Inorganics

12 pages, 3809 KiB

Open AccessArticle

Encapsulating Ultrafine In₂O₃ Particles in Carbon Nanofiber Framework as Superior Electrode for Lithium-Ion Batteries

by Wenhe Xie, Zhe An, Xuefeng Li, Qian Wang, Chen Hu, Yuanxiao Ma, Shenghong Liu, Haibin Sun and Xiaolei Sun

Inorganics 2024, 12(12), 336; https://doi.org/10.3390/inorganics12120336 - 23 Dec 2024

Viewed by 574

Abstract

Indium oxide (In₂O₃) is a promising anode material for next-generation lithium-ion batteries and is prized for its high electrical conductivity, environmental friendliness, and high theoretical capacity. However, its practical application is significantly limited by severe volume expansion and contraction [...] Read more.

Indium oxide (In₂O₃) is a promising anode material for next-generation lithium-ion batteries and is prized for its high electrical conductivity, environmental friendliness, and high theoretical capacity. However, its practical application is significantly limited by severe volume expansion and contraction during the lithium insertion/extraction process. This volume change disrupts the solid electrolyte interphase (SEI) and degrades contact with the current collector, undermining battery performance. Although the nano-structured design of In₂O₃ can mitigate the volume effect to some extent, pure In₂O₃ nanomaterials are prone to agglomeration during frequent charging and discharging. The pure In₂O₃-based electrode shows a sustained and rapid capacity degradation. In this study, we embed ultrafine In₂O₃ particles in a carbon nanofiber framework using electrospinning and thermal annealing. The 1D carbon nanofiber structure provides an effective electronic conductive network and reduces the length of lithium-iondiffusion, which enhances the reactivity of the nanocomposite and improves electrode kinetics. Additionally, the carbon nanofiber framework isolates ultrafine In₂O₃ particles, preventing their aggregation. The small volume changes due to the ultrafine size of the In₂O₃ are buffered by the carbon materials, allowing the overall structure of the In₂O₃/C composite nanofiber to remain largely intact without crushing during charging and discharging cycles. This stability helps avoid electrode fracture and excessive SEI growth, resulting in superior cycle and rate performance compared with the pure In₂O₃ nanofiber electrodes. Full article

(This article belongs to the Special Issue Inorganic Electrode Materials in High-Performance Energy Storage Devices)

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4 pages, 183 KiB

Open AccessEditorial

Rational Design of Metal-Based Pharmacologically Active Compounds

by Irena Kostova

Inorganics 2024, 12(12), 335; https://doi.org/10.3390/inorganics12120335 - 22 Dec 2024

Viewed by 549

Abstract

Metal-based pharmacologically active compounds have been associated with many processes in vivo, acting as active sites of metalloproteins [...] Full article

(This article belongs to the Special Issue Rational Design of Pharmacologically Active Metal-Based Compounds)

14 pages, 2302 KiB

Open AccessArticle

Thermoelectric Characteristics of β-Ag₂Se_1+x Prepared via a Combined Rapid Mechano-Thermal Approach

by Katarína Gáborová, Michal Hegedüs, Petr Levinský, František Mihok, Miloš Matvija, Karel Knížek, Ondrej Milkovič, Dagmara Vatraľová, Jiří Hejtmánek and Karel Saksl

Inorganics 2024, 12(12), 334; https://doi.org/10.3390/inorganics12120334 - 21 Dec 2024

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Abstract

This study investigates the thermoelectric properties of Se-rich β-Ag₂Se synthesized via a mechanochemical method followed by spark plasma sintering (SPS) in less than 30 min of the total reaction time. Importantly, only a short 10 min milling process followed by appropriate [...] Read more.

This study investigates the thermoelectric properties of Se-rich β-Ag₂Se synthesized via a mechanochemical method followed by spark plasma sintering (SPS) in less than 30 min of the total reaction time. Importantly, only a short 10 min milling process followed by appropriate SPS was enough to produce single-phase Ag₂Se_1+x samples with varying selenium content (where x = 0, 0.01, 0.02, 0.04). The introduction of excess selenium significantly influenced the thermoelectric performance, optimizing the carrier concentration during synthesis and resulting in substantial thermoelectric improvements. The sample with nominal composition Ag₂Se_1.01 exhibited a high dimensionless figure-of-merit (ZT) >0.9 at 385 K, which is nearly six times higher than the reference sample (β-Ag₂Se). Our findings bring valuable insight into the technology of optimization of thermoelectric characteristics of Se-rich β-Ag₂Se, highlighting its potential for applications in thermoelectric devices. The study demonstrates the energetically efficient and environmental advantage of our mechanochemical route to produce Se-rich β-Ag₂Se, providing a solvent-free and commercially viable alternative synthesis for energy (thermoelectric and solar energy). Full article

(This article belongs to the Special Issue Feature Papers in Inorganic Materials 2024)

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12 pages, 3851 KiB

Open AccessArticle

Complex Structure, Chemical Bonding, and Electrical Transport Properties of a La-Doped Zintl Phase

by Junsu Lee, Yunjeong Lee, Myung-Ho Choi, Kang Min Ok and Tae-Soo You

Inorganics 2024, 12(12), 333; https://doi.org/10.3390/inorganics12120333 - 20 Dec 2024

Viewed by 571

Abstract

The La-doped ternary Zintl phase Ca_10.43(3)La_0.57Sb_9.69(1) was successfully synthesized by arc melting, and the title compound adopted the Ho₁₁Ge₁₀-type structure with a tetragonal I4/mmm space group (Z = 4, Pearson code [...] Read more.

The La-doped ternary Zintl phase Ca_10.43(3)La_0.57Sb_9.69(1) was successfully synthesized by arc melting, and the title compound adopted the Ho₁₁Ge₁₀-type structure with a tetragonal I4/mmm space group (Z = 4, Pearson code tI84). The complex crystal structure is composed of (1) the four different kinds of cationic Ca or Ca/La mixed sites surrounded by seven or nine Sb atoms and (2) the 3-dimensional cage-shaped anionic frameworks built by the other two types of Sb atoms. In particular, the La dopants preferred to occupy the Ca4 and Ca1 sites, and this specific cationic-site preference can be rationalized by both electronic and size-factor criteria. Moreover, the ca. 16% occupational deficiency observed at the Sb3 site was attributed to the energetically unfavorable antibonding character of the Sb3–Sb3 bond in the [Sb3]₄ tetramers, according to a series of DFT calculations. A crystal Hamilton overlap population curve analysis also proved that the title compound Ca_10.43(3)La_0.57Sb_9.69(1) tried to keep the valence electron count below 71.02 to remain energetically stable in the Ho₁₁Ge₁₀-type phase. Measurements of temperature-dependent electrical transport properties revealed that the La doping indeed enhanced the electrical conductivity of Ca_10.43(3)La_0.57Sb_9.69(1) compared to the un-doped Ca₁₁Sb₁₀. However, unlike other rare earth metal (RE)-doped compounds in the Ca_11−xRE_xSb₁₀ (RE = Nd and Sm) system that display semiconducting behavior, the La-doped title compound showed poor metallic electrical properties. The positive values of Seebeck coefficients indicated the p-type character of the title compound despite the successful n-type La doping, and this should be attributed to Sb deficiency. Full article

(This article belongs to the Section Inorganic Solid-State Chemistry)

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11 pages, 3069 KiB

Open AccessArticle

Photoluminescence Properties of X-Ray Generated Divalent Sm in Mechanochemically Prepared Nanocrystalline CaF₂:Sm³⁺

by Z. Siti Rozaila, Nicolas Riesen and Hans Riesen

Inorganics 2024, 12(12), 332; https://doi.org/10.3390/inorganics12120332 - 20 Dec 2024

Viewed by 527

Abstract

In this study, the mechanochemical preparation of nanocrystalline CaF₂:Sm³⁺ by ball milling calcium acetate hydrate, samarium (III) acetate hydrate, and ammonium fluoride is reported. The photoluminescence of the as-prepared CaF₂:Sm³⁺ shows predominantly Sm^3+ 4G_5/2 → [...] Read more.

