemicals for various industrial purposes, is significant. Existing systems of bioremediation poorly solve the problem of eliminating pollution. This paper discusses the preparation of novel macroporous chitosan-based [...] Read more.
Pollution of the aquatic environment by halogen derivatives widely used as antiseptic compounds, as well as chemicals for various industrial purposes, is significant. Existing systems of bioremediation poorly solve the problem of eliminating pollution. This paper discusses the preparation of novel macroporous chitosan-based cryogels with in situ-immobilized Pd or Pt nanoparticles as a catalyst for dichlorination reactions. The formation mechanism of metal coordinated chitosan gels using Medusa software modelling and rheology (G’ and G’’) is discussed. Metal coordinated chitosan gels were subsequently converted into covalently cross-linked macroporous cryogels with in situ-immobilized Pd or Pt nanoparticles using the redox potentials difference of the reaction mixture. Noble metal nanoparticles of average size, 2.4 nm, were evenly distributed in the cryogel structure. The effectiveness of these gels as a catalyst for the decomposition of chloro-compounds o-chlorophenol, p-chlorophenol and 2,4-dichlorophenol was tested. The catalytic hydrogenation reaction was carried out using the “green reducing agent” formic acid. Increasing the excess of formic acid with heating increases the degree of conversion up to 80–90%. The CHI-GA-PdNPs cryogel at pH 6 showed better efficiency in the hydrogenation process compared to the CHI-GA-PtNPs cryogel; however, no significant difference in the degree of conversion at pH 3 was observed. The termination of a catalytic reaction in a batch mode have been studied. Several control tests were carried out to elucidate the mechanism of catalyst poisoning. The presented catalytic system may be of interest for studying reactions in a flow through mode, including the reactions for obtaining valuable chemicals. Full article
(This article belongs to the Special Issue Inorganics for Catalysts: Design, Synthesis and Applications)
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32 pages, 5390 KiB  
Review
Inorganic Finishing for Textile Fabrics: Recent Advances in Wear-Resistant, UV Protection and Antimicrobial Treatments
by Silvia Sfameni, Mariam Hadhri, Giulia Rando, Dario Drommi, Giuseppe Rosace, Valentina Trovato and Maria Rosaria Plutino
Inorganics 2023, 11(1), 19; https://doi.org/10.3390/inorganics11010019 - 1 Jan 2023
Cited by 38 | Viewed by 7815
Abstract
The surface modification of textile fabrics and therefore, the development of advanced textile materials featuring specific implemented and new properties, such as improved durability and resistance, is increasingly in demand from modern society and end-users. In this regard, the sol–gel technique has shown [...] Read more.
The surface modification of textile fabrics and therefore, the development of advanced textile materials featuring specific implemented and new properties, such as improved durability and resistance, is increasingly in demand from modern society and end-users. In this regard, the sol–gel technique has shown to be an innovative and convenient synthetic route for developing functional sol–gel coatings useful for the protection of textile materials. Compared with the conventional textile finishing process, this technique is characterized by several advantages, such as the environmentally friendly approaches based on one-step applications and low concentration of non-hazardous chemicals. The sol–gel method, starting from inorganic metal alkoxides or metal salts, leads to inorganic sols containing particles that enable a chemical or physical modification of fiber surfaces, giving rise to final multifunctional properties of treated textile fabrics. This review considered the recent developments in the synthesis of inorganic nanoparticles and nanosols by sol–gel approach for improving wear and UV resistance, as well as antibacterial or antimicrobial effects for textile applications. Full article
(This article belongs to the Special Issue New Advances into Nanostructured Oxides)
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16 pages, 4686 KiB  
Article
The Crystal Structure of Carbonic Acid
by Sebastian Benz, Da Chen, Andreas Möller, Michael Hofmann, David Schnieders and Richard Dronskowski
Inorganics 2022, 10(9), 132; https://doi.org/10.3390/inorganics10090132 - 3 Sep 2022
Cited by 8 | Viewed by 10839
Abstract
Ubiquitous carbonic acid, H2CO3, a key molecule in biochemistry, geochemistry, and also extraterrestrial chemistry, is known from a plethora of physicochemical studies. Its crystal structure has now been determined from neutron-diffraction data on a deuterated sample in a specially [...] Read more.
Ubiquitous carbonic acid, H2CO3, a key molecule in biochemistry, geochemistry, and also extraterrestrial chemistry, is known from a plethora of physicochemical studies. Its crystal structure has now been determined from neutron-diffraction data on a deuterated sample in a specially built hybrid clamped cell. At 1.85 GPa, D2CO3 crystallizes in the monoclinic space group P21/c with a = 5.392(2), b = 6.661(4), c = 5.690(1) Å, β = 92.66(3)°, Z = 4, with one symmetry-inequivalent anti-anti shaped D2CO3 molecule forming dimers, as previously predicted. Quantum chemistry evidences π bonding within the CO3 molecular core, very strong hydrogen bonding between the molecules, and a massive influence of the crystal field on all bonds; phonon calculations emphasize the locality of the vibrations, being rather insensitive to the extended structure. Full article
(This article belongs to the Special Issue Inorganics: 10th Anniversary)
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