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Inorganics, Volume 9, Issue 11 (November 2021) – 8 articles

Cover Story (view full-size image): Metal–organic frameworks (MOFs) are a family of porous crystalline materials increasing relevance as versatile platforms for catalysis. MOFs have reached great success as catalysts for CO2 chemical fixation through olefin epoxidation and carbon dioxide cycloaddition. Recent advances obtained with MOFs as heterogeneous catalysts make them promising materials to reduce excessive CO2 emissions. In this review, recent developments are discussed outlining the major challenges for this emerging field.View this paper
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Review
In Situ and In Operando Techniques to Study Li-Ion and Solid-State Batteries: Micro to Atomic Level
Inorganics 2021, 9(11), 85; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9110085 - 22 Nov 2021
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Abstract
This work summarizes the most commonly used in situ techniques for the study of Li-ion batteries from the micro to the atomic level. In situ analysis has attracted a great deal of interest owing to its ability to provide a wide range of [...] Read more.
This work summarizes the most commonly used in situ techniques for the study of Li-ion batteries from the micro to the atomic level. In situ analysis has attracted a great deal of interest owing to its ability to provide a wide range of information about the cycling behavior of batteries from the beginning until the end of cycling. The in situ techniques that are covered are: X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), and Scanning Transmission Electron Microscopy (STEM). An optimized setup is required to be able to use any of these in situ techniques in battery applications. Depending on the type of data required, the available setup, and the type of battery, more than one of these techniques might be needed. This study organizes these techniques from the micro to the atomic level, and shows the types of data that can be obtained using these techniques, their advantages and their challenges, and possible strategies for overcoming these challenges. Full article
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Article
Hybrid Metal-Organic Framework-Cellulose Materials Retaining High Porosity: [email protected] Nanofibrils
Inorganics 2021, 9(11), 84; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9110084 - 20 Nov 2021
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Abstract
Metal-organic frameworks have attracted a great deal of attention for future applications in numerous areas, including gas adsorption. However, in order for them to reach their full potential a substrate to provide an anchor may be needed. Ideally, this substrate should be environmentally [...] Read more.
Metal-organic frameworks have attracted a great deal of attention for future applications in numerous areas, including gas adsorption. However, in order for them to reach their full potential a substrate to provide an anchor may be needed. Ideally, this substrate should be environmentally friendly and renewable. Cellulose nanofibrils show potential in this area. Here we present a hybrid material created from the self-assembly of zeolitic imidazolate framework (ZIF-8) nanocrystals on cellulose nanofibrils (CNF) in aqueous medium. The CNF/ZIF-8 was freeze dried and formed free standing materials suitable for gas adsorption. A BET area of 1014 m2 g−1 was achieved for the CNF/ZIF-8 hybrid materials [email protected] which is comparable with reported values for free standing ZIF-8 materials, 1600 m2 g−1, considering the dilution with cellulose, and a considerable enhancement compared to CNF on its own, 32 m2 g−1. Full article
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Review
Cytochrome c: Using Biological Insight toward Engineering an Optimized Anticancer Biodrug
Inorganics 2021, 9(11), 83; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9110083 - 16 Nov 2021
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Abstract
The heme protein cytochrome c (Cyt c) plays pivotal roles in cellular life and death processes. In the respiratory chain of mitochondria, it serves as an electron transfer protein, contributing to the proliferation of healthy cells. In the cell cytoplasm, it activates intrinsic [...] Read more.