In this study, the mechanochemical preparation of nanocrystalline CaF₂:Sm³⁺ by ball milling calcium acetate hydrate, samarium (III) acetate hydrate, and ammonium fluoride is reported. The photoluminescence of the as-prepared CaF₂:Sm³⁺ shows predominantly Sm^3+ 4G_5/2 → ⁶H_J(J = 5/2, 7/2, 9/2, and 11/2) f-f luminescence, but intense electric dipole allowed 4f⁵5d (T_1u) → 4f^6 7F₁ (T_1g) luminescence by Sm²⁺ was generated upon X-irradiation. In comparison with the co-precipitated CaF₂:Sm³⁺, the conversion of Sm³⁺

\to

Sm²⁺ in the ball-milled sample upon X-irradiation is significantly lower. Importantly, the present results indicate that the crystallite size and X-ray storage phosphor properties of the lanthanide-doped nanocrystalline CaF₂ can be modified by adjusting the ball milling time, dopant concentration and post-annealing treatment, yielding crystallite sizes as low as 6 nm under specific experimental conditions. Full article

(This article belongs to the Special Issue Synthesis and Application of Luminescent Materials, 2nd Edition)

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10 pages, 1494 KiB

Open AccessArticle

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 1 | Viewed by 525

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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28 pages, 5753 KiB

Open AccessArticle

Ni(II) and Cu(II) Ion Coordination by the Novel (2E,2′E)-N,N′-(2-Hydroxypropane-1,3-diyl)bis[(2-hydroxyimino)propanamide] Ligand in the Solid State and in Aqueous Medium

by Igor Vasyl Nikolayenko, Carla Bazzicalupi, Thomas-John Theron and Craig Grimmer

Inorganics 2024, 12(12), 330; https://doi.org/10.3390/inorganics12120330 - 17 Dec 2024

Viewed by 704

Abstract

In the process of a systematic study of the bis-chelate oxime-amide ligands with different polymethylene spacers and their transition metal complexes, two new Ni(II) and Cu(II) complexes of the mhiea₂poh ligand have been isolated, and their molecular and crystal structures [...] Read more.

In the process of a systematic study of the bis-chelate oxime-amide ligands with different polymethylene spacers and their transition metal complexes, two new Ni(II) and Cu(II) complexes of the mhiea₂poh ligand have been isolated, and their molecular and crystal structures determined by single crystal X-ray diffraction. Potentiometric titrations were performed on a range of aqueous solutions in both systems, which allowed the identification of various complex species and afforded their stability constants. ESR spectra of samples with optimised concentrations of complexes in Cu(II)–L–H system were recorded. A distinguishing feature of both systems is the dimerization of anionic pseudo-macrocyclic complexes. The latter is caused either by centrosymmetric hydrogen bonding of the hydroxy group on the propane spacer to the oximato oxygen of the opposing unit or by back-to-back π-stacking of planar complex units. ESR measurements indicated likely coupling of Cu-Cu paramagnetic centres in the dimers. Full article

(This article belongs to the Special Issue Metal Complexes with N-donor Ligands, 2nd Edition)

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20 pages, 697 KiB

Open AccessArticle

Local Energy Minima and Density of Energy Barriers in Dense Clusters of Magnetic Nanoparticles

by Natalia L. Gorn, Elena K. Semenova and Dmitry Berkov

Inorganics 2024, 12(12), 329; https://doi.org/10.3390/inorganics12120329 - 17 Dec 2024

Viewed by 474

Abstract

In this paper, we focus on the properties of local energy minima and energy barriers in immobilized dense clusters of magnetic nanoparticles. Understanding of these features is highly interesting both for the fundamental physics of disordered systems with long-range interparticle interaction and for [...] Read more.

In this paper, we focus on the properties of local energy minima and energy barriers in immobilized dense clusters of magnetic nanoparticles. Understanding of these features is highly interesting both for the fundamental physics of disordered systems with long-range interparticle interaction and for numerous applications of modern ferrofluids consisting of such clusters. In particular, it is needed to predict the ac-susceptibility of these systems and their magnetization relaxation after a sudden change in the external field, because both processes occur via magnetization jumps over energy barriers that separate the energy minima. Due to the exponential increase in the corresponding jump time with barrier height (

t_{sw} \sim \exp (Δ E / k T)

), direct Langevin dynamics simulations of this process are not feasible. For this reason, we have developed efficient numerical methods both for finding as many energy minima as possible and for the reliable evaluation of energy barriers between them. Our results for the distribution of overlaps between the local energy minima imply that there is no spin-glass state in such clusters even when they consist of particles with a small anisotropy. Further, we show that the distributions of energy barrier heights are qualitatively different for clusters of particles with small, intermediate, and large anisotropies, which has important consequences for the magnetization dynamics of these systems. Full article

(This article belongs to the Section Inorganic Materials)

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2 pages, 174 KiB

Open AccessEditorial

Synthesis, Properties and Applications of Lanthanide and Actinide Molecular Compounds

by Leonor Maria and Joaquim Marçalo

Inorganics 2024, 12(12), 328; https://doi.org/10.3390/inorganics12120328 - 16 Dec 2024

Viewed by 680

Abstract

Lanthanides and actinides have unique physical and chemical properties, and their compounds continue to be extensively studied on a fundamental level during the search for applications that range from energy production and related environmental issues to the life sciences [...] Full article

(This article belongs to the Special Issue Synthesis, Properties and Applications of Lanthanide and Actinide Molecular Compounds)

8 pages, 2966 KiB

Open AccessArticle

Improved Photothermal Heating of NaNdF₄ Microcrystals via Low-Level Doping of Sm³⁺ for Thermal-Responsive Upconversion Luminescence Anti-Counterfeiting

by Ronghua Jian and Tao Pang

Inorganics 2024, 12(12), 327; https://doi.org/10.3390/inorganics12120327 - 13 Dec 2024

Viewed by 436

Abstract

This work reports the light-to-heat conversion (LHC) behavior of NaNdF₄ doped with Sm³⁺. Due to the cross-relaxation between Nd³⁺ and Sm³⁺, the improved LHC is obtainable by introducing 5% Sm³⁺. When the laser power density [...] Read more.

This work reports the light-to-heat conversion (LHC) behavior of NaNdF₄ doped with Sm³⁺. Due to the cross-relaxation between Nd³⁺ and Sm³⁺, the improved LHC is obtainable by introducing 5% Sm³⁺. When the laser power density is only 1.72 W/cm², the spot temperature of NaNdF₄:5%Sm³⁺ powder reaches as high as 138.7 ± 4.04 °C. More importantly, the photoheating response to the pump laser has favorable linear characteristics within a specific power range. A simple physical model is applied to analyze the relationship between photothermal heating and pump power. Finally, the temperature-responsive luminescence anti-counterfeiting is designed by combining the LHC material with the NaYF₄:Yb³⁺/Ho³⁺/Ce³⁺ microcrystals. This novel strategy only requires two laser beams, and thus is more convenient to apply. Full article

(This article belongs to the Special Issue Optical and Quantum Electronics: Physics and Materials)

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11 pages, 2426 KiB

Open AccessPerspective

Comparison of Gallium Cluster Polyhedra with Those of the Most Spherical Deltahedra: Effects of Bulky External Groups and Local Surface Curvature

by R. Bruce King

Inorganics 2024, 12(12), 326; https://doi.org/10.3390/inorganics12120326 - 13 Dec 2024

Viewed by 333

Abstract

Experimentally accessible stable polyhedral clusters of gallium differ from clusters of its lighter homologue boron by having sterically demanding external groups such as tBu₃Si, (Me₃Si)₃Si, (Me₃Si)₃C, (Me₃Si)₂N, and fluorenyl. [...] Read more.

Experimentally accessible stable polyhedral clusters of gallium differ from clusters of its lighter homologue boron by having sterically demanding external groups such as tBu₃Si, (Me₃Si)₃Si, (Me₃Si)₃C, (Me₃Si)₂N, and fluorenyl. This restricts closo deltahedral [Ga_nR_n]^z gallane chemistry to octahedral derivatives such as Ga₆R₆²⁻ (R = SiBuPh₂, SiBu^t₃) and Ga₆R₆ (R = SiMe(SiMe₃)₂) in which the bulky external silyl groups are spread out because of the relatively high local curvature of the degree 4 vertices of the central Ga₆ octahedron. The structures of larger gallium clusters are based on alternatives to closo deltahedra having exclusively high local curvature degree 4 vertices such as the 8-vertex square antiprismatic Ga₈R₈ (R = fluorenyl) or, more commonly, larger polyhedra or fused polyhedra with some bare gallium vertices. Some of the larger gallium clusters can be considered to be spherically aromatic systems with closed shells according to the jellium model. Examples include [Ga₁₃(SitBu₃)₆]⁻ with 8 cluster electrons corresponding to a filled 1S²1P⁶ shell as well as [Ga@Ga₁₈{C(SiMe₃)₃}₆]⁻ with 52 cluster electrons, Ga₂₂{E(SiMe₃)₃]₈, (E = C, Si) and Ga@Ga₁₁{GaN(SiMe₃)₂}₁₁ with 58 skeletal electrons, and [Ga₂₆{Si(SiMe₃)₃}₈]²⁻ with 72 cluster electrons. The 10-vertex species Ga₁₀{Si(SiMe₃)₃}₆, [Ga₁₀(SitBu₃)₆]⁻, and Ga₁₀(SitBu₃)₆ have structures consisting of a fusion of two polyhedra sharing bare gallium vertices with skeletal electron counts, suggesting a multicenter core bond in each of the two polyhedral cavities. Full article

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18 pages, 5027 KiB

Open AccessArticle

Immobilization of Bromelain on Gold Nanoparticles for Comprehensive Detection of Their Antioxidant, Anti-Angiogenic, and Wound-Healing Potentials

by Amal Ahmed Ausaj, Hanady S. Al-Shmgani, Wijdan Basheer Abid, Abdelalim A. Gadallah, Abadi M. Mashlawi, Mohsen A. Khormi, Abdullah Ali Alamri and Emad Abada

Inorganics 2024, 12(12), 325; https://doi.org/10.3390/inorganics12120325 - 13 Dec 2024

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Abstract

Bromelain (Br) is a proteolytic enzyme with various pharmacological properties, such as antibacterial, antioxidant, anti-inflammatory, anticancer, and anti-angiogenic properties. However, due to its low solubility and bioavailability, its absorption is low, so a delivery mechanism is needed to achieve the desired therapeutic effects. [...] Read more.

Bromelain (Br) is a proteolytic enzyme with various pharmacological properties, such as antibacterial, antioxidant, anti-inflammatory, anticancer, and anti-angiogenic properties. However, due to its low solubility and bioavailability, its absorption is low, so a delivery mechanism is needed to achieve the desired therapeutic effects. Bromelain was chemically synthesized and loaded onto gold nanoparticles (AuNPs). Different methods and techniques were used for detection and characterization, including color-change detection, UV spectroscopy, XRD, SEM, TEM, and FTIR. The in vitro antioxidant activity was detected using DPPH assays, and the wound-healing activity was investigated in mice. The current study revealed that the formulated AuNPs-Br showed effective antioxidant activity and the strongest wound-healing properties, as demonstrated by histopathological and in vivo studies, and showed anti-angiogenic effects. Full article

(This article belongs to the Section Bioinorganic Chemistry)

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14 pages, 2194 KiB

Open AccessArticle

Reactivity of [3+1+1] Uranyl-DGA Complex as Lewis-Acid Catalyst in Nucleophilic Acyl Substitution of Acid Anhydrides

by Shin Akashi and Koichiro Takao

Inorganics 2024, 12(12), 324; https://doi.org/10.3390/inorganics12120324 - 13 Dec 2024

Viewed by 576

Abstract

A UO₂²⁺ complex bearing N, N, N′, N′-tetraisopropyldiglycolamide (TiPDGA) and two DMF molecules was prepared to explore the catalytic activities of the Lewis-acidic U centre. The cationic complex, [UO₂(TiPDGA)(DMF)₂]²⁺, was obtained [...] Read more.

A UO₂²⁺ complex bearing N, N, N′, N′-tetraisopropyldiglycolamide (TiPDGA) and two DMF molecules was prepared to explore the catalytic activities of the Lewis-acidic U centre. The cationic complex, [UO₂(TiPDGA)(DMF)₂]²⁺, was obtained as a ClO₄⁻ salt under optimised reaction conditions with an appropriate mixing ratio between UO₂²⁺ and TiPDGA to maintain 1:1 stoichiometry, a non-coordinating ClO₄⁻ counteranion to reserve the coordination sites for substrate activation, and the presence of extra HClO₄ to suppress undesired hydrolysis of UO₂²⁺ competing with the expected complex formation. This UO₂²⁺ complex was characterised by IR, elemental analysis, X-ray crystallography, and ¹H NMR to confirm that the desired [3+1+1] equatorial coordination is actually formed in the solid state and is still maintained even after dissolution in CD₂Cl₂. [UO₂(TiPDGA)(DMF)₂]²⁺ was further subjected to nucleophilic acyl substitution reactions of acid anhydrides to assess its activity and capability as a Lewis-acid catalyst there. Although the observed reaction rates were not very rapid, some characteristic aspects to gain reaction- and substrate-selectivity appeared thanks to the equatorial coordination sphere sterically regulated by the tridentate auxiliary TiPDGA ligand and labile monodentate DMF molecules to activate an acid anhydride after ligand substitution. Full article