The heme protein cytochrome c (Cyt c) plays pivotal roles in cellular life and death processes. In the respiratory chain of mitochondria, it serves as an electron transfer protein, contributing to the proliferation of healthy cells. In the cell cytoplasm, it activates intrinsic apoptosis to terminate damaged cells. Insight into these mechanisms and the associated physicochemical properties and biomolecular interactions of Cyt c informs on the anticancer therapeutic potential of the protein, especially in its ability to subvert the current limitations of small molecule-based chemotherapy. In this review, we explore the development of Cyt c as an anticancer drug by identifying cancer types that would be receptive to the cytotoxicity of the protein and factors that can be finetuned to enhance its apoptotic potency. To this end, some information is obtained by characterizing known drugs that operate, in part, by triggering Cyt c induced apoptosis. The application of different smart drug delivery systems is surveyed to highlight important features for maintaining Cyt c stability and activity and improving its specificity for cancer cells and high drug payload release while recognizing the continuing limitations. This work serves to elucidate on the optimization of the strategies to translate Cyt c to the clinical market. Full article
(This article belongs to the Special Issue Metal-Based Anticancer Drugs)
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Article
The bis(Biphenyl)phosphorus Fragment in Trivalent and Tetravalent P-Environments
Inorganics 2021, 9(11), 82; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9110082 - 16 Nov 2021
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Abstract
Diaryl substituted phosphorus (III) compounds are commonly used motifs in synthesis. Although the basic synthetic routes to these molecules starting from PCl3 are well reported, sterically hindered aryl substituents can be difficult to introduce, especially if the P atom is in ortho [...] Read more.
Diaryl substituted phosphorus (III) compounds are commonly used motifs in synthesis. Although the basic synthetic routes to these molecules starting from PCl3 are well reported, sterically hindered aryl substituents can be difficult to introduce, especially if the P atom is in ortho position to another group. This work explores the chemistry of the bis(biphenyl)phosphorus(III) fragment. As third substituents, H, M, Cl, NR2, two group 14 element substituents and also Li were introduced in high-yielding processes offering a wide chemical variety of the bis(biphenyl) phosphine motif. In addition, also a tetravalent phosphine borane adduct was isolated. All structures were thoroughly investigated by heteronuclear NMR spectroscopic analysis. Furthermore, the reaction conditions are discussed in connection with the structures and four crystal structures of the aminophosphine, phosphine, phosphine borane and phosphide are provided. The latter crystallized as a dimer with a unique planar P2Li2 ring, which is stabilized by the non-covalent C⋯Li interaction arising from the biphenyl motif and represents a rare example of a donor-free planar P2Li2 ring. Full article
(This article belongs to the Section Organometallic Chemistry)
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Review
Metal Organic Frameworks as Heterogeneous Catalysts in Olefin Epoxidation and Carbon Dioxide Cycloaddition
Inorganics 2021, 9(11), 81; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9110081 - 15 Nov 2021
Viewed by 392
Abstract
Metal–organic frameworks (MOFs) are a family of porous crystalline materials that serve in some cases as versatile platforms for catalysis. In this review, we overview the recent developments about the use of these species as heterogeneous catalysts in olefin epoxidation and carbon dioxide [...] Read more.
Metal–organic frameworks (MOFs) are a family of porous crystalline materials that serve in some cases as versatile platforms for catalysis. In this review, we overview the recent developments about the use of these species as heterogeneous catalysts in olefin epoxidation and carbon dioxide cycloaddition. We report the most important results obtained in this field relating them to the presence of specific organic linkers, metal nodes or clusters and mixed-metal species. Recent advances obtained with MOF nanocomposites were also described. Finally we compare the results and summarize the major insights in specific Tables, outlining the major challenges for this emerging field. This work could promote new research aimed at producing coordination polymers and MOFs able to catalyse a broader range of CO2 consuming reactions. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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Article
Density Functional Theory Study on the Adsorption Mechanism of Sulphide Gas Molecules on α-Fe2O3(001) Surface
Inorganics 2021, 9(11), 80; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9110080 - 04 Nov 2021
Viewed by 255
Abstract
Sulphide gas is an impurity that affects the quality of natural gas, which needs reasonable storage and transportation. In this work, we investigated the adsorption structure and electronic behavior of hydrogen sulfide (H2S), carbonyl sulfur (COS), and methyl mercaptan (CH3 [...] Read more.