(This article belongs to the Section Coordination Chemistry)

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11 pages, 2926 KiB

Open AccessArticle

Magnetism of Manganese Complexes with Fluorinated Benzimidazole-Substituted Nitronyl Nitroxides

by Evgeny Tretyakov, Nadejda Bakuleva, Nikolay Efimov, Elizaveta Kulikova and Dominique Luneau

Inorganics 2024, 12(12), 323; https://doi.org/10.3390/inorganics12120323 - 12 Dec 2024

Viewed by 581

Abstract

A series of layered compounds of the formula {[Mn₂(radical)₃](ClO₄)}_n was obtained by a reaction (in methanol) of manganese(II) acetate with 2-(2-benzimidazolyl)-4,4,5,5-tetramethylimidazolidinyl-1-oxy-3-oxides fluorinated on the benzene ring and by successive addition of sodium perchlorate. This study showed [...] Read more.

A series of layered compounds of the formula {[Mn₂(radical)₃](ClO₄)}_n was obtained by a reaction (in methanol) of manganese(II) acetate with 2-(2-benzimidazolyl)-4,4,5,5-tetramethylimidazolidinyl-1-oxy-3-oxides fluorinated on the benzene ring and by successive addition of sodium perchlorate. This study showed that the magnetic properties of the complexes are sensitive to the number and arrangement of fluorine atoms in the paramagnetic ligands. It was found that the heterospin complex with 4-FBzIm-NN behaves as a magnet with Curie temperature T_C = 50 K, which is close to that of the {[Mn₂(BzIm-NN)₃](ClO₄)}_n complex containing a nonfluorinated ligand. Meanwhile, no 3D ordering was noted for complexes with difluorinated and 5-fluoro-substituted ligands. Full article

(This article belongs to the Section Coordination Chemistry)

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11 pages, 3525 KiB

Open AccessArticle

Effects of Ti and Sn Substitutions on Magnetic and Transport Properties of the TiFe₂Sn Full Heusler Compound

by Bogdan Popescu, Ilhame Assahsahi, Magdalena Galatanu and Andrei Galatanu

Inorganics 2024, 12(12), 322; https://doi.org/10.3390/inorganics12120322 - 11 Dec 2024

Viewed by 416

Abstract

The synthesis of polycrystalline TiFe₂Sn samples by a route including arc melting and spark plasma sintering with Hf, Y, and In substitutions at the Ti and Sn sites is investigated. For a reduced amount of substitution, around 2 at%, the samples [...] Read more.

The synthesis of polycrystalline TiFe₂Sn samples by a route including arc melting and spark plasma sintering with Hf, Y, and In substitutions at the Ti and Sn sites is investigated. For a reduced amount of substitution, around 2 at%, the samples are single phase, while for increased amounts, secondary phases segregate. As is characteristic of these compounds, the Fe-Ti atomic disorder generates a weak ferromagnetic ordering, which is also influenced by the type of substitutional atoms and the secondary phases in the samples with a higher Hf content. The Seebeck coefficient values show an increase for Ti_0.98Hf_0.02Fe₂Sn and for samples with an adjusted Sn content, resulting in slightly increased power factor values. These values reach a maximum for Ti_0.98Hf_0.02Fe₂Sn at approximately 300 K and for TiFe₂Sn_1.05 at approximately 325 K, namely, 2.69 × 10⁻⁴ Wm⁻¹K⁻² and 2.52 × 10⁻⁴ Wm⁻¹K⁻², respectively. The thermal conductivity of all the samples with substitutions increases with respect to the pristine sample. The highest figure of merit value of 0.016 is also obtained for Ti_0.98Hf_0.02Fe₂Sn at 325 K. Full article

(This article belongs to the Special Issue New Semiconductor Materials for Energy Conversion)

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14 pages, 2408 KiB

Open AccessArticle

Synthesis Comparative Electrochemistry and Spectroelectrochemistry of Metallocenyl β-Diketonato Dicarbonyl Complexes of Rhodium(I)—Cytotoxicity of [Rh(FcCOCHCOCF₃)(CO)₂]

by Eleanor Fourie, J. W. (Hans) Niemantsverdriet and Jannie C. Swarts

Inorganics 2024, 12(12), 321; https://doi.org/10.3390/inorganics12120321 - 11 Dec 2024

Viewed by 476

Abstract

The metallocenyl-containing β-diketonato rhodium(I) dicarbonyl complexes of [Rh(FcCOCHCOR)(CO)₂] where R = CF₃, 10; Fc = ferrocenyl = Fe^II(C₅H₅)(C₅H₄), 11; Rc = ruthenocenyl = Ru^II(C₅ [...] Read more.

The metallocenyl-containing β-diketonato rhodium(I) dicarbonyl complexes of [Rh(FcCOCHCOR)(CO)₂] where R = CF₃, 10; Fc = ferrocenyl = Fe^II(C₅H₅)(C₅H₄), 11; Rc = ruthenocenyl = Ru^II(C₅H₅)(C₅H₄), 12; and Oc = osmocenyl = Os^II(C₅H₅)(C₅H₄), 13 were synthesized. Complexes 10–13 were then subjected to an electrochemical study utilizing cyclic voltammetry (CV), square wave voltammetry (SWV), and linear sweep voltammetry (LSV) in the non-coordinating solvent/supporting electrolyte medium CH₂Cl₂/0.1 mol dm⁻³ [N(ⁿBu)₄][B(C₆F₅)₄]. The formal reduction potential for the electrochemical reversible Fc^0/+ couples in 10–13 was identified in the range 0.156 ≤ E^o′ ≤ 0.328 V while the electrochemically irreversible osmocenyl and ruthenocenyl oxidations were observed at peak anodic potentials of E_pa = 0.640 V and E_pa = 0.751 V, respectively. Resolution between the closely overlapping CV-determined Fc^0/+ and Rh^I/II couples was too poor for unambiguous measurement of the Rh^I/II redox potential, but square wave voltammetry allowed estimates of E^o′ (Rh^I/II) in the range 0.156 ≤ E^o′ ≤ 0.398 V. FT-IR spectroelectrochemistry confirmed the one-electron oxidation of Rh^I by the appearance of CO vibrational bands at stretching frequencies, which are associated with rhodium(II) and not rhodium(III). Cytotoxicity tests on 10 (IC₅₀ = 19.2 µM) showed it to be substantially less cytotoxic than the free β-diketone, FcCOCH₂COCF₃, and [Rh(FcCOCHCOCF₃)(cod)]. Full article

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14 pages, 2604 KiB

Open AccessArticle

Comparison of Photocatalytic Activity: Impact of Hydrophilic Properties on TiO₂ and ZrO₂ Thin Films

by Yuliana de Jesús Acosta-Silva, Misael Ian Lugo-Arredondo, Salvador Gallardo-Hernández, Juan Fernando Garcia-Trejo, Yasuhiro Matsumoto, Sandra Rivas, Ana Angélica Feregrino-Pérez, Luis A. Godínez and Arturo Méndez-López

Inorganics 2024, 12(12), 320; https://doi.org/10.3390/inorganics12120320 - 10 Dec 2024

Viewed by 569

Abstract

Thin films (TFs) of TiO₂ and ZrO₂ were prepared and characterized to evaluate their structural and optical (SO) properties and, later, to test their efficiency for the photocatalytic degradation (PD) of methylene blue (MB) in aqueous solution. The X-ray diffraction patterns [...] Read more.

Thin films (TFs) of TiO₂ and ZrO₂ were prepared and characterized to evaluate their structural and optical (SO) properties and, later, to test their efficiency for the photocatalytic degradation (PD) of methylene blue (MB) in aqueous solution. The X-ray diffraction patterns showed that the TiO₂ TFs had an anatase crystalline structure, unlike the ZrO₂ TFs, which showed a tetragonal crystalline structure that was verified by Raman spectroscopy. The band gap (BG) energies, as calculated from UV-Vis spectroscopy and diffuse reflectance spectroscopy, corresponded to 3.2 and 3.7 eV for the TiO₂ and ZrO₂ TFs, respectively. SEM examination of the obtained materials was also carried out to assess the surface morphology and topography. The comparative study of the FTIR spectra of the TiO₂ and ZrO₂ TFs successfully confirmed the composition of the two-metal oxide TFs. The electrical properties of the films were studied by conductivity measurements. The two films also showed a similar thickness of about 200 nm and a substantially different photocatalytic performance for the discoloration of MB in aqueous solution. The corresponding rate constants, as obtained from a pseudo-first-order kinetic model, revealed that TiO₂ films promote color removal of the model dye solution almost 20 times faster than the rate observed for ZrO₂ modified glass substrates. We suggest that this difference may be related to the hydrophilic character of the two films under study, which may affect the charge carrier injection process and, therefore, the overall photocatalytic performance. Full article

(This article belongs to the Special Issue Nanocomposites for Photocatalysis, 2nd Edition)

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12 pages, 4774 KiB

Open AccessArticle

A Novel TiO₂-Cuttlebone Photocatalyst for Highly Efficient Catalytic Degradation of Tetracycline Hydrochloride

by Qing Li, Penghui Liu, Huizhen Lin, Hun Xue and Jingyun Mao

Inorganics 2024, 12(12), 319; https://doi.org/10.3390/inorganics12120319 - 10 Dec 2024

Viewed by 498

Abstract

The harmful effects of antibiotics on aquatic environments have become a growing concern of modern society. Developing high-performance photocatalysts capable of degrading antibiotics under solar light is, therefore, crucial. In this study, TiO₂-cuttlebone composites are prepared via the sol–gel method, to [...] Read more.

The harmful effects of antibiotics on aquatic environments have become a growing concern of modern society. Developing high-performance photocatalysts capable of degrading antibiotics under solar light is, therefore, crucial. In this study, TiO₂-cuttlebone composites are prepared via the sol–gel method, to produce carbonate radicals (•CO₃⁻) under solar light irradiation. The •CO₃⁻ radicals exhibit high selectivity for the degradation of tetracycline hydrochloride (TC). Compared to TiO₂ alone, the TiO₂-cuttlebone composite demonstrates excellent solar-driven photocatalytic activity for TC degradation in both freshwater and seawater. The reaction pathways of TC degradation in seawater are elucidated using HPLC-MS/MS analysis. Moreover, a TiO₂-cuttlebone self-suspending photocatalyst device is fabricated using 3D printing technology and low-temperature deposition methods, with aluminum–plastic (AP) as a substrate. This innovative device is easily recyclable from photocatalytic solutions while maintaining high stability, making it highly desirable for practical applications. Full article

(This article belongs to the Special Issue Advanced Inorganic Semiconductor Materials, 2nd Edition)

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8 pages, 5101 KiB

Open AccessArticle

A Study on the Volume Expansion of Vanadium-Based Alloy Powders and Compacts During Hydrogen Sorption

by Mojia Li, Yunfeng Hu, Hanyang Kong, Qiuwei Huang, Yusong Chen and Yigang Yan

Inorganics 2024, 12(12), 318; https://doi.org/10.3390/inorganics12120318 - 8 Dec 2024

Viewed by 739

Abstract

Storing hydrogen in solid metal hydrides provides a safe and efficient storage approach. However, the large volume expansion of metal hydrides during hydrogen absorption imposes substantial stresses on the wall of a hydrogen storage tank. In this study, volume expansion behavior of a [...] Read more.

Storing hydrogen in solid metal hydrides provides a safe and efficient storage approach. However, the large volume expansion of metal hydrides during hydrogen absorption imposes substantial stresses on the wall of a hydrogen storage tank. In this study, volume expansion behavior of a V-based hydrogen storage alloy, V₆₁Cr₂₄Ti₁₂Ce₃, with body-centered-cubic, was investigated using a self-developed in situ expansion testing device. The lattice expansion of the V₆₁Cr₂₄Ti₁₂Ce₃ alloy after full hydrogenation was determined to be 37.85% using X-ray diffraction(XRD). The powder bed, composed of alloy powder with an average size of 3.35 mm in diameter, displays a large volume expansion ratio of 131% at the first hydrogen absorption cycle and 40–45% in the following four cycles. The stable compact bed, made of alloy powders, organic silicone gel, and graphite flakes, shows significantly smaller volume expansion ratio, which is 97% at the first cycle and 21% at the second cycle, and stabilizes at 13% in the following cycles. Also, the compact bed shows similar hydrogen absorption capacity, but faster absorption kinetics compared to the powder bed. Full article

(This article belongs to the Special Issue Feature Papers in Inorganic Materials 2024)

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11 pages, 2920 KiB

Open AccessArticle

The In Vitro Cytotoxic Potential of Biosynthesized Silver Nanoparticles in MIA PaCa-2 Cells Supported with an In Silico Study

by Angélica Sofía González-Garibay, Alba Adriana Vallejo-Cardona, Ariadna Abigail Villarreal-Amézquita, Iván Moisés Sánchez-Hernández, Omar Ricardo Torres-González and Eduardo Padilla-Camberos

Inorganics 2024, 12(12), 317; https://doi.org/10.3390/inorganics12120317 - 7 Dec 2024

Viewed by 988

Abstract

Pancreatic cancer affects many people and is quite aggressive. Metallic nanoparticles may be an alternative treatment for this disease. In this work, the antiproliferative activity of biosynthesized silver nanoparticles was evaluated. Stenocereus queretaroensis peel extract was used as a reducing agent for nanoparticle [...] Read more.