Sulphide gas is an impurity that affects the quality of natural gas, which needs reasonable storage and transportation. In this work, we investigated the adsorption structure and electronic behavior of hydrogen sulfide (H2S), carbonyl sulfur (COS), and methyl mercaptan (CH3SH) on sulphide gas molecules on pure and vacant α-Fe2O3(001) surfaces by density functional theory with geometrical relaxations. The results show that H2S and CH3SH are mainly adsorbed in the form of molecules on the pure Fe2O3(001) surface. On the vacant α-Fe2O3(001) surface, they can be adsorbed on Fe atoms in molecular form and by dissociation. The absolute value of the adsorption energy of H2S and CH3SH on the vacancy defect α-Fe2O3 surface is larger, and the density of states show that the electron orbital hybridization is more significant, and the adsorption is stronger. The charge differential density and Mulliken charge population analysis show that the charge is rearranged and chemical bonds are formed. The affinity of H2S to the vacancy α-Fe2O3(001) surface is slightly higher than that of CH3SH, while COS molecules basically do not adsorb on the α-Fe2O3(001) surface, which may be related to the stable chemical properties of the molecules themselves. Full article
(This article belongs to the Section Inorganic Solid-State Chemistry)
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Review
Pyridinesilver Tetraoxometallate Complexes: Overview of the Synthesis, Structure, and Properties of Pyridine Complexed AgXO4 (X = Cl, Mn, Re) Compounds
Inorganics 2021, 9(11), 79; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9110079 - 30 Oct 2021
Viewed by 241
Abstract
We reviewed the synthesis, structure, and properties of pyridine complexes of AgXO4 (X = Cl, Mn, and Re) compounds with various compositions ([AgPy2] XO4, [AgPy2XO4]·0.5Py, [AgPy4] XO4, and 4 [AgPy [...] Read more.
We reviewed the synthesis, structure, and properties of pyridine complexes of AgXO4 (X = Cl, Mn, and Re) compounds with various compositions ([AgPy2] XO4, [AgPy2XO4]·0.5Py, [AgPy4] XO4, and 4 [AgPy2XO4] [AgPy4] XO4). We also clarified the controversial information about the existence and composition of pyridine complexes of silver permanganate, used widely as mild and selective oxidants in organic chemistry. We discussed in detail the available structural and spectroscopic (IR, Raman, and UV) data and thermal behavior, including the existence and consequence of quasi-intramolecular reactions between the reducing ligand and anions containing oxygen. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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Article
The Effect of Vanadium Inhalation on the Tumor Progression of Urethane-Induced Lung Adenomas in a Mice Model
Inorganics 2021, 9(11), 78; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9110078 - 29 Oct 2021
Viewed by 241
Abstract
Lung cancer has the highest death rates. Aerosol drug delivery has been used for other lung diseases. The use of inhaled vanadium (V) as an option for lung cancer treatment is explored. Four groups of mice were studied: (1) Saline inhalation alone, (2) [...] Read more.
Lung cancer has the highest death rates. Aerosol drug delivery has been used for other lung diseases. The use of inhaled vanadium (V) as an option for lung cancer treatment is explored. Four groups of mice were studied: (1) Saline inhalation alone, (2) Single intraperitoneal (i.p.) dose of urethane, (3) V nebulization twice a week (Wk) for 8 Wk, and (4) A single dose of urethane and V nebulization for 8 Wk. Mice were sacrificed at the end of the experiment. Number and size of tumors, PCNA (proliferating cell nuclear antigen) and TUNEL (terminal deoxynucleotidyl tranferase dUTP nick-end labeling) immunohistochemistry were evaluated and compared within groups. Results: The size and number of tumors decreased in mice exposed to V-urethane and the TUNEL increased in this group; differences in the PCNA were not observed. Conclusions: Aerosol V delivery increased apoptosis and possibly the growth arrest of the tumors with no respiratory clinical changes in the mice. Full article
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