Pancreatic cancer affects many people and is quite aggressive. Metallic nanoparticles may be an alternative treatment for this disease. In this work, the antiproliferative activity of biosynthesized silver nanoparticles was evaluated. Stenocereus queretaroensis peel extract was used as a reducing agent for nanoparticle synthesis; the characterization was carried out using spectroscopic techniques, X-ray diffraction, and microscopy. The antiproliferative effect was evaluated in the MIA PaCa-2 pancreatic tumoral cell line, and a molecular docking test was run with the STAT3 protein. The results obtained show that it was possible to synthesize silver nanoparticles from the plant extract, which was confirmed through characterization studies. The average size of the nanoparticles was measured to be 48.8 nm, and they predominantly exhibited a spherical shape. The antiproliferative effect was demonstrated in the pancreatic cell line, with an IC₅₀ value of 15.66 µg/mL. The molecular docking analysis predicted a strong interaction with the STAT3 protein, with a binding energy value of −6.47 obtained. With these results, it is concluded that biosynthesized silver nanoparticles inhibit pancreatic tumor cell growth and may represent an innovative cancer treatment. Full article

(This article belongs to the Special Issue Metal-Based Compounds: Relevance for the Biomedical Field)

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26 pages, 2674 KiB

Open AccessReview

Guardians of the Genome: Iron–Sulfur Proteins in the Nucleus

by Lorena Novoa-Aponte, Andres Leon-Torres and Caroline C. Philpott

Inorganics 2024, 12(12), 316; https://doi.org/10.3390/inorganics12120316 - 6 Dec 2024

Viewed by 672

Abstract

Iron–sulfur (Fe-S) clusters are essential cofactors found in many proteins in the mitochondria, cytosol, and nucleus of the cell. These versatile cofactors may undergo reversible oxidation–reduction reactions to enable electron transfers; they may be structural and confer stability to a folded protein; they [...] Read more.

Iron–sulfur (Fe-S) clusters are essential cofactors found in many proteins in the mitochondria, cytosol, and nucleus of the cell. These versatile cofactors may undergo reversible oxidation–reduction reactions to enable electron transfers; they may be structural and confer stability to a folded protein; they may be regulatory and transduce an iron signal that alters the function or stability of a recipient protein. Of the nearly 70 proteins described in mammalian cells that bind Fe-S clusters, about half localize exclusively or partially to the nucleus, where they are required for DNA replication and repair, telomere maintenance, transcription, mitosis, and cell cycle control. Most nuclear Fe-S cluster proteins interact with DNA, including DNA polymerases, primase, helicases, and glycosylases. However, the specific roles of the clusters in the enzymatic activities of these proteins and their interplay with DNA remain a matter of debate. Defects in the metallation of nuclear Fe-S proteins cause genome instability and alter the regulation of cell division and proliferation, which are hallmarks of various genetic diseases and cancers. Here, we provide an inventory of the nuclear Fe-S cluster-binding proteins and discuss cluster types, binding sites, the process of cluster acquisition, and the potential roles of the cluster in the function of the proteins. However, many questions remain unresolved. We highlight critical gaps in our understanding of cluster delivery to nuclear client proteins, the potential for cluster repair, and the mechanistic roles that clusters play in these enzymes. Taken together, this review brings the focus to the nucleus of the human cell as a hotspot for Fe-S cluster proteins and aims to inspire new research on the roles of iron in DNA metabolism and the maintenance of genome integrity. Full article

(This article belongs to the Special Issue Iron-Sulfur Clusters: Assembly and Biological Roles)

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13 pages, 2826 KiB

Open AccessArticle

Theoretical Investigations of Para-Methoxystyrene/Styrene Polymerization Catalyzed by Cationic Methyl- and Dibenzobarrelene-Based α-Diimine Palladium Complexes

by Ling Zhu, Yi Luo, Xin Wen, Wenzhen Zhang and Guangli Zhou

Inorganics 2024, 12(12), 315; https://doi.org/10.3390/inorganics12120315 - 5 Dec 2024

Viewed by 476

Abstract

The polymerization mechanism of para-methoxystyrene catalyzed by cationic α-diimine palladium complexes with various ancillary ligands was rigorously examined using density functional theory. In the classical methyl-based α-diimine palladium complex [{(2,6-ⁱPr₂C₆H₃)-N=C(Me)-C(Me)=N-2,6-ⁱPr [...] Read more.

The polymerization mechanism of para-methoxystyrene catalyzed by cationic α-diimine palladium complexes with various ancillary ligands was rigorously examined using density functional theory. In the classical methyl-based α-diimine palladium complex [{(2,6-ⁱPr₂C₆H₃)-N=C(Me)-C(Me)=N-2,6-ⁱPr₂C₆H₃)}PdMe]⁺ (A⁺), the 2,1-insertion of para-methoxystyrene is favored over the 1,2-insertion, both thermodynamically and kinetically, during the chain initiation step. The resulting thermodynamically favored η³-π-benzyl intermediates face a substantial energy barrier, yielding only trace amounts of polymer, as experimentally verified. In contrast, the dibenzobarrelene-based α-diimine palladium complex [{(2,6-ⁱPr₂C₆H₃)-N=C(R)-C(R)=N-2,6-ⁱPr₂C₆H₃)}PdMe]⁺ (R = dibenzobarrelene, B⁺) shows similar energy barriers for both 2,1- and 1,2-insertions. Continuous 2,1/2,1 or 2,1/1,2 insertions are impeded by excessive energy barriers. However, theoretical calculations reveal that the 1,2-insertion product can seamlessly transition into the chain propagation stage, producing a polymer with high 1,2-regioselectivity. The observed activity of complexes A⁺ or B⁺ towards para-methoxystyrene polymerization stems from the energy barrier differences between the 1,2- and 2,1-insertions, influenced by the steric hindrance from the ancillary ligands. Further investigation into the effects of steric hindrance on the chain initiation stage involved computational modeling of analogous complexes with increased steric bulk. These studies established a direct correlation between the energy barrier difference ∆∆G (1,2–2,1) and the van der Waals volume of the ancillary ligand. Larger van der Waals volumes correspond to reduced energy barrier differences, thus enhancing the regioselectivity for para-methoxystyrene polymerization. Moreover, the experimental inertness of complex B⁺ towards styrene polymerization is attributed to the formation of stable kinetic and thermodynamic 2,1-insertion intermediates, which obstruct further styrene monomer insertion due to an extremely high reactive energy barrier. These findings contribute to a deeper understanding of the mechanistic aspects and offer insights for designing new transition metal catalysts for the polymerization of para-alkoxystyrenes. Full article

(This article belongs to the Special Issue Revealing Reaction Mechanisms in Homogeneous Transition Metal Catalysis, 2nd Edition)

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16 pages, 2915 KiB

Open AccessArticle

Phase Relations in the Pseudo-Binary BiFeO₃–EuFeO₃ System in the Subsolidus Region Derived from X-Ray Diffraction Data—A Machine Learning Approach

by Vasile-Adrian Surdu and Romuald Győrgy

Inorganics 2024, 12(12), 314; https://doi.org/10.3390/inorganics12120314 - 4 Dec 2024

Viewed by 622

Abstract

BiFeO₃ and EuFeO₃ are some of the most studied ferrites and part of the larger category of multiferroic and magnetic compounds. The instabilities reported for BiFeO₃ that hinder its use in practical applications can be overcome by substitution with rare-earth [...] Read more.

BiFeO₃ and EuFeO₃ are some of the most studied ferrites and part of the larger category of multiferroic and magnetic compounds. The instabilities reported for BiFeO₃ that hinder its use in practical applications can be overcome by substitution with rare-earth ions, such as Eu³⁺, on the Bi³⁺ site. This paper reports on the phase relations in the BiFeO₃-EuFeO₃ pseudo-binary system, which were not established previously. Solid-state reactions were employed to prepare different compositions according to the nominal formula Bi_1−xEu_xFeO₃ (where x = 0, 0.05, 0.10, 0.15, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1). Phase equilibria were studied at different temperatures between 800 and 1200 °C from X-ray diffraction (XRD) data. The analysis of the XRD patterns by machine learning approaches revealed eight defined clusters and four unclustered points. The validation test showed that most of the points could belong to several clusters and thus, traditional identification was employed. Phase identification and quantification by traditional approaches revealed six crystallization zones on the diagram. Although the machine learning approach offers speed in the process of classification of XRD patterns, validation by the traditional method was necessary for the construction of the phase diagram with high accuracy. Full article

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56 pages, 7554 KiB

Open AccessReview

The Integration of Thermal Energy Storage Within Metal Hydride Systems: A Comprehensive Review

by Matias Davis Cortina, Manuel Romero de Terreros Aramburu, Andre Martins Neves, Lourdes Hurtado, Julian Jepsen and Ulrich Ulmer

Inorganics 2024, 12(12), 313; https://doi.org/10.3390/inorganics12120313 - 3 Dec 2024

Viewed by 1625

Abstract

Hydrogen storage technologies are key enablers for the development of low-emission, sustainable energy supply chains, primarily due to the versatility of hydrogen as a clean energy carrier. Hydrogen can be utilized in both stationary and mobile power applications, and as a low-environmental-impact energy [...] Read more.

Hydrogen storage technologies are key enablers for the development of low-emission, sustainable energy supply chains, primarily due to the versatility of hydrogen as a clean energy carrier. Hydrogen can be utilized in both stationary and mobile power applications, and as a low-environmental-impact energy source for various industrial sectors, provided it is produced from renewable resources. However, efficient hydrogen storage remains a significant technical challenge. Conventional storage methods, such as compressed and liquefied hydrogen, suffer from energy losses and limited gravimetric and volumetric energy densities, highlighting the need for innovative storage solutions. One promising approach is hydrogen storage in metal hydrides, which offers advantages such as high storage capacities and flexibility in the temperature and pressure conditions required for hydrogen uptake and release, depending on the chosen material. However, these systems necessitate the careful management of the heat generated and absorbed during hydrogen absorption and desorption processes. Thermal energy storage (TES) systems provide a means to enhance the energy efficiency and cost-effectiveness of metal hydride-based storage by effectively coupling thermal management with hydrogen storage processes. This review introduces metal hydride materials for hydrogen storage, focusing on their thermophysical, thermodynamic, and kinetic properties. Additionally, it explores TES materials, including sensible, latent, and thermochemical energy storage options, with emphasis on those that operate at temperatures compatible with widely studied hydride systems. A detailed analysis of notable metal hydride–TES coupled systems from the literature is provided. Finally, the review assesses potential future developments in the field, offering guidance for researchers and engineers in advancing innovative and efficient hydrogen energy systems. Full article

(This article belongs to the Special Issue Feature Papers in Inorganic Materials 2024)

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10 pages, 1251 KiB

Open AccessReview

Metal Halide Perovskites for Applications in Biomimetic Devices

by Wending Chu and Lei Su

Inorganics 2024, 12(12), 312; https://doi.org/10.3390/inorganics12120312 - 28 Nov 2024

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Abstract

Metal halide perovskites have demonstrated exceptional multifunctionality, finding applications in photovoltaics, light-emitting devices and sensors, which has stimulated intense research interest. Recently, their integration into biomimetic devices has emerged as a promising frontier, exploiting the unique optoelectronic properties of perovskites to mimic biological [...] Read more.

Metal halide perovskites have demonstrated exceptional multifunctionality, finding applications in photovoltaics, light-emitting devices and sensors, which has stimulated intense research interest. Recently, their integration into biomimetic devices has emerged as a promising frontier, exploiting the unique optoelectronic properties of perovskites to mimic biological functions. This review provides a comprehensive analysis of recent advances in the use of metal halide perovskites for biomimetic applications, focusing on their role in different device configurations and fabrication techniques. We elucidate the mechanisms that drive their performance and demonstrate their potential as versatile materials for high performance biomimetic devices. By exploring the intricate interplay between material properties and device functionality, we highlight the transformative potential of metal halide perovskites in creating more efficient, adaptable and biologically inspired technologies. Finally, we discuss future research directions to maximise their application scope, with the aim of bridging materials science and bioengineering for innovative device development. Full article

(This article belongs to the Special Issue The State of the Art of Research on Perovskites Materials)

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19 pages, 10302 KiB

Open AccessArticle

Investigation of Magnesium-Potassium Phosphates as Potential Nuclear Waste Form for the Immobilization of Minor Actinides

by Hans-Conrad zur Loye, Petr Vecernik, Monika Kiselova, Vlastislav Kašpar, Hana Korenkova, Vlastimil Miller, Petr Bezdicka, Jan Šubrt, Natalija Murafa, Volodymyr Shkuropatenko and Sergey Sayenko

Inorganics 2024, 12(12), 311; https://doi.org/10.3390/inorganics12120311 - 28 Nov 2024

Viewed by 723

Abstract

Several recent studies have evaluated technologies of spent nuclear fuel processing specifically for solidifying transuranic (TRU) waste as a by-product of fission. Of the TRU group, plutonium and the minor actinides will be responsible for the bulk of the radiotoxicity and heat generation [...] Read more.

Several recent studies have evaluated technologies of spent nuclear fuel processing specifically for solidifying transuranic (TRU) waste as a by-product of fission. Of the TRU group, plutonium and the minor actinides will be responsible for the bulk of the radiotoxicity and heat generation of spent nuclear fuel in the long term (300 to 20,000 years). In this study, we investigated magnesium potassium phosphate (MKP)-based compounds as host waste forms for the encapsulation of inactive trivalent Nd and Sm as analogues of the minor trivalent actinides, Am and Cm. Waste forms were fabricated under ambient atmospheric conditions by adding 5 wt.% of substances containing Nd or Sm via the following two routes: powder oxides and aqueous solutions of nitrate salts. Waste form performance was established using strength and aqueous medium leaching tests of MKP-based specimens. The MKP materials were analyzed by X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM and TEM), energy-dispersive X-ray spectroscopy (EDS), and Raman spectroscopy. The waste forms exhibited a compressive strength of ≥30 MPa and were durable in an aqueous environment. The leachability indices for Nd and Sm, as per the ANS 16.1 procedure, were 19.55–19.78 and 19.74–19.89, respectively, which satisfy the acceptable criteria (>6). The results of the present room temperature leaching study suggest that MKPs can be effectively used as a host material to immobilize actinides (Am and Cm) contained in TRU waste. Full article

(This article belongs to the Section Inorganic Materials)

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8 pages, 2451 KiB

Open AccessArticle

Large-Scale Synthesis of Carbon Dots Driven by Schiff Base Reaction at Room Temperature

by Jifen Shi, Shuai Chang, Yating Gao, Jian Lv, Ruocan Qian, Binbin Chen and Dawei Li

Inorganics 2024, 12(12), 310; https://doi.org/10.3390/inorganics12120310 - 27 Nov 2024

Viewed by 543

Abstract

Photoluminescent carbon dots (CDs) have received increasing attention because of their admirable photophysical performances. The current strategies for synthesizing CDs typically require high energy consumption levels, and the ability to synthesize CDs at ambient temperature would be highly desirable. Herein, we design an [...] Read more.

Photoluminescent carbon dots (CDs) have received increasing attention because of their admirable photophysical performances. The current strategies for synthesizing CDs typically require high energy consumption levels, and the ability to synthesize CDs at ambient temperature would be highly desirable. Herein, we design an energy-efficient approach to synthesize CDs through a Schiff base crosslinking between 2,5-dihydroxy-1,4-benzoquinone and tetraethylenepentamine at room temperature. The obtained CDs possess maximum photoluminescence (PL) emissions of 492 nm. Moreover, the proposed CDs possess good stability and a concentration-dependent PL and their maximum emissions can redshift from 492 to 621 nm as the CDs concentration increases. Because of their good luminescent properties, the CDs can be employed as optical probes for doxorubicin detection using the inner filter effect. This study develops a powerful approach for the large-scale synthesis of CDs with a superior performance. Full article

(This article belongs to the Special Issue Synthesis and Application of Luminescent Materials, 2nd Edition)

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10 pages, 6891 KiB

Open AccessArticle

Oxidative Addition to Group 1 (K, Rb, Cs) Alumanyl Anions as a Route to o-Carboranyl (hydrido)aluminates

by Han-Ying Liu, Kyle G. Pearce, Michael S. Hill and Mary F. Mahon

Inorganics 2024, 12(12), 309; https://doi.org/10.3390/inorganics12120309 - 27 Nov 2024

Viewed by 757

Abstract

The kinetic stability provided by the sterically demanding {SiN^Dipp}²⁻ dianion (SiN^Dipp = {CH₂SiMe₂NDipp}₂; Dipp = 2,6-i-Pr₂C₆H₃) is intrinsic to the isolation of not only the [...] Read more.

The kinetic stability provided by the sterically demanding {SiN^Dipp}²⁻ dianion (SiN^Dipp = {CH₂SiMe₂NDipp}₂; Dipp = 2,6-i-Pr₂C₆H₃) is intrinsic to the isolation of not only the group 1 alumanyl reagents ([{SiN^Dipp}AlM]₂; M = K, Rb, Cs) but also facilitates the completely selective oxidative addition of a C-H bond of 1,2-C₂B₁₀H₁₂ to the aluminium centre. In each case, the resultant compounds comprise a four-coordinate o-carboranyl (hydrido)aluminate anion, [(SiN^Dipp)Al(H)(1,2-C₂B₁₀H₁₁)]⁻, in which the carboranyl cage is bonded to aluminium by an Al-C σ bond. Although the anions further assemble as extended network structures based on Al-H∙∙∙M, B-H∙∙∙M, and C-H∙∙∙M interactions, each structure is unique due to the significant variation in M⁺ ionic radius as group 1 is descended. The potassium derivative crystallises as a one-dimensional polymer, its rubidium analogue is a dimer due to the polyhapto-sequestration of a molecule of benzene solvent within the alkali metal coordination sphere, and the caesium species is a two-dimensional assembly of hexameric aggregates. Full article

(This article belongs to the Special Issue Development and Applications of Sterically Demanding Ligands in Main Group Chemistry)

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20 pages, 2103 KiB

Open AccessReview

Naturally Occurring Microbiota-Accessible Borates: A Focused Minireview

by Andrei Biţă, Ion Romulus Scorei, George Dan Mogoşanu, Ludovic Everard Bejenaru, Cristina Elena Biţă, Venera Cristina Dinescu, Gabriela Rău, Maria Viorica Ciocîlteu, Cornelia Bejenaru and Octavian Croitoru

Inorganics 2024, 12(12), 308; https://doi.org/10.3390/inorganics12120308 - 26 Nov 2024

Viewed by 871

Abstract

Recently, we discovered and proved the essentiality of organic boron species (OBS), such as borate–pectic polysaccharides and borate–phenolic esters, for healthy symbiosis (HS) between microbiota and human/animal (H/A) host. The essentiality of OBS will provide new options for B supplementation in H/A nutrition [...] Read more.

Recently, we discovered and proved the essentiality of organic boron species (OBS), such as borate–pectic polysaccharides and borate–phenolic esters, for healthy symbiosis (HS) between microbiota and human/animal (H/A) host. The essentiality of OBS will provide new options for B supplementation in H/A nutrition for a healthy and long life. New knowledge on the essentiality of naturally occurring microbiota-accessible borate species for HS between microbiota and H/A host will allow the use of natural B-based dietary supplements to target the H/A microbiome (the gut, skin, oral, scalp, and vaginal microbiome). In the literature, there is evidence that certain bacteria need B (autoinducer-2 borate) for communication and our preliminary data show that HS takes place when the colonic mucus gel layer contains B. Subsequently, OBS become novel prebiotic candidates and target the colon as novel colonic foods. Full article

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12 pages, 2879 KiB

Open AccessArticle

Interaction of Phenanthroline-Containing Copper Complexes with Model Phospholipid Membranes

by Priscilla Freddi, Natalia Alvarez, Gianella Facchin and Antonio J. Costa-Filho

Inorganics 2024, 12(12), 307; https://doi.org/10.3390/inorganics12120307 - 26 Nov 2024

Viewed by 827

Abstract

Medicinal Inorganic Chemistry has provided oncology with metallodrugs for cancer treatment, including several promising candidate drugs. In particular, copper(II) coordination compounds with phenanthroline stand out as potential anticancer agents. In this work, we used Differential Scanning Calorimetry and Electron Spin Resonance to investigate [...] Read more.

Medicinal Inorganic Chemistry has provided oncology with metallodrugs for cancer treatment, including several promising candidate drugs. In particular, copper(II) coordination compounds with phenanthroline stand out as potential anticancer agents. In this work, we used Differential Scanning Calorimetry and Electron Spin Resonance to investigate the interaction of the copper phenanthroline complexes [Cu(phen)]²⁺ and [Cu(L-dipeptide)(phenanthroline) (L-dipeptide: L-Ala-Gly and L-Ala-Phe)) with model lipid membranes (1,2-dipalmitoyl-sn-glycero-3-phosphocholine, DPPC, and 1,2-dipalmitoyl-sn-glycero-3-phospho-(1′-rac-glycerol) sodium salt, DPPG). Our results showed that the complexes interact with the membrane models, fluidizing them. The [Cu(phen)]²⁺ presented a different localization than the free ligand phen. The dipeptide modulated the localization of the complex in the membrane and the modifications induced in the physicochemical properties of the lipid vesicles. A stronger interaction with DPPG anionic membranes was observed, which mimic membranes with negatively charged surfaces, as found on several tumor cells. Full article

(This article belongs to the Special Issue Evaluation of the Potential Biological Activity of Metallo-Drugs)

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Inorganics, Volume 12, Issue 12 (December 2024) – 38 articles

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